阅读说明：本技术 二次电池、电池包、电动车辆、电动工具以及电子设备 (Secondary cell, battery pack, electric vehicle, electric tool and electronic equipment ) 是由 林直辉 池田泰大 于 2017-10-11 设计创作，主要内容包括：提供一种二次电池、电池包、电动车辆、电动工具以及电子设备。该二次电池在具备正极及负极的同时具备电解液,该负极包含第一负极活性物质、第二负极活性物质和负极粘结剂。第一负极活性物质包括中心部和被覆部,该中心部含有包含硅作为构成元素的材料,该被覆部设置于该中心部的表面并且含有盐化合物及导电性物质。盐化合物含有聚丙烯酸盐及羧甲基纤维素盐中的至少一者,并且导电性物质含有碳材料及金属材料中的至少一者。第二负极活性物质含有包含碳作为构成元素的材料。负极粘结剂含有聚偏二氟乙烯、聚酰亚胺及芳香族聚酰胺中的至少一种。(A kind of secondary cell, battery pack, electric vehicle, electric tool and electronic equipment are provided.The secondary cell has electrolyte while having anode and cathode, which includes the first negative electrode active material, the second negative electrode active material and negative electrode binder.First negative electrode active material includes central part and coating portion, which contains the material comprising silicon as constitution element, which is set to the surface of the central part and contains salt compound and conductive material.Salt compound contains at least one of polyacrylate and carboxymethyl cellulose salt, and conductive material contains at least one of carbon material and metal material.Second negative electrode active material contains the material comprising carbon as constitution element.Negative electrode binder contains at least one of polyvinylidene fluoride, polyimides and aromatic polyamide.)

1. a kind of secondary cell, which is characterized in that

Have electrolyte while having anode and cathode,

The cathode includes the first negative electrode active material, the second negative electrode active material and negative electrode binder,

First negative electrode active material includes central part and coating portion, and the central part contains first as constituting comprising silicon (Si) The material of element, the coating portion are set to the surface of the central part and contain salt compound and conductive material,

The salt compound contains at least one of polyacrylate and carboxymethyl cellulose salt,

The conductive material contains at least one of carbon material and metal material,

Second negative electrode active material contains the material comprising carbon (C) as constitution element,

The negative electrode binder contains at least one of polyvinylidene fluoride, polyimides and aromatic polyamide.

2. secondary cell according to claim 1, which is characterized in that

The cathode is while comprising multiple first negative electrode active materials, comprising passing through multiple first negative electrode actives Substance is close to each other and the compound particle that is formed.

3. secondary cell according to claim 2, which is characterized in that

The specific surface area of described compound particle is 0.1m²/ g or more and 10m²/ g or less.

4. secondary cell according to claim 1, which is characterized in that

The polyacrylate includes at least one of Lithium polyacrylate, Sodium Polyacrylate and polyacrylic acid potassium,

The carboxymethyl cellulose salt include carboxymethyl cellulose lithium, sodium carboxymethylcellulose and potassium carboxymethylcellulose in extremely Few one kind.

5. secondary cell according to claim 1, which is characterized in that

Relative to the weight of the central part, ratio shared by the weight of the salt compound included in the coating portion W1 is 0.1 weight % more than and less than 20 weight %.

6. secondary cell according to claim 1, which is characterized in that

The carbon material includes at least one of carbon nanotube, carbon nano-fiber, carbon black and acetylene black.

7. secondary cell according to claim 6, which is characterized in that

The average tube diameter of the carbon nanotube is 1nm or more and 300nm or less.

8. secondary cell according to claim 6, which is characterized in that

Relative to the weight of the central part, in the coating portion as the conductive material and comprising the carbon material Weight shared by ratio W2 be 0.1 weight % more than and less than 15 weight %.

9. secondary cell according to claim 1, which is characterized in that

The carbon material includes single-walled carbon nanotube.

10. secondary cell according to claim 9, which is characterized in that

The average tube diameter of the single-walled carbon nanotube is 0.1nm or more and 5nm or less.

11. secondary cell according to claim 9, which is characterized in that

Relative to the weight of the central part, in the coating portion as the conductive material and comprising the carbon material Weight shared by ratio W2 be 0.001 weight % more than and less than 1 weight %.

12. secondary cell according to claim 1, which is characterized in that

The carbon material includes fibrous carbon material,

The avarage fiber diameter of the fibrous carbon material be 0.1nm or more and 50nm hereinafter,

The cathode includes multiple first negative electrode active materials,

Multiple first negative electrode active materials pass through multiple via extending between multiple first negative electrode active materials Interconnecting piece and be connected with each other to form three-dimensional mesh structure,

The multiple interconnecting piece respectively includes fiber portion and protection portion, and the fiber portion is in multiple first negative electrode active materials Between extend and contain the fibrous carbon material, the protection portion is set to the surface in the fiber portion and containing described Salt compound.

13. secondary cell according to claim 12, which is characterized in that

The fibrous carbon material includes at least one of carbon nanotube, carbon nano-fiber and single-walled carbon nanotube.

14. secondary cell according to claim 12, which is characterized in that

Ratio shared by weight relative to weight salt compound included in the coating portion of the central part W1 and weight relative to the central part in the coating portion as the conductive material and comprising the threadiness Ratio W2 shared by the weight of carbon material meets W1/W2≤200, and

Sectional area S1 and the protection portion prolonging in the interconnecting piece of the interconnecting piece on the extending direction of the interconnecting piece The sectional area S2 stretched on direction meets S2/S1 >=0.5.

15. secondary cell according to claim 1, which is characterized in that

The metal material includes at least one of tin (Sn), aluminium (Al), germanium (Ge), copper (Cu) and nickel (Ni).

16. secondary cell according to claim 15, which is characterized in that

Relative to the weight of the central part, in the coating portion as the conductive material and comprising the metal material Ratio W3 shared by the weight of material is 0.1 weight % more than and less than 10 weight % or less.

17. a kind of battery pack, has:

Secondary cell；

Control unit controls the movement of the secondary cell；And

Switch portion switches the movement of the secondary cell according to the instruction of the control unit,

The secondary cell has electrolyte while having anode and cathode,

The cathode includes the first negative electrode active material, the second negative electrode active material and negative electrode binder,

First negative electrode active material includes central part and coating portion, and the central part contains comprising silicon as constitution element Material, the coating portion are set to the surface of the central part and contain salt compound and conductive material,

The salt compound contains at least one of polyacrylate and carboxymethyl cellulose salt,

The conductive material contains at least one of carbon material and metal material,

Second negative electrode active material contains the material comprising carbon as constitution element,

The negative electrode binder contains at least one of polyvinylidene fluoride, polyimides and aromatic polyamide.

18. a kind of electric vehicle, has:

Secondary cell；

The electrical power conversion supplied from the secondary cell is driving force by converter section；

Driving portion is driven according to the driving force；And

Control unit controls the movement of the secondary cell,

The secondary cell has electrolyte while having anode and cathode,

The cathode includes the first negative electrode active material, the second negative electrode active material and negative electrode binder,

First negative electrode active material includes central part and coating portion, and the central part contains comprising silicon as constitution element Material, the coating portion are set to the surface of the central part and contain salt compound and conductive material,

The salt compound contains at least one of polyacrylate and carboxymethyl cellulose salt,

The conductive material contains at least one of carbon material and metal material,

Second negative electrode active material contains the material comprising carbon as constitution element,

The negative electrode binder contains at least one of polyvinylidene fluoride, polyimides and aromatic polyamide.

19. a kind of electric tool, has:

Secondary cell；And

Movable part is supplied electric power from the secondary cell,

The secondary cell has electrolyte while having anode and cathode,

The cathode includes the first negative electrode active material, the second negative electrode active material and negative electrode binder,

First negative electrode active material includes central part and coating portion, and the central part contains comprising silicon as constitution element Material, the coating portion are set to the surface of the central part and contain salt compound and conductive material,

The salt compound contains at least one of polyacrylate and carboxymethyl cellulose salt,

The conductive material contains at least one of carbon material and metal material,

Second negative electrode active material contains the material comprising carbon as constitution element,

The negative electrode binder contains at least one of polyvinylidene fluoride, polyimides and aromatic polyamide.

20. a kind of electronic equipment, have secondary cell as power supply source,

The secondary cell has electrolyte while having anode and cathode,

The cathode includes the first negative electrode active material, the second negative electrode active material and negative electrode binder,

First negative electrode active material includes central part and coating portion, and the central part contains comprising silicon as constitution element Material, the coating portion are set to the surface of the central part and contain salt compound and conductive material,

The salt compound contains at least one of polyacrylate and carboxymethyl cellulose salt,

The conductive material contains at least one of carbon material and metal material,

Second negative electrode active material contains the material comprising carbon as constitution element,

The negative electrode binder contains at least one of polyvinylidene fluoride, polyimides and aromatic polyamide.

Technical field

This technology be related to having used the secondary cell of cathode and used the battery pack of the secondary cell, electric vehicle, Electric tool and electronic equipment.

Background technique

The various electronics such as portable phone and portable information terminal equipment (PDA) have been able to widely available, it is desirable that Miniaturization, lightweight and the long lifetime of the electronic equipment.Therefore, as power supply, promoting battery, particularly it is small-sized and Light weight, can obtain high-energy density secondary cell exploitation.

The application of secondary cell is not limited to above-mentioned electronic equipment, is also studying the application to other purposes.Its An example of its purposes are as follows: be dismantledly equipped on the electric vehicles such as the battery pack, electric car of electronic equipment etc., home-use electric power The electric tools such as the accumulating systems such as server and electric drill.

The secondary cell has electrolyte while having anode and cathode, which contains negative electrode active material and bear Pole binder etc..The composition of cathode can bring very big influence, therefore the composition about the cathode to battery behavior, carry out Various researchs.

Specifically, in order to improve cycle characteristics etc., using the granulations such as polyacrylic acid with binder come to active matter plasmid Son is granulated (for example, referring to patent document 1).

Summary of the invention

The increasingly high performance and multifunction such as electronic equipment.It is accompanied by this, the frequency of use of electronic equipment etc. is no Break and increasing, and the use environment of these electronic equipments etc. is constantly expanding.Accordingly, with respect to the battery behavior of secondary cell, There is still room for improvement.

Accordingly, it is desirable to provide a kind of secondary cell, battery pack, electric vehicle, electricity that can obtain excellent battery behavior Power driven tools and electronic equipment.

The secondary cell of one embodiment of this technology has electrolyte while having anode and cathode, the cathode packet Containing the first negative electrode active material, the second negative electrode active material and negative electrode binder.First negative electrode active material include central part and Coating portion, the central part contain the material comprising silicon (Si) as constitution element, which is set to the surface of the central part And contain salt compound and conductive material.Salt compound contains at least one in polyacrylate and carboxymethyl cellulose salt Person, conductive material contain at least one of carbon material and metal material.Second negative electrode active material contains to be made comprising carbon (C) For the material of constitution element.Negative electrode binder contains at least one in polyvinylidene fluoride, polyimides and aromatic polyamide Kind.

Battery pack, electric vehicle, electric tool and the electronic equipment of one embodiment of this technology are each provided with secondary Battery, which has similarly is constituted with the secondary cell of an embodiment of above-mentioned this technology.

According to the secondary cell of an embodiment of this technology, cathode is living comprising the first negative electrode active material, the second cathode Property substance and negative electrode binder, the first negative electrode active material, the second negative electrode active material and negative electrode binder respectively have above-mentioned Composition, therefore excellent battery behavior can be obtained.In addition, the battery pack of an embodiment of this technology, electric vehicle, Electric tool and electronic equipment respectively in, can also obtain same effect.

It should be noted that effect recited herein may not be restricted, it can be documented any effect in this technology Fruit.

Detailed description of the invention

Fig. 1 is the sectional view for showing the composition of the secondary battery cathode of an embodiment of this technology.

Fig. 2 is the section for schematically showing the first negative electrode active material and the respective composition of the second negative electrode active material Figure.

Fig. 3 is the sectional view for schematically showing the composition of compound particle.

Fig. 4 is the vertical view constituted for schematically showing the three-dimensional mesh structure formed by multiple first negative electrode active materials Figure.

Fig. 5 is the sectional view for the composition that amplification shows interconnecting piece shown in Fig. 4.

Fig. 6 is the sectional view of the composition of the secondary cell (cylinder type) for the embodiment for showing this technology.

Fig. 7 is the sectional view of a part that amplification is shown in the composition of rolled electrode bodies shown in Fig. 6.

Fig. 8 is the perspective view of the composition of the secondary cell (laminated membrane type) for the embodiment for showing this technology.

Fig. 9 is the sectional view for showing the composition of the rolled electrode bodies along IX-IX line shown in fig. 8.

Figure 10 is the perspective view for showing the composition of application examples (battery pack: monocell) of secondary cell.

Figure 11 is the block diagram for showing the composition of battery pack shown in Figure 10.

Figure 12 is the block diagram for showing the composition of application examples (battery pack: assembled battery) of secondary cell.

Figure 13 is the block diagram for showing the composition of application examples (electric vehicle) of secondary cell.

Figure 14 is the block diagram for showing the composition of application examples (accumulating system) of secondary cell.

Figure 15 is the block diagram for showing the composition of application examples (electric tool) of secondary cell.

Figure 16 is the sectional view for showing the composition of secondary cell (Coin shape) of test.

Specific embodiment

Hereinafter, one embodiment of this technology is described in detail referring to attached drawing.It should be noted that explanation is suitable Sequence is as described below.

1. secondary battery cathode

1-1. constituting

1-2. manufacturing method

1-3. functions and effects

2. secondary cell

2-1. lithium ion secondary battery (cylinder type)

2-2. lithium ion secondary battery (laminated membrane type)

3. the purposes of secondary cell

3-1. battery pack (monocell)

3-2. battery pack (assembled battery)

3-3. electric vehicle

3-4. accumulating system

3-5. electric tool

1. secondary battery cathode > of <

Firstly, being illustrated to the secondary battery cathode of an embodiment of this technology.

Secondary battery cathode (hreinafter referred to as " cathode ") described herein is for example for secondary cell.Use cathode The type of secondary cell be not particularly limited, for example, lithium ion secondary battery etc..

< 1-1. constitutes >

Fig. 1 shows the section constitution of cathode.The cathode is including such as negative electrode collector 1 and is set to the negative electrode collector Negative electrode active material layer 2 on 1.

It should be noted that negative electrode active material layer 2 can both be only arranged at the single side of negative electrode collector 1, can also set It is placed in the two sides of negative electrode collector 1.In fig. 1 it is shown that for example negative electrode active material layer 2 is set to the two of negative electrode collector 1 The case where face.

[negative electrode collector]

Negative electrode collector 1 containing in such as conductive material any one or it is two or more.The type of conductive material It is not particularly limited, for example, copper (Cu), aluminium (Al), nickel (Ni) and stainless steel etc., or alloy.It needs to illustrate It is that negative electrode collector 1 can be single layer, or multilayer.

The surface of negative electrode collector 1 is preferably roughened.This is because being improved negative using so-called anchoring effect Close property of the pole active material layer 2 to negative electrode collector 1.In this case, if at least with negative electrode active material layer 2 it is opposite Region in the surface of negative electrode collector 1 is roughened.Roughened method be, for example, using electrolysis handle come Form the method etc. of particle.In electrolysis processing, formed on the surface of negative electrode collector 1 using electrolysis method in a cell micro- Grain, therefore bumps are set on the surface of the negative electrode collector 1.Electrolytic copper foil is commonly referred to as using the copper foil that electrolysis method makes.

[negative electrode active material layer]

Negative electrode active material layer 2 contains the two kinds of negative electrode active materials (first that can occlude and discharge electrode reaction substance Negative electrode active material 200 and the second negative electrode active material 300) and negative electrode binder.It should be noted that negative electrode active material layer 2 can be single layer, or multilayer.

" electrode reaction substance " is the substance for participating in the discharge and recharge reaction of secondary cell, specifically, in lithium ion two Electrode reaction substance used in primary cell is lithium.

Fig. 2 schematically shows the first negative electrode active material 200 and the respective section structure of the second negative electrode active material 300 At.Negative electrode active material layer 2 contains for example a variety of first negative electrode active materials 200 and a variety of second negative electrode active materials 300.

First negative electrode active material 200 includes the coating portion 202 of central part 201 with the surface for being set to the central part 201, And the central part 201 contains aftermentioned silicon systems material.Second negative electrode active material 300 contains aftermentioned carbon-based material.

The reason of negative electrode active material layer 2 is containing the first negative electrode active material 200 and the second negative electrode active material 300 exist In while ensuring high theoretical capacity (in other words battery capacity), when charge and discharge, cathode is not easy dilation, and is electrolysed Liquid becomes difficult to decompose.

Specifically, carbon-based material contained in the second negative electrode active material 300 has and is not easy to expand in charge and discharge The advantages of making electrolyte decomposition is shunk and is difficult to, but then, with the low worry of theoretical capacity.In contrast, first Silicon systems material contained in central part 201 in negative electrode active material 200 has the advantages that theoretical capacity is high, but another party Face has the worry for being easy to dilation in charge and discharge and being easy to make electrolyte decomposition.Therefore, by and with containing silicon systems First negative electrode active material 200 of material and the second negative electrode active material 300 containing carbon-based material can obtain high theory While capacity, inhibits dilation of the cathode in charge and discharge and inhibit the decomposition reaction of electrolyte.

The mixing ratio (weight ratio) of first negative electrode active material 200 and the second negative electrode active material 300 is not particularly limited, 200: the second negative electrode active material 300=1:99~99:1 of for example, the first negative electrode active material.This is because if by first Negative electrode active material 200 and the second negative electrode active material 300 are mixed, then can be obtained and be used in combination independent of blending ratio The advantages of the first above-mentioned negative electrode active material 200 and the second negative electrode active material 300.

Wherein, it includes carbon-based material that the mixing ratio of the first negative electrode active material 200 comprising silicon systems material, which is preferably smaller than, The mixing ratio of second negative electrode active material 300.Specifically, the first negative electrode active material 200 and the second negative electrode active material 300 Mixing ratio (weight ratio) be preferably 200: the second negative electrode active material 300=5:95~40:60 of the first negative electrode active material.This It is because the ratio of the silicon systems material as the main reason for generating the dilation of cathode is opposite to tail off, therefore can fill The dilation for dividing ground to inhibit the cathode, and the decomposition reaction of electrolyte can be adequately suppressed.

The negative electrode active material layer 2 is formed for example, by any one or the two or more methods in rubbing method etc.. So-called rubbing method, for example, following method: preparation contains the negative electrode active material, negative electrode binder, water of particle (powder) shape The dispersion liquid (slurry) of property solvent or non-aqueous solvent (such as organic solvent) etc., is then coated on cathode current collection for the dispersion liquid Body 1.

It should be noted that in the secondary cell for having used cathode, in order to inhibit during the charging process unexpectedly negative Electrode reaction substance is precipitated in the surface of pole, and the preferably chargeable capacity of negative electrode active material is greater than positive discharge capacity.Change speech It, can occlude and discharge electrode reaction substance negative electrode active material electrochemical equivalent be preferably greater than anode electrochemistry work as Amount.

(the first negative electrode active material)

As described above, the first negative electrode active material 200 includes central part 201 and coating portion 202.

The shape of first negative electrode active material 200 is not particularly limited, for example, threadiness, spherical (particle shape) and scale Shape etc..In Fig. 2, such as show a case that the shape of the first negative electrode active material 200 is spherical.It is of course also possible to mix In the presence of the first negative electrode active material 200 with two or more shapes.

Fig. 3 schematically shows the section constitution of compound particle 200C.Contain multiple first in negative electrode active material layer 2 In the case where negative electrode active material 200, multiple first negative electrode active material 200 is preferably as shown in Figure 3 by tight each other It pastes and forms aggregate (compound particle 200C).Compound particle 200C is by making to multiple first negative electrode active materials 200 Grain and formed structural body.It should be noted that the quantity of compound particle 200C contained in negative electrode active material layer 2 does not have Especially limitation, can be only one, or more than two.In fig. 3 it is shown that a compound particle 200C.

Compound particle 200C described herein is not the condensate of simple multiple first negative electrode active materials 200.This is multiple Close particle 200C be by via the coating portion 202 to play a role as binder by multiple first negative electrode active materials 200 The structural body for being mutually firmly attached and being formed.

When multiple first negative electrode active materials 200 form compound particle 200C, in the inside of compound particle 200C Ensure the movement routine (occluding release way) of electrode reaction substance.The resistance of compound particle 200C reduces as a result, and should Each central part 201 contained in compound particle 200C becomes prone to occlude and discharge electrode reaction substance.Therefore, even if repeatedly Charge and discharge are carried out, secondary cell is also not easy to expand, and discharge capacity is difficult to decrease.

It should be noted that foring the quantity of the first negative electrode active material 200 of a compound particle 200C without spy It does not limit.In Fig. 3, for example, showing through 11 the first negative electrode active materials 200 for simplified illustration content come shape The case where at a compound particle 200C.But negative electrode active material layer 2 can also contain compound particle 200C while, The first negative electrode active material 200 also containing the formation for having neither part nor lot in compound particle 200C.That is, and the first not all cathode Active material 200 necessarily all has been formed compound particle 200C, and there may also be have not formed compound particle 200C first is negative Pole active material 200.

Such as specific method is used by the forming method as the first negative electrode active material 200, it is easily formed this Compound particle 200C.The specific method is, for example, spray drying process etc..The details of the forming method of compound particle 200C will be It describes below.

The specific surface area of compound particle 200C is not particularly limited, for example, 0.1m²/ g~10m²/g.This is because making In secondary cell with cathode, while ensuring discharge capacity, the resistance of cathode is reduced.Specifically, in specific surface area Greater than 10m²In the case where/g, the specific surface area is excessive, therefore the damage of guiding discharge capacity in the presence of the generation due to side reaction A possibility that mistake becomes larger.On the other hand, it is less than 0.1m in specific surface area²In the case where/g, the specific surface area is too small, therefore, deposits A possibility that resistance of cathode when the deficiency due to response area leads to high load capacity becomes larger." specific surface described herein as Product " is so-called BET specific surface area.

(central part)

Central part 201 containing in silicon systems material any one or it is two or more.Being somebody's turn to do " silicon systems material " is made comprising silicon For the general name of the material of constitution element.

Central part 201 is that the silicon systems material has the suction of excellent electrode reaction substance containing the reason of silicon systems material Releasability is stayed, therefore can get high-energy density.

Silicon systems material can be elementary silicon, or silicon alloy can also be silicon compound.In addition, silicon systems material It can material at least part containing any one or two or more phases in above-mentioned simple substance, alloy and compound.It needs It is noted that silicon systems material can be crystalline, or noncrystalline (amorphous), can also containing crystalline part with Both amorphous fractions.

But the simple substance of " simple substance " described herein only in general sense.That is, the purity of simple substance is not necessarily necessary It is 100%, which can also contain micro impurity.

Silicon alloy can contain two or more metallic elements as constitution element, can also contain more than one metals member Element and more than one semimetallic elements are as constitution element.In addition, the alloy of above-mentioned silicon can also contain more than one non-gold Belong to element as constitution element.The tissue of the alloy of silicon be, for example, solid solution, eutectic (eutectic mixture), intermetallic compound with And the two or more concurrents etc. in them.

Include metallic element in silicon alloy as constitution element and semimetallic elements be, for example, can be anti-with electrode Answer substance formed alloy metallic element and semimetallic elements in any one or it is two or more.Specifically, for example, magnesium (Mg), boron (B), aluminium, gallium (Ga), indium (In), germanium (Ge), tin (Sn), lead (Pb), bismuth (Bi), cadmium (Cd), silver-colored (Ag), zinc (Zn), Hafnium (Hf), zirconium (Zr), yttrium (Y), palladium (Pd) and platinum (Pt) etc..

Silicon alloy for example containing tin, nickel, copper, iron (Fe), cobalt (Co), manganese (Mn), zinc, indium (In), silver, titanium (Ti), germanium, Any one in bismuth, antimony (Sb) and chromium (Cr) etc. or the two or more constitution elements as in addition to silicon.

Silicon compound is for example containing any one or the two or more composition members as in addition to silicon in carbon and oxygen (O) etc. Element.It should be noted that silicon compound can for example contain about any one in series of elements illustrated by silicon alloy Or the two or more constitution elements as in addition to silicon.

Silicon alloy and silicon compound are, for example, SiB₄、SiB₆、Mg₂Si、Ni₂Si、TiSi₂、MoSi₂、CoSi₂、NiSi₂、 CaSi₂、CrSi₂、Cu₅Si、FeSi₂、MnSi₂、NbSi₂、TaSi₂、VSi₂、WSi₂、ZnSi₂、SiC、Si₃N₄、Si₂N₂O、SiO_v(0 V≤2 <) and LiSiO etc..It should be noted that SiO_vIn v can be 0.2 < v < 1.4.

The details of shape about central part 201 for example with the above-mentioned shape about the first negative electrode active material 200 Details are the same.That is, the shape of central part 201 is, for example, fibrous, spherical (particle shape) and flakey etc., in Fig. 2, such as show The shape for having gone out central part 201 is spherical situation.It is of course also possible to be mixed the central part with two or more shapes 201。

In the case where the shape of central part 201 is particle shape, the average grain diameter of the central part 201 is not particularly limited, For example, about 1 μm~10 μm." average grain diameter " described herein is so-called median diameter D50 (μm), later same.

(coating portion)

Coating portion 202 is set to part or all in the surface of central part 201.That is, coating portion 202 both can only by A part in the surface of central part 201 is covered, the whole that can also be coated in the surface of the central part 201.Certainly, in coating portion In the case where a part in the surface of 202 coating central parts 201, it can also be provided on the surface of the central part 201 multiple Coating portion 202, that is, be also possible to the surface that multiple coating portions 202 are coated central part 201.

Wherein, it is coated portion 202 and is preferably only arranged at a part in the surface of central part 201.In this case, because not It is being all coated by coating portion 202 in the surface of central part 201, therefore, a part in the surface of the central part 201 has been revealed Out.The exposed portion in central part 201 ensures the movement routine (occluding release way) of electrode reaction substance as a result, therefore The central part 201 is easy to occlude and discharge electrode reaction substance.Therefore, even if charge and discharge are repeated, secondary cell is also not easy Expansion, and discharge capacity is difficult to decrease.It should be noted that the quantity of exposed portion can be only at one, or two It is more than place.

Contain salt compound and conductive material in the coating portion 202.The type of salt compound both can be only one kind, can also Think two or more.The type of conductive material both can be only one kind, or two or more.

(salt compound)

Salt compound includes one or both of polyacrylate and carboxymethyl cellulose salt.This is because salt chemical combination The envelope of object plays function same as SEI (Solid Electrolyte Interphase: solid-electrolyte interphace) film. Even if being equipped with coating portion 202 on the surface of central part 201 as a result, occlusion of the electrode reaction substance in the central part 201 and release Putting will not be hindered by coating portion 202, and the decomposition reaction of the electrolyte as caused by the reactivity of the central part 201 is by coating portion 202 inhibit.In this case, particularly, even if in electric discharge latter stage, the envelope of salt compound is also difficult to be decomposed, therefore even if In the electric discharge latter stage, the decomposition reaction of electrolyte is also adequately suppressed.

The type of polyacrylate is not particularly limited.The type of the polyacrylate both can be only one kind, can also be with It is two or more.

Specifically, polyacrylate is for example including metal salt and salt etc..But polyacrylate described herein is not It is confined to the compound that whole carboxyls (- COOH) contained in polyacrylic acid all form salt, or the polyacrylic acid Contained in a part of carboxyl form the compound of salt.That is, the polyacrylate of the latter can also contain one or two Above carboxyl.

The type of metal ion contained in metal salt is not particularly limited, for example, alkali metal ion etc., the alkali metal Ion is, for example, lithium ion, sodium ion and potassium ion etc..Specifically, polyacrylate is, for example, Lithium polyacrylate, polypropylene Sour sodium and polyacrylic acid potassium etc..

There is no particular restriction for the type of ion contained in salt, for example, ammonium ion He phosphonium ion etc..Specifically, Polyacrylate is, for example, ammonium polyacrylate and Ju Bing Xi Suan Phosphonium etc..

It should be noted that polyacrylate can only contain metal ion in a molecule, can also only contain Ion can also contain the two.Even in this case, polyacrylate can also as described above containing one or two with On carboxyl.

The type of carboxymethyl cellulose salt is not particularly limited.The type of the carboxymethyl cellulose salt both can be only one Kind, or it is two or more.

Specifically, carboxymethyl cellulose salt is for example comprising metal salt etc..Wherein, carboxymethyl cellulose salt described herein as It is not limited to the compound that whole hydroxyls (- OH) contained in carboxymethyl cellulose all form salt, or carboxymethyl A part of hydroxyl contained in cellulose forms the compound of salt.That is, the carboxymethyl cellulose salt of the latter can also contain One or more hydroxyl.

The type of metal ion contained in metal salt is not particularly limited, for example, alkali metal ion etc., the alkali metal Ion is, for example, lithium ion, sodium ion and potassium ion etc..Specifically, carboxymethyl cellulose salt is, for example, carboxymethyl cellulose Lithium, sodium carboxymethylcellulose and potassium carboxymethylcellulose etc..

(conductive material)

Conductive material contains one or both of carbon material and metal material.This is because carbon material and metal material Material plays excellent electric conductivity in the state of by containing in coating portion 202 (envelope of salt compound).Even if as a result, in The surface of center portion 201 is equipped with coating portion 202, can also ensure that the electric conductivity of the first negative electrode active material 200.In this case, Particularly, even if in electric discharge latter stage, also can by the envelope of salt compound respectively contained in conductive material maintain to lead Electrically, therefore even if in the electric discharge latter stage, discharge capacity is also difficult to reduce.

The type of carbon material is not particularly limited.The type of the carbon material both can be only one kind, or two kinds with On.

Specifically, carbon material is, for example, carbon nanotube, carbon nano-fiber, carbon black and acetylene black etc..Carbon nanotube is put down Equal pipe diameter is not particularly limited, wherein preferably 1nm~300nm.This is because electric conductivity further increases.But carbon materials Material can containing in carbon nanotube as escribed above, carbon nano-fiber, carbon black and acetylene black any one or it is two or more While, also contain aftermentioned single-walled carbon nanotube.

Alternatively, carbon material may be such as single-walled carbon nanotube.The average tube diameter of single-walled carbon nanotube is not special Limitation, wherein preferably 0.1nm~5nm.In addition, the average length of single-walled carbon nanotube is not particularly limited, wherein preferably It is 5 μm~100 μm.This is because electric conductivity can further increase.

Particularly, the average tube diameter of single-walled carbon nanotube is smaller than the average tube diameter of carbon nanotube, therefore by using Single-walled carbon nanotube is as carbon material, compared with using the case where carbon nanotube is as carbon material, can also be filled even if on a small quantity The electric conductivity divided, and the capacity of per unit weight is inhibited to reduce.

The mixture of carbon material (single-walled carbon nanotube) described herein or carbon nanotube and single-walled carbon nanotube. But the ratio of single-walled carbon nanotube is set as such as 70 weight % or more.

The type of metal material is not particularly limited.The type of the metal material both can be only one kind, or two Kind or more.Specifically, metal material is, for example, tin, aluminium, germanium, copper and mickel etc..The state of metal material is not particularly limited, example For example particle (powder) shape etc..The average grain diameter (median diameter D50) of metal material is not particularly limited, wherein preferably 30nm~3000nm, more preferably 30nm~1000nm, further preferably 50nm~500nm.

The thickness in coating portion 202 and covering rate etc. can arbitrarily be set.During the thickness in coating portion 202 does not hinder preferably Center portion 201 occlude and release electrode reaction substance and the thickness of the central part 201 can be protected.The covering rate in coating portion 202 is excellent Be selected as not hindering central part 201 occlude and release electrode reaction substance and the covering rate of the central part 201 can be protected.

(ratio W1, W2, W3)

Here, ratio shared by weight of the weight of each material contained in coating portion 202 relative to central part 201 does not have There is special limitation.Wherein, above-mentioned ratio has preferably carried out optimizing to meet defined condition.

Specifically, first, it is coated weight of the weight of salt compound contained in portion 202 relative to central part 201 Shared ratio W1 is preferably 0.1 weight % more than and less than 20 weight %.This is because the central part based on coating portion 202 201 amount of coating is optimised, therefore in electric discharge, cathode is not easy to expand and shrink, and electrolyte is not easily decomposed.The ratio W1 is calculated by W1 (weight %)=(weight of weight/central part 201 of salt compound) × 100.

Second, in the case where carbon material contains carbon nanotube etc., relative to the weight of central part 201, in coating portion 202 Ratio W2 shared by the weight of the middle carbon material contained as conductive material is preferably 0.1 weight % more than and less than 15 weights Measure %.This is because the resistance of cathode can reduce in high load capacity, and multiple first negative electrode active materials 200 are easily formed Compound particle 200C.Ratio W2 passes through W2 (weight %)=(weight/central part 201 of the carbon material as conductive material Weight) × 100 calculate.

Third, in the case where carbon material contains single-walled carbon nanotube, relative to the weight of central part 201, in coating portion Ratio W2 shared by the weight of the carbon material contained in 202 as conductive material is preferably 0.001 weight % or more and small In 1 weight %.This is because can get the advantage same as the situation that carbon material contains carbon nanotube etc..

4th, relative to the weight of central part 201, the metal material contained in coating portion 202 as conductive material Ratio W3 shared by the weight of material is preferably 0.1 weight of weight %~10 %.This is because in high load capacity cathode resistance meeting It reduces, and multiple first negative electrode active materials 200 are easily formed compound particle 200C.Ratio W3 by W3 (weight %)= (weight of weight/central part 201 of the metal material as conductive material) × 100 calculate.

(composition of preferred first negative electrode active material)

Wherein, multiple first negative electrode active materials 200 preferably form aftermentioned three-dimensional mesh structure.This is because more A first negative electrode active material 200 is securely joined with each other, and is led between multiple first negative electrode active material 200 Electrically improve.As a result, in charge and discharge, cathode is more difficult to dilation, and the resistance of the cathode is more difficult to increase.

It in this case, particularly, will be for multiple central parts of primary particle by forming above-mentioned three-dimensional mesh structure 201 are securely joined with each other, and electric conductivity can improve between multiple central parts 201 of primary particle at this.Therefore, Cathode is not easy significant dilation, and the resistance of the cathode is not easy to dramatically increase.

Fig. 4 schematically shows the vertical view structures of the three-dimensional mesh structure formed by multiple first negative electrode active materials 200 At, and Fig. 5 is exaggerated the section constitution of interconnecting piece 203 shown in Fig. 4.

Negative electrode active material layer 2 for example contains multiple first negative electrode active materials 200 as described above, therefore, multiple the One negative electrode active material 200 includes for example multiple central parts 201 and multiple coating portions 202.In this case, multiple first is negative Pole active material 200 preferably forms above-mentioned three-dimensional mesh structure for example, as shown in figure 4.This is because can get above-mentioned Advantage.

Here, conductive material contain in such as fibrous carbon material any one or it is two or more as carbon material. It is somebody's turn to do the general name that " fibrous carbon material " refers to the carbon material of the three-dimensional shape with threadiness.The average fiber of fibrous carbon material Diameter is not particularly limited, for example, 0.1nm~50nm.Specifically, fibrous carbon material is, for example, that the carbon having already described above is received Mitron, carbon nano-fiber and single-walled carbon nanotube etc..

In this case, for example, multiple first negative electrode active materials 200 are mutual via multiple interconnecting pieces 203 each other Connection, thus forms three-dimensional mesh structure.Multiple interconnecting piece 203 is for example between multiple first negative electrode active materials 200 Extend.Three-dimensional mesh structure for example can both have been formed by a part in multiple first negative electrode active materials 200, can also be by more Being completely formed in a first negative electrode active material 200.

In Fig. 4, for simplified illustration content, a part (two-dimentional netting knot in three-dimensional mesh structure is illustrated only Structure).In fact, also being deposited other than multiple first negative electrode active materials 200 shown in Fig. 4 in the nearby side of the paper of Fig. 4 There are multiple first negative electrode active materials 200, and there is also there are multiple first negative electrode active materials in the inboard of the paper of Fig. 4 200, these a series of first negative electrode active materials 200 are connected with each other via multiple interconnecting pieces 203.

The quantity for the first other negative electrode active material 200 that one the first negative electrode active material 200 is connected is without spy It does not limit, such as can be only one, or is more than two.

Multiple first negative electrode active materials 200 for example can be by utilizing multiple interconnecting pieces 203 like that as described in this Three-dimensional mesh structure is formed, so as to form compound particle 200C shown in Fig. 3.

(interconnecting piece)

Multiple interconnecting pieces 203 extend between multiple first negative electrode active materials 200 as described above.In this case, phase Mutually two adjacent the first negative electrode active materials 200 are mutually connected via interconnecting piece 203 each other.Therefore, interconnecting piece The surface of 203 the first negative electrode active material 200 between two the first negative electrode active materials 200 from a side extends to another party The first negative electrode active material 200 surface.

As shown in Figure 4 and 5, the interconnecting piece 203 is for example including fiber portion 204 and protection portion 205.

(fiber portion)

Fiber portion 204 extends for example between two adjacent to each other coating portions 202 from the surface in the coating portion 202 of a side To the surface in the coating portion 202 of another party.Think, the fiber portion 204 is mainly by such as getting off to be formed: in negative electrode active material layer It will be in fibrous carbon material in a manner of being interconnected with one another two adjacent to each other coating portions 202 in 2 formation process A part is drawn out to the outside in coating portion 202.

In addition, fiber portion 204 for example containing in above-mentioned fibrous carbon material any one or it is two or more.This be because To be easily formed interconnecting piece 203 using fibrous carbon material.It should be noted that threadiness contained in fiber portion 204 The radical of carbon material is not particularly limited, and can be only one, or two or more.

In the case where fibrous carbon material includes the pipings materials such as carbon nanotube and single-walled carbon nanotube, the fibrous carbon The avarage fiber diameter (average tube diameter) of material is not particularly limited, but is preferably as described above 0.1nm~50nm, more preferably For 0.1nm~10nm.This is because a part in fibrous carbon material is easy to be drawn out to the outside in coating portion 202, and The fibrous carbon material is easy to be coated by salt compound, therefore is easily formed interconnecting piece 203.Moreover, this is because even if conductive Property substance (fibrous carbon material) amount be to be also easy to form interconnecting piece 203 on a small quantity, therefore be able to suppress the appearance of per unit weight Amount reduces.

In addition, in the case where fibrous carbon material contains the fibers based material such as carbon nano-fiber, the fibrous carbon material Avarage fiber diameter (average fiber diameter) be not particularly limited, but as described above be preferably 0.1nm~ 50nm, more preferably 0.1nm~10nm.This is because the case where can get with fibrous carbon material as piping material is same Advantage.

That is, in the case where conductive material contains fibrous carbon material as carbon material, if the fibrous carbon material In average tube diameter or the above-mentioned appropriate range of each leisure of avarage fiber diameter, then make it easy in multiple first negative electrode active materials Multiple interconnecting pieces 203 are formed between 200.As a result, multiple first negative electrode active materials 200 be easy to using multiple interconnecting pieces 203 come Form three-dimensional mesh structure.

(protection portion)

Protection portion 205 is set to part or all in the surface in fiber portion 204, therefore is coated the fiber portion 204 Outer peripheral surface.That is, protection portion 205 both can only be coated a part in the surface in fiber portion 204, the fiber portion can also be coated Whole in 204 surface.It certainly, can also in the case where a part in the surface that protection portion 205 is coated fiber portion 204 Surface in the fiber portion 204 is provided with multiple protection portion 205, i.e. multiple protection portion 205 are coated the surface in fiber portion 204.

Wherein, protection portion 205 is preferably disposed on the whole in the surface in fiber portion 204.This is because fiber portion 204 Whole meeting protected portion 205 is reinforced, therefore the physical strength of interconnecting piece 203 improves.

The protection portion 205 for example containing in above-mentioned salt compound any one or it is two or more.It is therefore contemplated that protecting Shield portion 205 is mainly by such as getting off to be formed: as described above, in the formation process of negative electrode active material layer 2, when by fibrous carbon When a part in material has been drawn out to the outside in coating portion 202, a part in salt compound can be coated fibrous carbon material.

(ratio ratio W1/W2 and sectional area ratio S1/S2)

Here, three-dimensional mesh structure is formd using multiple interconnecting pieces 203 in multiple first negative electrode active materials 200 In the case of, ratio (ratio ratio) W1/W2 of above-mentioned ratio W1, W2 and the sectional area S2 of protection portion 205 are relative to interconnecting piece 203 Ratio (sectional area ratio) S2/S1 of sectional area S1 is not particularly limited.It is somebody's turn to do " the sectional area S1 of interconnecting piece 203 " and refers to interconnecting piece 203 Sectional area on the extending direction of interconnecting piece 203, and " the sectional area S2 of protection portion 205 " refers to that protection portion 205 is connecting Sectional area on the extending direction in portion 203.

Wherein, ratio ratio W1/W2 preferably satisfies the relationship of W1/W2≤200, and sectional area ratio S2/S1 preferably satisfies S2/ The relationship of S1 >=0.5.This is because multiple first negative electrode active materials 200 are easy to be easy landform using multiple interconnecting pieces 203 At three-dimensional mesh structure, and it is easy to maintain the three-dimensional mesh structure.Multiple first negative electrode active materials 200 phase each other as a result, It mutually more firmly combines, and electric conductivity further increases between multiple first negative electrode active material 200.

It should be noted that the value of ratio ratio W1/W2 is set as the value after value deputy after decimal point rounds up.Separately Outside, the value of sectional area ratio S2/S1 is set as the value after the value of third position after decimal point rounds up.

As described below, sectional area S1, S2 described herein are each based on the observation knot in the section of interconnecting piece 203 Fruit and simply find out.

When finding out sectional area S1, firstly, by using in microscope etc. any one or it is two or more come such as Fig. 5 institute Show that observation includes the section of the interconnecting piece 203 of fiber portion 204 and protection portion 205.The cross sectional shape of interconnecting piece 203 is predominantly by growing Substantially elliptical as defined in axis a and short axle b, and the cross sectional shape in fiber portion 204 is mainly as defined in long axis c and short axle d Substantially elliptical.Then, the size of the size L1 and short axle b of long axis a are measured according to the observation result in the section of interconnecting piece 203 L2 is each, and the diameter of the interconnecting piece 203 is then calculated according to calculating formula as diameter=(L1+L2)/2.Here it calculates " diameter " assumes that the section for interconnecting piece 203 is the diameter in the case where justifying.Then, according to the straight of above-mentioned interconnecting piece 203 Diameter calculates the area (sectional area) of the interconnecting piece 203.Finally, by the process weight of the sectional area of above-mentioned calculating interconnecting piece 203 It is 10 times multiple, the average value of 10 sectional areas is then calculated, thus as the sectional area S1 of the interconnecting piece 203.

It should be noted that microscopical type is not particularly limited, for example, transmission electron microscope (TEM) etc.. Specifically, such as being able to use transmission electron microscope JEM-ARM200F anufactured by Japan Electron Optics Laboratory(JEOL).

When finding out sectional area S2, the step same as the above-mentioned program for finding out sectional area S1 is used.In such case Under, firstly, as shown in figure 5, the section of observation interconnecting piece 203.Then, cutting for interconnecting piece 203 is calculated through the above steps Area.Then, it is measured according to the observation result in the section in fiber portion 204 in the size L4 of size L3 and short axle d of long axis c Each, the diameter in fiber portion 204 is then calculated according to calculating formula as diameter=(L3+L4)/2.What is calculated herein is " straight Diameter " assumes that the section for fiber portion 204 is the diameter in the case where justifying.Then, according to the diameter in above-mentioned fiber portion 204 come Calculate the area (sectional area) in the fiber portion 204.Then, the section in fiber portion 204 is subtracted from the sectional area of interconnecting piece 203 Thus product calculates the sectional area of protection portion 205.Finally, the process of the sectional area of above-mentioned calculating protection portion 205 is repeated 10 It is secondary, the average value of 10 sectional areas is then calculated, thus as the sectional area S2 of the protection portion 205.

(the second negative electrode active material)

Second negative electrode active material 300 containing in carbon-based material any one or it is two or more.Being somebody's turn to do " carbon-based material " is General name comprising carbon as the material of constitution element.

Second negative electrode active material 300 is containing the reason of carbon-based material, in the occlusion of electrode reaction substance and releases When putting, carbon-based material is not easy dilation.The crystal structure of carbon-based material is difficult to change as a result, therefore can stably obtain High-energy density.Moreover, carbon-based material is also functioned as aftermentioned cathode conductive agent, therefore negative electrode active material layer 2 Electric conductivity improves.

The type of carbon-based material is not particularly limited, for example, easy graphitized carbon, difficult graphitized carbon and graphite etc., still, The face interval in (002) face about difficult graphitized carbon is preferably such as 0.37nm or more, and about relevant (002) face of graphite Face interval be preferably such as 0.34nm or less.

More specifically, carbon-based material is, for example, and is pyrolyzed carbons, coke class, glass carbon fiber, organic high molecular compound to forge Burn product, active carbon and carbon black class etc..The coke class is including, for example, pitch coke, needle coke and petroleum coke etc..Organic polymer Firing (carbonization) object that object firing product is high-molecular compound is closed, which is, for example, phenolic resin and furans tree In rouge etc. any one or it is two or more.In addition to this, carbon-based material for example can be at about 1000 DEG C of temperature below The low-crystalline carbon being heat-treated, or amorphous carbon.

The shape of second negative electrode active material 300 is not particularly limited, for example, threadiness, spherical (particle shape) and scale Shape etc..In fig. 2 it is shown that the shape of such as the second negative electrode active material 300 is spherical situation.It is of course also possible to mix In the presence of the second negative electrode active material 300 with two or more shapes.

In the case where the shape of the second negative electrode active material 300 is particle shape, which is put down Equal partial size (median diameter D50) is not particularly limited, and for example, about 5 μm~40 μm.

(negative electrode binder)

Negative electrode binder contain any one or two kinds in polyvinylidene fluoride, polyimides and aromatic polyamide with On.This is because the first negative electrode active material 200 and the second negative electrode active material 300 etc. can be bonded fully.

It should be noted that cathode uses as described later contains the first negative electrode active material 200, the second negative electrode active material 300 and the non-aqueous dispersion of negative electrode binder manufacture.In the non-aqueous dispersion, 200 He of the first negative electrode active material Second negative electrode active material 300 is respectively dispersed self, and negative electrode binder has been dissolved.

(other materials)

It should be noted that negative electrode active material layer 2 can also containing in other materials any one or it is two or more.

Other materials are, for example, the other negative electrode active materials that can occlude and discharge electrode reaction substance.Other cathode are living Property substance include metal based material in any one or it is two or more.Being somebody's turn to do " metal based material " is comprising metallic element and half gold Belong to the general name of any one or the two or more materials as constitution element in element.This is because it is close to can get high-energy Degree.But " metal based material " middle exclusion that above-mentioned silicon systems material illustrates from there.

Metal based material can be simple substance, or alloy can also be compound.In addition, metal based material can also Think the material containing any one or two or more phases in above-mentioned simple substance, alloy and compound at least part Material.Wherein, the meaning of " simple substance " is as described above.

Alloy can contain two or more metallic elements as constitution element, can also contain more than one metallic elements With more than one semimetallic elements as constitution element.In addition, above-mentioned alloy can also contain more than one nonmetalloids As constitution element.The tissue of alloy be, for example, solid solution, eutectic (eutectic mixture), intermetallic compound and they in Two or more concurrents etc..

The metallic element and semimetallic elements contained in metal based material as constitution element is, for example, can be with electricity Pole reactive material formed alloy metallic element and semimetallic elements in any one or it is two or more.Specifically, for example For magnesium, boron, aluminium, gallium, indium, silicon, germanium, tin, lead, bismuth, cadmium, silver, zinc, hafnium, zirconium, yttrium, palladium and platinum etc..

Wherein, preferred tin.This is because tin has occlusion and the releasability of excellent electrode reaction substance, therefore can Obtain high-energy density.

For example as described above about the details of tin alloy and tin compound.

Tin alloy for example containing in nickel, copper, iron, cobalt, manganese, zinc, indium, silver, titanium, germanium, bismuth, antimony and chromium etc. any one or The two or more constitution elements as in addition to tin.Tin compound for example containing in carbon and oxygen etc. any one or it is two or more As the constitution element in addition to tin.It should be noted that tin compound can also contain for example illustrated by tin alloy Any one in series of elements or the two or more constitution elements as in addition to tin.

Tin alloy and tin compound are, for example, SnO_w(w≤2 O <), SnSiO₃, LiSnO and Mg₂Sn etc..

Containing tin as the material of constitution element may be for example while containing the tin as the first constitution element Material (tin-containing material) containing the second constitution element and third constitution element.Second constitution element be, for example, cobalt, iron, magnesium, titanium, Vanadium (V), chromium, manganese, nickel, copper, zinc, gallium, zirconium, niobium, molybdenum (Mo), silver, indium, caesium (Cs), hafnium, tantalum (Ta), tungsten (W), bismuth and silicon etc. In any one or it is two or more.Third constitution element is, for example, any one or two kinds in boron, carbon, aluminium and phosphorus (P) etc. More than.This is because can get high battery capacity and excellent cycle characteristics etc..

Wherein, tin-containing material preferably contains the material (stanniferous cobalt carbon material) of tin, cobalt and carbon as constitution element.It is stanniferous The composition of cobalt carbon material is for example as described below.The content of carbon is the 9.9 mass % of mass %~29.7, the content ratio of tin and cobalt (Co/ (Sn+Co)) is 20 mass of mass %~70 %.This is because can get high-energy density.

Stanniferous cobalt carbon material has the phase containing tin, cobalt and carbon, this is mutually preferably low-crystalline or noncrystalline.The Xiang Weineng It is enough to can get in stanniferous cobalt carbon material with the phase (reacting phase) of electrode reaction substance reaction since there are the reaction phases Excellent characteristic.It, should in the case where using CuK alpha ray as specific X-ray and scanning speed being set as 1 °/min The half-peak breadth (2 θ of the angle of diffraction) for reacting the diffraction maximum as obtained from X-ray diffraction of phase is preferably 1 ° or more.This is because electric Pole reactive material is easy to be occluded and discharge, and reduces with the reactivity of electrolyte.It should be noted that stanniferous cobalt carbon material Sometimes also contain other layers while containing low-crystalline or amorphous phase.Other layers include for example, each constitution element The phase of simple substance and include the equal of a part in each constitution element.

About the diffraction maximum as obtained from X-ray diffraction whether correspond to reaction phase, can be with electrode reaction substance The phase of reaction, by comparing with the X-ray diffractogram before and after the electrochemical reaction of electrode reaction substance and can easily determine.Example Such as, if the position of diffraction maximum is changed, then can be judged as before and after with the electrochemical reaction of electrode reaction substance Corresponding to reaction phase.In this case, such as in the range of 2 θ=20 °~50 ° low-crystalline or amorphous anti-is detected Answer the diffraction maximum of phase.The reaction mutually contains a series of constitution element as escribed above, it is believed that mainly due to the presence of carbon and Low crystallization or decrystallized has occurred.

In stanniferous cobalt carbon material, preferably as in the carbon of constitution element part or all with as other compositions member The metallic element or semimetallic elements of element are bonded.This is because being able to suppress cohesion and crystallization of tin etc. etc..About The bond styles of element, such as be able to use X-ray photoelectron spectroscopy (XPS) and confirmed.For commercially available device, Such as Al-K alpha ray used as grenz ray and Mg-K alpha ray etc..Part or all in carbon with metallic element or In the case that semimetallic elements etc. is bonded, the peak of the composite wave of the 1s track (C1s) of carbon appears in lower than 284.5eV Region.It but will be as follows as condition: being carried out in a manner of obtaining the peak of 4f track (Au4f) of gold atom at 84.0eV Energy calibration.In this case, usually in material surface, there are surface contamination carbons, therefore by the C1s of the surface contamination carbon Peak as energy reference (284.8eV).XPS measurement in, the waveform at the peak of C1s include the peak as caused by surface contamination carbon and The peak as caused by the carbon in stanniferous cobalt carbon material.Thus, for example, being analyzed by using commercially available software peak and by two The peak of person separates.In the analysis of waveform, using the position of the main peak existing for minimum binding energy side as energy reference (284.8eV)。

In the stanniferous cobalt carbon material, such as other than tin, cobalt and carbon, can also contain silicon, iron, nickel, chromium, indium, niobium, In germanium, titanium, molybdenum, aluminium, phosphorus, gallium and bismuth etc. any one or it is two or more be used as constitution element.

Other than stanniferous cobalt carbon material, further preferably contain material (the stanniferous cobalt of tin, cobalt, iron and carbon as constitution element Iron carbon material).The group of the stanniferous ferro-cobalt carbon material becomes arbitrary.

Composition in the case where the content of iron is set to few is for example just as described below.The content of carbon is 9.9 mass % ~29.7 mass %.The content of iron is 0.3 mass of mass %~5.9 %.The content ratio (Co/ (Sn+Co)) of tin and cobalt is 30 The mass of quality %~70 %.This is because can get high-energy density.

Composition in the case where the content of iron is set to more is for example just as described below.The content of carbon is 11.9 mass % ~29.7 mass %.The content ratio ((Co+Fe)/(Sn+Co+Fe)) of tin, cobalt and iron is 26.4 mass of mass %~48.5 %. The content ratio (Co/ (Co+Fe)) of cobalt and iron is 9.9 mass of mass %~79.5 %.This is because it is close to can get high-energy Degree.

It should be noted that the physical property (conditions such as half-peak breadth) of stanniferous ferro-cobalt carbon material and above-mentioned stanniferous cobalt carbon material Physical property is the same.

In addition, other negative electrode active materials are, for example, metal oxide and high-molecular compound etc..Metal oxide is for example For iron oxide, ruthenium-oxide and molybdenum oxide etc..High-molecular compound is, for example, polyacetylene, polyaniline and polypyrrole etc..

In addition, other materials are, for example, other negative electrode binders.Other negative electrode binders are, for example, synthetic rubber and high score Sub- compound etc..Synthetic rubber is, for example, fluorine class rubber and ethylene propylene diene rubber etc..High molecular material be, for example, polyimides and Polyacrylate etc..Details about the type of polyacrylate for being used as negative electrode binder etc. are for example with above-mentioned about coating The details of the type of polyacrylate contained in portion 202 etc. are the same.

In addition, other materials are, for example, cathode conductive agent.The cathode conductive agent contains any one in such as carbon material Kind is two or more.The carbon material is, for example, graphite, carbon black, acetylene black and Ketjen black etc..In addition, carbon material may be for example Fibrous carbon etc. containing carbon nanotube.But as long as cathode conductive agent is conductive material, or gold Belong to material and Electroconductivity of Conducting Polymers etc..

< 1-2. manufacturing method >

The cathode is for example manufactured by steps described below.Hereinafter, being wanted about a series of composition for constituting cathode The forming material of element, has been carried out detailed description, therefore omit the explanation about the forming material at any time.

Firstly, central part 201, salt compound and conductive material containing silicon systems material and aqueous solvent etc. are mixed, Then the mixture is stirred.Stirring means and stirring condition are not particularly limited, and blender etc. can be used for example and stir Mix device.

Central part 201 and conductive material are scattered in aqueous solvent as a result, and salt compound is molten by the aqueous solvent Solution, therefore it is prepared for the aqueous liquid dispersion comprising central part 201, salt compound and conductive material.

The type of aqueous solvent is not particularly limited, for example, pure water etc..As salt compound, can be used for example non-molten Object is solved, dissolved matter also can be used.The dissolved matter is, for example, by pure water etc. by salt compound dissolved solution, is so-called Salt compound aqueous solution.

Then, it is made it dry while stirring aqueous liquid dispersion.Stirring means are for example as described above.Stirring condition and dry Dry condition is not particularly limited.

In aqueous liquid dispersion, the coating portion 202 containing salt compound and conductive material is formed in the table of central part 201 Face, therefore form the first negative electrode active material 200.

Then, by the first negative electrode active material 200, the second negative electrode active material 300 containing carbon-based material, containing poly- inclined Negative electrode binder, non-aqueous solvent and cathode conductive agent as needed of difluoroethylene etc. etc. are mixed, then to this Mixture is stirred.Stirring means and stirring condition are not particularly limited, and the agitating devices such as blender can be used for example.

As long as the type of non-aqueous solvent can make the first negative electrode active material 200 and the second negative electrode active material 300 Each self-dispersing and can make negative electrode binder dissolve material in any one or it is two or more, then just do not limit especially System.The non-aqueous solvent is, for example, the organic solvents such as n-methyl-2-pyrrolidone.

Negative electrode binder is dissolved by non-aqueous solvent as a result, therefore is prepared for comprising the first negative electrode active material 200, the The non-aqueous dispersion of two negative electrode active materials 300 and negative electrode binder.The state of non-aqueous dispersion is not particularly limited, example For example paste.The non-aqueous dispersion of paste is so-called slurry.

Finally, manufacturing cathode using non-aqueous dispersion.At this point, for example, non-aqueous in the coating of the two sides of negative electrode collector 1 Property dispersion liquid, then make the non-aqueous dispersion dry.It is formed as a result, living containing the first negative electrode active material 200, the second cathode The negative electrode active material layer 2 of property substance 300 and negative electrode binder, therefore cathode is made.

Hereafter, roll squeezer etc. can be used, compression forming is carried out to negative electrode active material layer 2.In such a case it is possible to right Negative electrode active material layer 2 is heated, and multiple compression forming can also be repeated.Contractive condition and heating condition be not special Limitation.

It should be noted that in the manufacturing method of above-mentioned cathode, can with the first negative electrode active material 200 in order to obtain and Use other methods.In such a case it is possible to and with two or more methods.

Specifically, spray drying process can be used for example.Using spray drying process, for example, using spray Aqueous liquid dispersion is sprayed by mist drying device, then makes the spraying object dry.Quilt is formed on the surface of central part 201 as a result, Portion 202 is covered, therefore the first negative electrode active material 200 can be obtained.

Particularly, can be while forming multiple first negative electrode active material 200 by using spray drying process, shape At the compound particle 200C of the aggregate as multiple first negative electrode active material 200.In this case, for example, using fine It ties up shape carbon material and three-dimensional mesh structure shown in Fig. 4 is consequently formed as conductive material (carbon material), therefore formed compound Particle 200C.

Alternatively, it is also possible to use such as comminuting method.When using comminuting method, for example, keeping aqueous liquid dispersion dry, then make Dried object is crushed with pulverizer.Coating portion 202 is formed on the surface of central part 201 as a result, therefore obtains the first negative electrode active Substance 200.The type of pulverizer is not particularly limited, for example, planetary ball mill etc..

< 1-3. effect and effect >

According to the cathode, contain the first negative electrode active material 200, the second negative electrode active material 300 and negative electrode binder.The One negative electrode active material 200 includes the central part 201 containing silicon systems material and the quilt containing salt compound and conductive material Cover portion 202.Second negative electrode active material 300 contains carbon-based material.Negative electrode binder contains polyvinylidene fluoride etc..

In this case, as described above, ensuring the first negative electrode active material 200 and the second negative electrode active material 300 Deng caking property while, it is ensured that the electric conductivity in coating portion 202, and central part 201 becomes prone to occlude and to discharge electrode anti- Substance is answered, while being able to suppress the decomposition reaction of the electrolyte as caused by the reactivity of the central part 201.Therefore, even if repeatedly Charge and discharge are carried out, secondary cell is also not easy to expand, and discharge capacity is difficult to decrease, therefore can be improved and used the two of cathode The battery behavior of primary cell.

Particularly, if multiple first negative electrode active materials 200 form compound particle 200C, compound particle 200C's Resistance can reduce, and each central part 201 contained in compound particle 200C becomes prone to occlude and discharge electrode reaction Substance, therefore higher effect can be obtained.

In this case, if the specific surface area of compound particle 200C is 0.1m²/ g~10m²/ g, then be able to suppress and put The loss of capacitance, and the resistance for being able to suppress the cathode in high load capacity increases, therefore can obtain higher effect.

In addition, if polyacrylate includes carboxymethyl cellulose lithium comprising Lithium polyacrylate etc., carboxymethyl cellulose salt Deng can then ensure occlusion and release of the electrode reaction substance in central part 201, and by coating portion 202 come fully Inhibit the decomposition reaction of the electrolyte as caused by the reactivity of the central part 201, therefore higher effect can be obtained.

In addition, in charge and discharge, cathode is not easy to expand if ratio W1 is 0.1 weight % more than and less than 20 weight % And contraction, and electrolyte is not easily decomposed, therefore can obtain higher effect.

In addition, the electric conductivity in coating portion 202 can fully improve, therefore energy if carbon material contains carbon nanotube etc. Enough obtain higher effect.In this case, if the average tube diameter of carbon nanotube is 1nm~300nm, electric conductivity can be into One step improves, therefore can obtain higher effect.In addition, if ratio W2 is 0.1 weight % more than and less than 15 weight %, It then can inhibit the resistance in high load capacity to increase, therefore higher effect can be obtained.

In addition, the electric conductivity in coating portion 202 can fully improve, therefore if carbon material contains single-walled carbon nanotube Higher effect can be obtained.In this case, conductive if the average tube diameter of single-walled carbon nanotube is 0.1nm~5nm Property can further increase, therefore can obtain higher effect.In addition, if ratio W2 is 0.001 weight % more than and less than 1 Weight % then can inhibit the resistance in high load capacity and increase, therefore can obtain higher effect.

In addition, if carbon material contain fibrous carbon material, the fibrous carbon material avarage fiber diameter be 0.1nm~ 50nm and by using including multiple interconnecting pieces 203 of fiber portion 204 and protection portion 205 by multiple first negative electrode active materials Matter 200 is connected each other to form three-dimensional mesh structure, then in charge and discharge, cathode is more difficult to dilation, and this is negative The resistance of pole is more difficult to increase, therefore can obtain higher effect.

In this case, if fibrous carbon material contains the carbon nanotube etc. with above-mentioned avarage fiber diameter, hold Interconnecting piece 203 is easily formed, thus, it is possible to inhibit the capacity of per unit weight to reduce, therefore further high effect can be obtained. In addition, if ratio ratio W1/W2 meets W1/W2≤200 and sectional area ratio S2/S1 meets S2/S1 >=0.5, just easily In being readily formed above-mentioned three-dimensional mesh structure, and it is easy to maintain the three-dimensional mesh structure, therefore can obtains further High effect.

In addition, the electric conductivity in coating portion 202 can fully improve, therefore can obtain if metal material contains tin etc. Obtain higher effect.In this case, it if ratio W3 is the 0.1 weight % of weight %~10, can inhibit electric in high load capacity Resistance increases, therefore can obtain higher effect.

2. secondary cell > of <

Then, the secondary cell for the cathode for having used above-mentioned this technology is illustrated.

< 2-1. lithium ion secondary battery (cylinder type) >

Fig. 6 shows the section constitution of secondary cell, and Fig. 7 is exaggerated the section structure of rolled electrode bodies 20 shown in Fig. 6 A part in.

Secondary cell described herein is for example, obtained by the occlusion of the lithium as electrode reaction substance and release negative The lithium ion secondary battery of the capacity of pole 22.

[overall structure]

The secondary cell has the battery structure of cylinder type, for example, as shown in fig. 6, the secondary cell is in hollow cylindrical The inside of battery case 11 be accommodated with a pair of of insulation board 12,13 and the rolled electrode bodies 20 as cell device.In rolled electrode In body 20, for example, being wound with the anode 21 and cathode 22 being laminated across diaphragm 23.Contain in the rolled electrode bodies 20 and is soaked with example Such as the electrolyte of liquid electrolyte.

The hollow structure that battery case 11 has such as one end closing and the other end open, and including, for example, iron, In aluminium and their alloy etc. any one or it is two or more.It can be with nickel plating etc. on the surface of the battery case 11.It is a pair of exhausted Listrium 12,13 clips rolled electrode bodies 20, and extends perpendicular to the winding circumferential surface of the rolled electrode bodies 20.

Battery cover 14, relief valve mechanism 15 and thermistor member are riveted across gasket 17 in the open end of battery case 11 Part (PTC element) 16.It is as a result, that battery case 11 is closed.Battery cover 14 is for example comprising material same as battery case 11.Safety valve Mechanism 15 and thermistor element 16 are respectively disposed at the inside of battery cover 14, and the relief valve mechanism 15 is via thermistor element 16 and be electrically connected with battery cover 14.For the relief valve mechanism 15, when due to internal short-circuit or from external heating etc. And when internal pressure being caused to reache a certain level above, disc plate 15A overturning.Battery cover 14 and rolled electrode bodies are cut off as a result, 20 electrical connection.The abnormal heating as caused by high current in order to prevent, the resistance of thermistor element 16 increase with temperature and Increase.Gasket 17 for example includes insulating material, and pitch etc. can be coated on the surface of the gasket 17.

In the space for being formed in the winding center of rolled electrode bodies 20 for example inserted with centrepin 24.But it is also possible to not It is inserted into centrepin 24.It is connected with positive wire 25 on anode 21, and is connected with negative wire 26 on cathode 22.Anode draws Line 25 is including, for example, conductive materials such as aluminium.The positive wire 25 is for example connected to relief valve mechanism 15, and with battery cover 14 It conducts.Negative wire 26 is including, for example, conductive materials such as nickel.The negative wire 26 is for example connected to battery case 11, and with The battery case 11 conducts.

(anode)

Anode 21 for example includes positive electrode collector 21A and the positive-active on positive electrode collector 21A as shown in Figure 7 Material layer 21B.

It should be noted that positive electrode active material layer 21B can both be only arranged at the single side of positive electrode collector 21A, it can also To be set to the two sides of positive electrode collector 21A.In Fig. 7, such as shows positive electrode active material layer 21B and be set to positive pole current collections The case where two sides of body 21A.

Positive electrode collector 21A for example comprising in conductive material any one or it is two or more.The kind of conductive material Class is not particularly limited, for example, aluminium, nickel and stainless steel and other metal materials, or comprising two kinds in the metal material with On alloy.It should be noted that positive electrode collector 21A both can be single layer, or multilayer.

Positive electrode active material layer 21B include can occlude and discharge in the positive electrode of lithium any one or it is two or more As a positive electrode active material.But positive electrode active material layer 21B can also be other comprising positive electrode binder and positive conductive agent etc. In material any one or it is two or more.It should be noted that positive electrode active material layer 21B both can be single layer, it can also be with For multilayer.

Positive electrode be preferably in lithium-containing compound any one or it is two or more.The type of the lithium-containing compound does not have Especially limitation, wherein preferred lithium-contained composite oxide and phosphate cpd containing lithium.This is because can get high-energy density.

" lithium-contained composite oxide " is the oxide for containing lithium and one or more kinds of other elements as constitution element, " other elements " is the element in addition to lithium.Lithium-containing oxides has any one in such as rocksalt-type and spinel-type Kind or two or more crystal structures.

" phosphate cpd containing lithium " is the phosphorylation for containing lithium and one or more kinds of other elements as constitution element Close object.The phosphate cpd containing lithium has any one or two or more crystal structures in such as olivine-type.

The type of other elements as long as in arbitrary element (in addition to lithium) any one or it is two or more just without special It does not limit.Wherein, other elements are preferably belonging to appointing in the second family in long period type periodic table~the 15th race element Meaning is one or more kinds of.More specifically, other elements be more preferably any one or two kinds in nickel, cobalt, manganese and iron with Upper metallic element.This is because can get high voltage.

Lithium-contained composite oxide with rocksalt-type crystal structure is, for example, by following formula (1)~formula (3) respective table The compound etc. shown.

Li_a Mn_(1-b-c)Ni_b M1_c O_(2-d)F_d……(1)

(M1 is at least one of cobalt, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, zirconium, molybdenum, tin, calcium, strontium and tungsten.A~ E meets 0.8≤a≤1.2,0 <b < 0.5,0≤c≤0.5, (b+c) < 1, -0.1≤d≤0.2 and 0≤e≤0.1.But The composition of lithium is different according to charging and discharging state, and a is the value of complete discharge condition.)

Li_a Ni_(1-b)M2_b O_(2-c)F_d……(2)

(M2 is at least one of cobalt, manganese, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and tungsten.A~ D meets 0.8≤a≤1.2,0.005≤b≤0.5, -0.1≤c≤0.2 and 0≤d≤0.1.But the composition of lithium is according to filling Discharge condition and it is different, a be complete discharge condition value.)

Li_aCo_(1-b)M3_b O_(2-c)F_d……(3)

(M3 is at least one of nickel, manganese, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and tungsten.A~ D meets 0.8≤a≤1.2,0≤b < 0.5, -0.1≤c≤0.2 and 0≤d≤0.1.But the composition of lithium is according to charge and discharge State and it is different, a be complete discharge condition value.)

Lithium-contained composite oxide with rocksalt-type crystal structure is, for example, LiNiO₂、LiCoO₂、 LiCo_0.98Al_0.01Mg_0.01O₂、LiNi_0.5Co_0.2Mn_0.3O₂、LiNi_0.8Co_0.15Al_0.05O₂、LiNi_0.33Co_0.33Mn_0.33O₂、 Li_1.2Mn_0.52Co_0.175Ni_0.1O₂And Li_1.15(Mn_0.65Ni_0.22Co_0.13)O₂Deng.

It should be noted that containing nickel, cobalt, manganese and aluminium in the lithium-contained composite oxide with rocksalt-type crystal structure In the case where constitution element, the atom ratio of the nickel is preferably 50 atom % or more.This is because it is close to can get high-energy Degree.

Lithium-contained composite oxide with spinel type crystal structure is, for example, the compound etc. indicated by following formula (4).

Li_aMn_(2-b)M4_bO_cF_d……(4)

(M4 is at least one of cobalt, nickel, magnesium, aluminium, boron, titanium, vanadium, chromium, iron, copper, zinc, molybdenum, tin, calcium, strontium and tungsten.A~ D meets 0.9≤a≤1.1,0≤b≤0.6,3.7≤c≤4.1 and 0≤d≤0.1.But the composition of lithium is according to charge and discharge shape State and it is different, a be complete discharge condition value.)

Lithium-contained composite oxide with spinel type crystal structure is, for example, LiMn₂O₄Deng.

Phosphate cpd containing lithium with olivine-type crystal structure is, for example, the compound etc. indicated by following formula (5).

Li_aM5PO₄……(5)

(M5 is at least one of cobalt, manganese, iron, nickel, magnesium, aluminium, boron, titanium, vanadium, niobium, copper, zinc, molybdenum, calcium, strontium, tungsten and zirconium. A meets 0.9≤a≤1.1.But the composition of lithium is different according to charging and discharging state, a is the value of complete discharge condition.)

Phosphate cpd containing lithium with olivine-type crystal structure is, for example, LiFePO₄、LiMnPO₄、 LiFe_0.5Mn_0.5PO₄And LiFe_0.3Mn_0.7PO₄Deng.

It should be noted that lithium-contained composite oxide may be the compound etc. indicated by following formula (6).

(Li₂MnO₂)_x(LiMnO₂)_1-x……(6)

(x meets 0≤x≤1.But the composition of lithium is different according to charging and discharging state, x is the value of complete discharge condition.)

In addition to this, positive electrode may be such as oxide, disulphide, chalkogenide and electroconductive polymer Deng.Oxide is, for example, titanium oxide, vanadium oxide and manganese dioxide etc..Disulphide is, for example, titanium disulfide and molybdenum sulfide etc..Sulphur Race's compound is, for example, selenizing niobium etc..Electroconductive polymer is, for example, Sulfur, polyaniline and polythiophene etc..

But positive electrode is not limited to above-mentioned material, or other materials.

Details about positive electrode binder for example with the above-mentioned details about negative electrode binder and other negative electrode binders Equally.In addition, the details about positive conductive agent are for example as the above-mentioned details about cathode conductive agent.

(cathode)

Cathode 22 has the composition as the cathode of above-mentioned this technology.

Specifically, cathode 22 for example includes negative electrode collector 22A and is set to negative electrode collector 22A as shown in Figure 7 On negative electrode active material layer 22B.The composition of negative electrode collector 22A is as the composition of negative electrode collector 1, and negative electrode active The composition of material layer 22B is as the composition of negative electrode active material layer 2.

(diaphragm)

Diaphragm 23 is configured between anode 21 and cathode 22.Diaphragm 23 prevents connecing by the anode 21 and cathode 22 as a result, Pass through lithium ion while the generation of short circuit caused by touching.

Diaphragm 23 including, for example, in the perforated membranes such as synthetic resin and ceramics any one or it is two or more, or two Kind or more perforated membrane stacked film.Synthetic resin is, for example, polytetrafluoroethylene (PTFE), polypropylene and polyethylene etc..

It should be noted that diaphragm 23 also may include perforated membrane as escribed above (substrate layer) and be arranged in the substrate layer On high-molecular compound layer.This is because 23 pairs of anodes 21 of diaphragm and the respective close property of cathode 22 improve, therefore wind electricity Polar body 20 is unlikely to deform.Inhibit the decomposition reaction of electrolyte as a result, and also inhibits the leakage containing the electrolyte being immersed in substrate layer Liquid, therefore, even if charge and discharge are repeated, resistance is also not easy to increase, and secondary cell is also difficult to heave.

High-molecular compound layer can be only arranged at the single side of substrate layer, also can be set in the two sides of substrate layer.The height Molecular compound layer including, for example, in the high molecular materials such as polyvinylidene fluoride any one or it is two or more.This is because Polyvinylidene fluoride is excellent on physical strength, and electrochemically stable.When forming high-molecular compound layer, such as in substrate Then solution obtained by coating is dissolved high molecular material by organic solvent etc. on layer makes the substrate layer dry.It needs It is noted that can also make the substrate layer dry again after being impregnated in substrate layer in solution.

(electrolyte)

Electrolyte contains such as solvent and electrolytic salt.The type of solvent can be only one kind, or two or more. The type of electrolytic salt can be only one kind, or two or more.It should be noted that electrolyte can also contain addition In a variety of materials such as agent any one or it is two or more.

Solvent includes the nonaqueous solvents such as organic solvent.Electrolyte comprising nonaqueous solvents is so-called nonaqueous electrolytic solution.

The solvent is, for example, cyclic carbonate, linear carbonate, lactone, chain carboxylate and nitrile (mononitrile) etc..This be because To can get excellent battery capacity, cycle characteristics and preservation characteristics etc..

Cyclic carbonate is, for example, ethylene carbonate, propylene carbonate and butylene carbonate etc..Linear carbonate is, for example, Dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and methyl propyl carbonate etc..Lactone is, for example, in gamma-butyrolacton and γ-penta Ester etc..Chain carboxylate is, for example, methyl acetate, ethyl acetate, methyl propionate, ethyl propionate, propyl butyrate, methyl butyrate, different Methyl butyrate, methyl trimethylacetate and tri-methyl ethyl acetate etc..Nitrile is, for example, acetonitrile, methoxyacetonitrile and 3- methoxy propyl Nitrile etc..

In addition to this, solvent can also be such as 1,2- dimethoxy-ethane, tetrahydrofuran, 2- methyltetrahydrofuran, four Hydrogen pyrans, 1,3- dioxolanes, penta ring of 4- methyl-1,3-dioxy, 1,3- dioxanes, 1,4- dioxanes, N, N- dimethyl formyl Amine, N-Methyl pyrrolidone, N- methyl oxazolidone, N, N'- dimethyl-imidazolinone, nitromethane, nitroethane, ring fourth Sulfone, trimethyl phosphate and dimethyl sulfoxide etc..This is because can get same advantage.

Wherein, preferred carbon such as ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate In acid esters any one or it is two or more.This is because can get superior battery capacity, cycle characteristics and preservation characteristics Deng.

In this case, more preferable ethylene carbonate and propylene carbonate etc. are (high as the high viscosity of cyclic carbonate Dielectric constant) conducts such as solvent (such as relative dielectric constant ε >=30) and dimethyl carbonate, methyl ethyl carbonate and diethyl carbonate The combination of the low viscosity solvent (such as viscosity≤1mPas) of linear carbonate.This is because the dissociative of electrolytic salt and from Transport factor improves.

In addition, solvent may be unsaturated cyclic carbonic ester, halocarbonate, sulphonic acid ester, acid anhydrides, dinitrile compound, Diisocyanate cpd and phosphate etc..This is because the chemical stability of electrolyte improves.

Unsaturated cyclic carbonic ester is the cyclic carbonate with one or more unsaturated bond (carbon-to-carbon double bond). The unsaturated cyclic carbonic ester is, for example, vinylene carbonate (1,3- dioxole -2- ketone), vinyl ethylene carbonate (4- vinyl -1,3- dioxolan-2-one) and carbonic acid methylene ethyl (4- methylene -1,3- dioxolan-2-one) etc.. The content of unsaturated cyclic carbonic ester in a solvent is not particularly limited, for example, 0.01 weight of weight %~10 %.

Halocarbonate is comprising one or more halogen as the ring-type of constitution element or the carbonic ester of chain.Halogen The type of element is not particularly limited, for example, any one in fluorine (F), chlorine (Cl), bromine (Br) and iodine (I) etc. or two kinds with On.Cyclic halo carbonic ester is, for example, the fluoro- 1,3- dioxolan-2-one of 4- and the fluoro- 1,3- dioxolan-2-one of 4,5- bis- etc.. Chain halocarbonate is, for example, carbonic acid methyl fluoride methyl esters, bis- (methyl fluoride) esters of carbonic acid and carbonic acid difluoromethyl methyl esters etc..Halogen It is not particularly limited for the content of carbonic ester in a solvent, for example, 0.01 weight of weight %~50 %.

Sulphonic acid ester is, for example, single sulphonic acid ester and disulfonate etc..Single sulphonic acid ester can be cyclic annular single sulphonic acid ester, or Chain list sulphonic acid ester.Cyclic annular list sulphonic acid ester is, for example, the sultone such as 1,3- propane sultone and 1,3- propene sultone.Chain list Sulphonic acid ester is, for example, to make cyclic annular single sulphonic acid ester compound obtained from the fracture of centre etc..Disulfonate can be cyclic disulfonic acid Ester, or chain disulfonate.The content of sulphonic acid ester in a solvent is not particularly limited, for example, 0.5 weight of weight %~5 Measure %.

Acid anhydrides is, for example, carboxylic acid anhydrides, disulfonic acid acid anhydride and carboxylic acid sulphonic acid anhydride etc..Carboxylic acid anhydrides for example succinic anhydride, glutaric anhydride With maleic anhydride etc..Disulfonic acid acid anhydride is, for example, ethane disulfonic acid acid anhydride and propanedisulfonic acid acid anhydride etc..Carboxylic acid sulphonic acid anhydride is, for example, sulfo group Benzoyl oxide, Sulfo propionic acid acid anhydride and sulfo group butyric anhydride etc..The content of acid anhydrides in a solvent is not particularly limited, for example, 0.5 weight Measure the weight of %~5 %.

Dinitrile compound is, for example, the compound indicated by NC-R1-CN (R1 is any one of alkylidene and arlydene). The dinitrile compound is, for example, succinonitrile (NC-C₂H₄- CN), glutaronitrile (NC-C₃H₆- CN), adiponitrile (NC-C₄H₈ ) and phthalonitrile (NC-C CN₆H₅- CN) etc..The content of dinitrile compound in a solvent is not particularly limited, and for example, 0.5 The weight of weight %~5 %.

Diisocyanate cpd is, for example, by OCN-R2-NCO (R2 is any one of alkylidene and arlydene) table The compound shown.The diisocyanate cpd is, for example, hexamethylene diisocyanate (OCN-C₆H₁₂- NCO) etc..Two is different The content of cyanate esters in a solvent is not particularly limited, for example, 0.5 weight of weight %~5 %.

The specific example of phosphate is trimethyl phosphate, triethyl phosphate and phosphoric acid triallyl ester etc..Phosphate is molten Content in agent is not particularly limited, for example, 0.5 weight of weight %~5 %.

Electrolytic salt including, for example, in lithium salts any one or it is two or more.But electrolytic salt also may include example Salt such as in addition to lithium salts.The salt in addition to lithium salts is, for example, the salt etc. of the light metal in addition to lithium.

Lithium salts is, for example, lithium hexafluoro phosphate (LiPF₆), LiBF4 (LiBF₄), lithium perchlorate (LiClO₄), hexafluoro arsenic Sour lithium (LiAsF₆), tetraphenylboronic acid lithium (LiB (C₆H₅)₄), Loprazolam lithium (LiCH₃SO₃), trifluoromethayl sulfonic acid lithium (LiCF₃SO₃), tetrachloro-lithium aluminate (LiAlCl₄), two lithium (Li of hexafluorosilicic acid₂SiF₆), lithium chloride (LiCl) and lithium bromide (LiBr) etc..This is because can get excellent battery capacity, cycle characteristics and preservation characteristics etc..

Wherein, any one preferably in lithium hexafluoro phosphate, LiBF4, lithium perchlorate and hexafluoroarsenate lithium or two Kind or more, more preferable lithium hexafluoro phosphate.This is because internal resistance reduces, therefore it can get higher effect.

The content of electrolytic salt is not particularly limited, still, wherein preferably with respect to solvent content and be 0.3mol/ Kg~3.0mol/kg.This is because can get high ionic conductivity.

[movement]

The secondary cell for example acts in the following manner.

In charging, lithium ion is discharged from anode 21, and the lithium ion is occluded by electrolyte by cathode 22.It is another Aspect discharges lithium ion from cathode 22, and the lithium ion is occluded by electrolyte by anode 21 in electric discharge.

[manufacturing method]

The secondary cell is for example manufactured according to following step.

In production anode 21, firstly, by the way that positive active material, positive electrode binder and positive conductive agent etc. are mixed To prepare anode mixture.Then, anode mixture is added in organic solvent etc., then the organic solvent is stirred, by This is made for the anode mixture slurry of paste.Finally, being coated with anode mixture slurry on the two sides of positive electrode collector 21A, then Keep the anode mixture slurry dry, positive electrode active material layer 21B is consequently formed.Hereafter, roll squeezer etc. can be used to come to anode Active material layer 21B carries out compression forming.It, can also be in such a case, it is possible to positive electrode active material 21B is heated Repeat multiple compression forming.

When making cathode 22, according to the step same as the manufacturing method of the cathode of above-mentioned this technology in cathode current collection Negative electrode active material layer 22B is formed on the two sides of body 22A.

In secondary cell for assembling, it connect positive wire 25 with positive electrode collector 21A using welding etc., and benefit Negative wire 26 is connect with negative electrode collector 22A with welding etc..Then, make 21 He of anode being laminated across diaphragm 23 Cathode 22 is wound, and rolled electrode bodies 20 are consequently formed.Then, it is inserted in the space of winding center for being formed in rolled electrode bodies 20 Enter centrepin 24.

Then, the rolled electrode bodies 20 are stored in the state of clipping rolled electrode bodies 20 with a pair of of insulation board 12,13 In the inside of battery case 11.In this case, it connect positive wire 25 with relief valve mechanism 15 using welding etc., and Negative wire 26 is connect with battery case 11 using welding etc..Then, electrolyte is injected in the inside of battery case 11, thus Contain the electrolyte to be dipped into rolled electrode bodies 20.Finally, riveting battery in the open end of battery case 11 across gasket 17 Lid 14, relief valve mechanism 15 and thermistor element 16.The secondary cell of cylinder type is made as a result,.

[effect and effect]

According to the secondary cell, since cathode 22 has the composition as the cathode of above-mentioned this technology, even if anti- Charge and discharge are carried out again, and secondary cell is also not easy to expand, and discharge capacity is difficult to decrease.Therefore, it can be improved secondary cell Battery behavior.

Functions and effects in addition to this are as the functions and effects about the cathode of this technology.

< 2-2. lithium ion secondary battery (laminated membrane type) >

Fig. 8 shows the three-dimensional composition of other secondary cells, and Fig. 9 shows the winding electricity along IX-IX line shown in fig. 8 The section constitution of polar body 30.It should be noted that showing in Fig. 8 is separated from each other rolled electrode bodies 30 with outer package member 40 State afterwards.

The constituent element of the secondary cell for the cylinder type having been described above is quoted in the following description at any time.

[overall structure]

Secondary cell is the lithium ion secondary battery of the battery structure with laminated membrane type.The secondary cell is for example such as Fig. 8 The shown inside in membranaceous outer package member 40 is accommodated with the rolled electrode bodies 30 as cell device.In rolled electrode bodies 30 In, it is wound with the anode 33 and cathode 34 being for example laminated across diaphragm 35 and electrolyte layer 36.It is connected with just on anode 33 Pole lead 31, and negative wire 32 is connected on cathode 34.The outermost of rolled electrode bodies 30 is protected using protective glue band 37 Circumference.

Positive wire 31 and negative wire 32 respectively for example draw from the interior of outer package member 40 in the same direction Out.Positive wire 31 containing in the conductive material such as aluminium any one or it is two or more.Negative wire 32 is containing for example In the conductive materials such as copper, nickel and stainless steel any one or it is two or more.These conductive materials be, for example, it is lamellar or Mesh-shape.

Outer package member 40 is, for example, the film that can be folded along the direction of arrow R shown in fig. 8, in the outer packing The recess portion for storing rolled electrode bodies 30 is provided in a part of component 40.The outer package member 40 is, for example, will fusion Laminated film obtained from layer, metal layer and sealer stack gradually.In the manufacturing process of secondary cell, with fused layers that This folds outer package member 40 across the opposite mode of rolled electrode bodies 30, and the outer peripheral edge portion of the fused layers is melted each other It closes.But outer package member 40 or two laminated films being connected to each other via bonding agent etc..Fused layers are including, for example, poly- In the films such as ethylene and polypropylene any one or it is two or more.Metal layer is including, for example, any one in the metal foils such as aluminium foil Or it is two or more.Sealer including, for example, any one of films such as nylon and polyethylene terephthalate or two kinds with On.

Wherein, aluminium layer pressure obtained from outer package member 40 preferably stacks gradually polyethylene film, aluminium foil and nylon membrane Film.But outer package member 40 or the laminated film with other stepped constructions, it can be the polymeric membranes such as polypropylene, It may be metal film.

Between outer package member 40 and positive wire 31 for example in order to prevent the intrusion of extraneous gas and inserted with being close to Film 41.In addition, being close to film 41 inserted with as escribed above between outer package member 40 and negative wire 32.The abutting film 41 contains Have to positive wire 31 and negative wire 32 both with close property material in any one or it is two or more.With tight The material of patch property is, for example, polyolefin resin etc., is polyethylene, polypropylene, modified poly ethylene and modified poly- third more specifically Alkene etc..

(the positive electrode, the negative electrode and the separator)

Anode 33 for example includes positive electrode collector 33A and positive electrode active material layer 33B as shown in Figure 9.Cathode 34 have with The same composition of the cathode of above-mentioned this technology, such as shown in Figure 9 include negative electrode collector 34A and negative electrode active material layer 34B. Positive electrode collector 33A, positive electrode active material layer 33B, negative electrode collector 34A and the respective configuration example of negative electrode active material layer 34B Such as with positive electrode collector 21A, positive electrode active material layer 21B, negative electrode collector 22A and the respective structure of negative electrode active material layer 22B At the same.The composition of diaphragm 35 is for example as the composition of diaphragm 23.

(electrolyte layer)

Electrolyte layer 36 contains electrolyte and high-molecular compound.The electrolyte have in above-mentioned cylindrical secondary battery Used in the same composition of electrolyte.Electrolyte layer 36 described herein is so-called gelatinous electrolyte, in the electrolysis In matter layer 36, electrolyte is kept using high-molecular compound.This is because can get high ionic conductivity (for example, being at room temperature 1mS/cm or more), and prevent the leakage of electrolyte.It should be noted that electrolyte layer 36 can also containing additive etc. its In its material any one or it is two or more.

High-molecular compound include in homopolymer and copolymer etc. any one or it is two or more.Homopolymer is, for example, poly- Acrylonitrile, polyvinylidene fluoride, polytetrafluoroethylene (PTFE), polyhexafluoropropylene, polyethylene oxide, polypropylene oxide, polyphosphazene, poly- silicon oxygen Alkane, polyvinyl fluoride, polyvinyl acetate, polyvinyl alcohol, polymethyl methacrylate, polyacrylic acid, polymethylacrylic acid, benzene second Alkene-butadiene rubber, nitrile rubber, polystyrene and polycarbonate etc..Copolymer is, for example, vinylidene fluoride and hexafluoropropene Copolymer etc..Wherein, homopolymer is preferably polyvinylidene fluoride, and copolymer is preferably vinylidene fluoride and hexafluoropropene Copolymer.This is because electrochemically stable.

In the electrolyte layer 36 as gelatinous electrolyte, " solvent " contained in electrolyte is not only including liquid Material and also including can make electrolytic salt dissociate the material with ionic conductivity broad sense concept.Therefore, make In the case where the high-molecular compound with ionic conductivity, which is also included in solvent.

It should be noted that electrolyte layer 36 directly can be replaced using electrolyte.In the case, electrolyte is impregnated with In rolled electrode bodies 30.

[movement]

The secondary cell for example acts in the following manner.

In charging, lithium ion is discharged from anode 33, and the lithium ion is occluded by electrolyte layer 36 by cathode 34.Separately On the one hand, in electric discharge, lithium ion is discharged from cathode 34, and the lithium ion is occluded by electrolyte layer 36 by anode 33.

[manufacturing method]

The secondary cell for having gelatinous electrolyte layer 36 is for example manufactured by following three kinds of processes.

During the first, anode 33 is made by process same as anode 21 and the respective manufacturing process of cathode 22 With cathode 34.Specifically, positive electrode active material layer 33B is formed on the two sides of positive electrode collector 33A in production anode 33, And when making cathode 34, negative electrode active material layer 34B is formed on the two sides of negative electrode collector 34A.Then, by that will be electrolysed Liquid, high-molecular compound and organic solvent etc. mix and prepare precursor solution.Then, it is coated with precursor solution on anode 33, so After keep the precursor solution dry, gelatinous electrolyte layer 36 is consequently formed.In addition, being coated with precursor solution on cathode 34, so After keep the precursor solution dry, gelatinous electrolyte layer 36 is consequently formed.Then, using welding etc. make positive wire 31 with Positive electrode collector 33A connection, and negative wire 32 is connect with negative electrode collector 34A using welding etc..Then, across The anode 33 and cathode 34 that diaphragm 35 is laminated are wound, and rolled electrode bodies 30 are consequently formed, then in the rolled electrode bodies 30 Outermost circumference paste protective glue band 37.Then, outer package member 40 is folded in a manner of clipping rolled electrode bodies 30, then The outer peripheral edge portion of outer package member 40 is set to be bonded to each other using hot melt connection etc., it is outer that rolled electrode bodies 30 are thus sealing into this The inside of packaging element 40.In the case, it is inserted between positive wire 31 and outer package member 40 and is close to film 41, and Film 41 is close in insertion between negative wire 32 and outer package member 40.

In second process, it connect positive wire 31 with anode 33 using welding etc., and make using welding etc. Negative wire 32 is connect with cathode 34.Then, the anode 33 and cathode 34 that are laminated across diaphragm 35 are wound, are thus made Then the coiling body of presoma as rolled electrode bodies 30 pastes protective glue band 37 in the outermost circumference of the coiling body.Then, Outer package member 40 is folded in a manner of clipping rolled electrode bodies 30, it then will be in outer package member 40 using hot melt connection etc. In addition to the outer peripheral edge portion on one side remaining outer peripheral edge portion bonding, thus coiling body is accommodated in bag-shaped outer package member 40 Inside.Then, by by electrolyte, the monomer of raw material as high-molecular compound, polymerization initiator and as needed The mixing of the other materials such as polymerization inhibitor and prepare electrolyte composition.Then, it is infused in the inside of bag-shaped outer package member 40 Enter electrolyte composition, is then sealed outer package member 40 using hot melt connection etc..Then, and making monomer thermal polymerization Form high-molecular compound.Electrolyte is kept using high-molecular compound as a result, therefore forms gelatinous electrolyte layer 36。

During the third, in addition to use perforated membrane (substrate layer) be formed with the diaphragm 35 of high-molecular compound layer with Outside, coiling body is made by the process as above-mentioned second process, then coiling body is housed in bag-shaped outsourcing Fill the inside of component 40.Then, electrolyte is injected in the inside of outer package member 40, then utilizes hot melt connection etc. by outer packing The opening portion of component 40 seals.Then, outer package member 40 is heated while applying weight to outer package member 40, It is close to diaphragm 35 with anode 33, and is close to diaphragm 35 with cathode 34.Electrolyte is closed containing producing high-molecular is dipped into as a result, In nitride layer, and gelation occurs for the high-molecular compound layer, therefore forms electrolyte layer 36.

Compared with the first process, secondary cell becomes difficult to heave the third process.In addition, the third process and the Two kinds of processes are compared, and solvent and monomer (raw material of high-molecular compound) etc. become difficult to remain in electrolyte layer 36, therefore The formation process of high-molecular compound can be well controllled.Therefore, anode 33, cathode 34 and diaphragm 35 be respectively and electrolyte layer 36 are sufficiently close to.

[effect and effect]

According to the secondary cell, cathode 34 has the composition as the secondary battery cathode of above-mentioned this technology, therefore Even if charge and discharge are repeated, secondary cell is also not easy to expand, and discharge capacity is difficult to decrease.Therefore, it can be improved secondary The battery behavior of battery.

Effect in addition to this and effect are as the effect of the cathode about this technology and effect.

The purposes > of 3. secondary cell of <

Then, the application examples of above-mentioned secondary cell is illustrated.

It can be using the secondary cell as driving power or the storage of electric power storage as long as the purposes of secondary cell is Machinery, equipment, device, device and system (aggregate of multiple equipment etc.) of power supply etc. etc., are just not particularly limited.As electricity The secondary cell in source can be main power source, or accessory power supply.Main power source refers to no matter whether there is or not other power supplys all preferentially to make Power supply.Accessory power supply for example can be the power supply used instead of main power source, or cut as needed from main power source The power supply changed.In the case where using secondary cell as accessory power supply, the type of main power source is not limited to secondary cell.

The purposes of secondary cell is for example as described below: video camera, digital camera, pocket telephone, notebook type are personal The electronic equipments such as computer, wireless phone, stereophone, portable radio, portable television and portable data assistance (including portable electronic device)；The portable life appliance such as electric shaver；The storage devices such as backup power source and storage card；Electricity It bores and the electric tools such as electric saw；The battery pack for being equipped on subnotebook PC etc. as detachable power supply；Pacemaker With the medical electronic equipment such as hearing aid；The electric vehicles such as electric car (including hybrid vehicle)；It and is emergency Deng accumulating systems such as the household batteries systems for preparing and electric power being stored in advance.Certainly, the purposes of secondary cell may be except upper Purposes other than stating.

Wherein, secondary cell is applied to battery pack, electric vehicle, accumulating system, electric tool and electronic equipment etc. is Effectively.This is because at these with excellent battery behavior is required on the way, therefore, by using the secondary cell of this technology, Performance raising can be effectively realized.It should be noted that battery pack is the power supply for having used secondary cell.As described later, should Monocell can be used in battery pack, and assembled battery also can be used.Electric vehicle be using secondary cell as driving power and The vehicle of (traveling) is acted, as described above, or have both automobile (the hybrid power vapour of the driving source in addition to secondary cell Vehicle etc.).Accumulating system is to use secondary cell as the system of storage source.For example, in Household accumulation system, as storage source Secondary cell in store electric power, therefore household electrical appliance etc. can be used using the electric power.Electric tool is by secondary cell The tool for acting movable part (such as drill bit etc.) as driving power.Electronic equipment is to use secondary cell as driving Power supply (power supply) and the equipment for playing various functions.

Here, some application examples to secondary cell are specifically described.It should be noted that application examples described below Composition only an example, therefore, which is configured to suitably change.

< 3-1. battery pack (monocell) >

Figure 10 shows the three-dimensional composition for having used the battery pack of monocell.Figure 11 shows the block of battery pack shown in Figure 10 It constitutes.It should be noted that showing the state after decomposing battery pack in Figure 10.

Battery pack described herein is to have used the battery pack of the simple type of secondary cell an of this technology (so-called soft Packet), it is equipped on such as using smart phone as the electronic equipment of representative.The battery pack for example has as shown in Figure 10: as layer The power supply 111 of the secondary cell of press mold type and the circuit substrate 116 being connect with the power supply 111.It is equipped with just on the power supply 111 Pole lead 112 and negative wire 113.

A pair of of adhesive tape 118,119 is pasted on two sides of power supply 111.It is formed on circuit substrate 116 Protect circuit (PCM:Protection Circuit Module protects circuit module).The circuit substrate 116 passes through tab 114 And it is connect with anode 112, and connect by tab 115 with negative wire 113.In addition, circuit substrate 116 with for outside The lead 117 of the Belt connector of connection connects.It should be noted that the state being had connected in circuit substrate 116 and power supply 111 Under, the circuit substrate 116 is protected using label 120 and insulating trip 121.By pasting the label 120, by 116 He of circuit substrate Insulating trips 121 etc. are fixed.

In addition, battery pack for example has power supply 111 and circuit substrate 116 as shown in figure 11.Circuit substrate 116 has for example Control unit 121, switch portion 122, PTC element 123 and temperature detecting part 124.Power supply 111 can be by positive terminal 125 and negative Extreme son 127 and and external connection, therefore the power supply 111 carries out charge and discharge by positive terminal 125 and negative terminal 127.Temperature Degree test section 124 detects temperature using temperature detection terminal (so-called T terminal) 126.

Control unit 121 controls the movement (use state including power supply 111) of battery pack entirety.The control unit 121 include such as central processing unit (CPU) and memory.

For example, the control unit 121 is and disconnecting switch portion 122 when cell voltage reaches and overcharges electro-detection voltage Make charging current without flow through the current path of power supply 111.In addition, for example, when charging when high current flow through when, control unit 121 Charging current is cut off and disconnecting switch portion 122.

On the other hand, for example, control unit 121 is by making switch portion 122 when cell voltage reaches over-discharge electro-detection voltage It disconnects and makes discharge current without flow through the current path of power supply 111.In addition, for example, being controlled when in electric discharge, high current flows through Portion 121 processed cuts off discharge current and disconnecting switch portion 122.

It should be noted that overcharging electro-detection voltage is, for example, 4.2V ± 0.05V, and over-discharge electro-detection voltage is, for example, 2.4V±0.1V。

Switch portion 122 is according to the instruction of control unit 121 and the use state of Switching power 111, i.e. power supply 111 are set with outside It is standby whether to connect.The switch portion 122 includes such as charging control switch and discharge control switch.Charging control switch and electric discharge Control switch is respectively, for example, to have used the semiconductor switch such as the field effect transistor (MOSFET) of metal-oxide semiconductor (MOS).It needs It is noted that charging and discharging currents are for example detected based on the connection resistance of switch portion 122.

Temperature detecting part 124 measures the temperature of power supply 111, and the measurement result of the temperature is output to control unit 121. The temperature detecting part 124 includes the temperature detecting element such as thermistor.It should be noted that utilizing temperature detecting part 124 The measurement result of the temperature of measurement is used for the case where control unit 121 carries out charge and discharge control in abnormal heating, remains in calculating The case where control unit 121 is corrected processing when covolume amount etc..

It should be noted that circuit substrate 116 can not have PTC element 123.In this case, it is possible to separately in electricity PTC element is set up on base board 116.

< 3-2. battery pack (assembled battery) >

The block that Figure 12 shows the battery pack for having used assembled battery is constituted.

The battery pack for example the inside of cabinet 60 have control unit 61, power supply 62, switch portion 63, amperometric determination portion 64, Temperature detecting part 65, voltage detection department 66, switching controlling part 67, memory 68, temperature detecting element 69, current sense resistor 70 And positive terminal 71 and negative terminal 72.The cabinet 60 is including, for example, plastic material etc..

Control unit 61 controls the movement (use state including power supply 62) of battery pack entirety.The control unit 61 packet It includes such as CPU.Power supply 62 be include two or more this technologies secondary cell assembled battery, this is two or more secondary The type of attachment of battery can be series connection, or it is in parallel, it can also be serial-parallel mixed type.If enumerating an example, power supply 62 include by two parallel connections and three it is concatenated in a manner of 6 secondary cells connecting.

Switch portion 63 is with external equipment come the use state of Switching power 62, i.e. power supply 62 according to the instruction of control unit 61 No connection.The switch portion 63 includes such as charging control switch, discharge control switch, charging diode and electric discharge diode Deng.Charging control switch and discharge control switch are respectively, for example, the field effect transistor for having used metal-oxide semiconductor (MOS) (MOSFET) semiconductor switch such as.

Amperometric determination portion 64 measures electric current using current sense resistor 70, and the measurement result of the electric current is output to control Portion 61 processed.Temperature detecting part 65 utilizes 69 measuring temperature of temperature detecting element, and the measurement result of the temperature is output to control Portion 61 processed.The measurement result of the temperature is used for the case where for example control unit 61 carries out charge and discharge control in abnormal heating, In The case where control unit 61 is corrected processing when calculating residual capacity etc..Voltage detection department 66 measures the secondary cell in power supply 62 Voltage, and supply the measurement result of voltage after analog-to-digital conversion is carried out to control unit 61.Switching controlling part 67 according to from Signal that amperometric determination portion 64 and voltage detection department 66 respectively input and the movement in control switch portion 63.

For example, the switching controlling part 67 is by (charging switch portion 63 when cell voltage reaches and overcharges electro-detection voltage Control switch) it disconnects and flows through charging current without flow through the current path of power supply 62.Power supply 62 can only pass through electric discharge as a result, It is discharged with diode.It should be noted that for example, the cutting of switching controlling part 67 is filled when flowing through high current in charging Electric current.

In addition, for example, when cell voltage reaches over-discharge electro-detection voltage, switching controlling part 67 is by by switch portion 63 (discharge control switch) disconnects and makes discharge current without flow through the current path of power supply 62.Power supply 62 only can be by filling as a result, Electricity is charged with diode.It should be noted that for example, switching controlling part 67 is cut off when flowing through high current in electric discharge Discharge current.

It should be noted that overcharging electro-detection voltage is, for example, 4.2V ± 0.05V, and over-discharge electro-detection voltage is, for example, 2.4V±0.1V。

Memory 68 includes such as the EEPROM as nonvolatile memory.It is stored with for example in the memory 68 The numerical value calculated by control unit 61, the secondary cell measured in manufacturing process's stage information (such as original state is interior Resistance etc.) etc..It should be noted that if storing the fully charged capacity of secondary cell, 61 energy of control unit in memory 68 Enough grasp the information such as residual capacity.

Temperature detecting element 69 measures the temperature of power supply 62, and the measurement result of the temperature is output to control unit 61. The temperature detecting element 69 includes such as thermistor.

Positive terminal 71 and negative terminal 72 are respectively with battery pack is used external equipment (such as the notebook type operated PC etc.), the terminals of the connections such as external equipment (such as charger etc.) for charging to battery pack.Power supply 62 is logical It crosses positive terminal 71 and negative terminal 72 carries out charge and discharge.

< 3-3. electric vehicle >

The block that Figure 13 is shown as the hybrid vehicle of an example of electric vehicle is constituted.

The electric vehicle for example has in the inside of made of metal cabinet 73: control unit 74, engine 75, power supply 76, driving With motor 77, differential gear 78, generator 79, gearbox 80 and clutch 81, inverter 82,83 and various sensors 84.In addition to this, electric vehicle has for example: front-wheel drive shaft 85 and the front-wheel connecting with differential gear 78 and gearbox 80 86 and rear-wheel drive shaft 87 and rear-wheel 88.

The electric vehicle can for example be travelled using any one in engine 75 and motor 77 as driving source. Engine 75 is main power source, for example, petrol engine etc..By engine 75 as power source, such as The driving force (rotary force) of engine 75 is transmitted and differential gear 78, gearbox 80 and clutch 81 as driving portion To front-wheel 86 and rear-wheel 88.It should be noted that since the rotary force of engine 75 is transferred to generator 79, thus generator 79 generate alternating current using the rotary force, and the alternating current is converted into direct current by inverter 83, therefore in power supply 76 Middle storage direct current.It on the other hand, will be from power supply 76 in the case where the motor 77 of converter section will be used as power source The electric power (direct current) of supply is converted into alternating current by inverter 82, therefore motor 77 is driven using the alternating current. Using the motor 77 from electrical power conversion at driving force (rotary force) for example by as the differential gear 78 of driving portion, speed change Case 80 and clutch 81 are transferred to front-wheel 86 and rear-wheel 88.

It should be noted that the resistance when deceleration is in the form of rotary force when electric vehicle is slowed down by arrestment mechanism It is transferred to motor 77, therefore, motor 77 can use the rotary force to generate alternating current.The alternating current passes through inverter 82 And it is converted into direct current, it is therefore preferable that the straight regeneration electric power is stored in power supply 76.

Control unit 74 controls the movement of electric vehicle entirety.The control unit 74 includes such as CPU.Power supply 76 wraps Include the secondary cell of one or more kinds of this technologies.The power supply 76 can be by connecting and from the external electrical with external power supply Source receives power supply and accumulates electric power.Various sensors 84 are for for example controlling the revolving speed of engine 75 and controlling throttle valve Aperture (accelerator open degree).The various sensors 84 include that such as velocity sensor, acceleration transducer and engine speed pass In sensor etc. any one or it is two or more.

It should be noted that, although list the case where electric vehicle is hybrid vehicle as an example, but the electricity Motor-car or the vehicle (electric car) acted without using engine 75 using only power supply 76 and motor 77.

< 3-4. accumulating system >

The block that Figure 14 shows accumulating system is constituted.

The accumulating system for example has in the inside in the houses such as ordinary residence and commercial building 89: control unit 90, power supply 91, Intelligent electric meter 92 and power hub 93.

Here, power supply 91 can be connect with the electrical equipment 94 for the inside that house 89 is for example arranged in, and can with stop Electric vehicle 96 in the outside in house 89 connects.In addition, power supply 91 for example by power hub 93 be arranged in house Self power generation in 89 is connected with generator 95, and can pass through intelligent electric meter 92 and power hub 93 and external concentration Type power supply system 97 connects.

It should be noted that electrical equipment 94 includes for example one or more kinds of household electrical appliance, the household electrical appliance example For example refrigerator, air-conditioning, television set and water heater etc..Self power generation generator 95 includes that such as solar generator and wind-force are sent out In motor etc. any one or it is two or more.Electric vehicle 96 includes such as electric car, electric bicycle and hybrid power In automobile etc. any one or it is two or more.Concentrated power supply system 97 includes such as heat power station, nuclear power station, waterpower hair In power station and wind power station etc. any one or it is two or more.

Control unit 90 controls the movement (use state including power supply 91) of accumulating system entirety.The control unit 90 Including such as CPU etc..Power supply 91 includes the secondary cell of one or more kinds of this technologies.Intelligent electric meter 92 is, for example, to be arranged The kilowatt meter of Web-compatible type in the house of electric power demand side 89, and can be communicated with power supply side.Along with this, Intelligent electric meter 92 for example controls the balance of the demand and supply of the electric power in house 89 while with PERCOM peripheral communication, thus, it is possible to Carry out efficient and stable energy supply.

For the accumulating system, for example, passing through intelligent electric meter from the concentrated power supply system 97 as external power supply 92 and power hub 93 electric power is stored in power supply 91, and pass through electricity from the self power generation generator 95 as independent current source Source hub 93 stores electric power in power supply 91.The electric power stored in power supply 91 is supplied to according to the instruction of control unit 90 Electrical equipment 94 and electric vehicle 96, therefore the electrical equipment 94 can act, and the electric vehicle 96 can charge.That is, Accumulating system is the system for being able to use power supply 91 to carry out storage and the supply of the electric power in house 89.

The electric power stored in power supply 91 can use as needed.Thus it is for example possible to pre- in the late into the night that the charge for electricity is small Electric power is stored in power supply 91 from concentrated power supply system 97 first, has been stored in the power supply 91 in the use on daytime that the electric lighting bill is heavy Electric power.

It should be noted that above-mentioned accumulating system can be arranged by each family (one family), it can also be by every more families (multiple families) setting.

< 3-5. electric tool >

The block that Figure 15 shows electric tool is constituted.

Electric tool described herein is, for example, electric drill.The electric tool for example has control in the inside of tool body 98 Portion 99 and power supply 100.It is equipped with for example as the bit head of movable part 101 with can operating (rotation) on the tool body 98.

Tool body 98 is including, for example, plastic material etc..Control unit 99 is to the movement of electric tool entirety (including power supply 100 Use state) controlled.The control unit 99 includes such as CPU.Power supply 100 includes one or more kinds of this technology Secondary cell.The control unit 99 is supplied by electric power from power supply 100 to bit head 101 according to the operation of step switch.