阅读说明：本技术 全固体锂离子二次电池 (All-solid-state lithium-ion secondary battery ) 是由 尾濑德洋 长谷川元 大泷光俊 近都佑介 于 2018-04-13 设计创作，主要内容包括：本发明的目的在于提供循环特性良好的全固体锂离子二次电池,其具有包含选自可与Li形成合金的金属、该金属的氧化物和该金属与Li的合金中的至少一个作为负极活性物质的负极。全固体锂离子二次电池,其中,负极含有负极活性物质、导电材料和固体电解质,上述负极活性物质包含选自可与Li形成合金的金属、该金属的氧化物和该金属与Li的合金中的至少一种的活性物质,上述固体电解质是BET比表面积为1.8～19.7m<Sup>2</Sup>/g的粒子。(The purpose of the present invention is to provide the good all-solid-state lithium-ion secondary battery of cycle characteristics, there is cathode of at least one of the alloy comprising the oxide and the metal and Li that are selected from the metal that can form alloy with Li, the metal as negative electrode active material.All-solid-state lithium-ion secondary battery, wherein, cathode contains negative electrode active material, conductive material and solid electrolyte, above-mentioned negative electrode active material includes the active material for being selected from least one of alloy that the metal of alloy, the oxide of the metal and the metal and Li can be formed with Li, and above-mentioned solid electrolyte be that BET specific surface area is 1.8~19.7m 2 The particle of/g.)

1. all-solid-state lithium-ion secondary battery, wherein cathode contains negative electrode active material, conductive material and solid electrolyte, on Stating negative electrode active material includes in the alloy that can form the metal of alloy, the oxide of the metal and the metal and Li with Li At least one active material, above-mentioned solid electrolyte be BET specific surface area be 1.8~19.7m²The particle of/g.

2. all-solid-state lithium-ion secondary battery according to claim 1, wherein above-mentioned solid electrolyte particles by following Range of the value A that formula (1) is found out 12.4~56.7:

Formula (1) A=BET specific surface area (m²/ g) × median diameter D50 (μm) × density (g/cm³)。

3. all-solid-state lithium-ion secondary battery according to claim 1 or 2, wherein above-mentioned negative electrode active material includes choosing From the active material of at least one of the alloy of Si simple substance and Si and Li.

4. all-solid-state lithium-ion secondary battery according to any one of claim 1-3, wherein above-mentioned solid electrolyte is Sulfide solid electrolyte.

5. all-solid-state lithium-ion secondary battery described in any one of -4 according to claim 1, wherein above-mentioned conductive material is choosing From the carbon system raw material of at least one of carbon black, carbon nanotube and carbon nano-fiber.

Technical field

This disclosure relates to all-solid-state lithium-ion secondary battery.

Background technique

Active material (alloy system active material) and carbon-based negative electrode activity containing metals such as the Si that can form alloy with Li Substance is compared, and the theoretical capacity of unit volume is big, thus propose by such alloy system active material be used for the lithium of cathode from Sub- battery.

Patent Document 1 discloses use average grain diameter to be 10 μm of alloy system active materials below as negative electrode active The secondary battery cathode of material powder close material and all-solid lithium with the negative electrode layer comprising the negative electrode active material powder from Sub- battery.

Summary of the invention

Subject to be solved by the invention

But for disclosed in patent document 1 it is such, use alloy system active material as the complete of negative electrode active material For solid lithium-ion secondary cell, capacity maintenance rate when repeated charge-discharge cycles is low.

The disclosure is in view of above-mentioned actual conditions, and it is an object of the present invention to provide the secondary electricity of the good all-solid-state lithium-ion of cycle characteristics Pond, have comprising in the alloy that can form the metal of alloy, the oxide of the metal and the metal and Li with Li extremely A kind of cathode of few active material as negative electrode active material.

Means for solving the problems

In the all-solid-state lithium-ion secondary battery of the disclosure, cathode contains negative electrode active material, conductive material and solid electricity Xie Zhi, above-mentioned negative electrode active material include to be selected from that the metal of alloy, the oxide of the metal and the metal and Li can be formed with Li At least one of alloy active material, above-mentioned solid electrolyte is that BET specific surface area is 1.8~19.7m²The grain of/g Son.

In the all-solid-state lithium-ion secondary battery of the disclosure, the value A of above-mentioned solid electrolyte found out by following formula (1) can In 12.4~56.7 range.

Formula (1) A=BET specific surface area (m²/ g) × median diameter D50 (μm) × density (g/cm³) disclosure all-solid lithium In ion secondary battery, above-mentioned negative electrode active material may include the work of at least one of alloy selected from Si simple substance and Si and Li Property substance.

In the all-solid-state lithium-ion secondary battery of the disclosure, above-mentioned solid electrolyte can be sulfide solid electrolyte.

In the all-solid-state lithium-ion secondary battery of the disclosure, above-mentioned conductive material can for selected from carbon black, carbon nanotube and The carbon system raw material of at least one of carbon nano-fiber.

Invention effect

According to the disclosure, it is capable of providing the good all-solid-state lithium-ion secondary battery of cycle characteristics, is had comprising being selected from The active material that at least one of the metal of alloy, the oxide of the metal and the metal and the alloy of Li can be formed with Li is made For the cathode of negative electrode active material.

Detailed description of the invention

Fig. 1 is the schematic diagram of the configuration example of all-solid-state lithium-ion secondary battery.

Specific embodiment

In the all-solid-state lithium-ion secondary battery of the disclosure, cathode contains negative electrode active material, conductive material and solid electricity Xie Zhi, above-mentioned negative electrode active material include to be selected from that the metal of alloy, the oxide of the metal and the metal and Li can be formed with Li At least one of alloy active material, above-mentioned solid electrolyte is that BET specific surface area is 1.8~19.7m²The grain of/g Son.

Since the ionic conductivity and electronic conductivity that can form the metal itself of alloy with Li are low, usually by the gold Belong in the case where being used as negative electrode active material, contains conductive material and solid electrolytic together with negative electrode active material in cathode Matter.

Use the metal that can form alloy with Li (will can form the gold of alloy with Li sometimes below as negative electrode active material Category is recorded as M.) in the case where, with the charging of lithium ion secondary battery, occurs shown in following formula (2) in cathode, is so-called Electrochemically alloying reaction.

Formula (2) xLi⁺+xe^-+yM→Li_xM_y

In addition, with the electric discharge of lithium ion secondary battery, in cathode, as shown in following formula (3), occur Li from What son was detached from from the alloy of above-mentioned M and Li reacts.

Formula (3) Li_xM_y→xLi⁺+xe^-+yM

It is and above-mentioned in having used lithium ion secondary battery of the metal as negative electrode active material that can form alloy with Li It is big that the insertion of Li shown in formula (2) and formula (3) is detached from the volume change for reacting associated.

In patent document 1, following purports: the average grain of the powder of ionic conductivity substance (solid electrolyte) are described Diameter is smaller, and the contact point of negative electrode active material and solid electrolyte is more increased, therefore preferably.

But this researchers has found: if containing negative electrode active material, conductive material and solid electrolyte having The average grain diameter of solid electrolyte is exceedingly set to become smaller in the all-solid-state lithium-ion secondary battery of cathode, then sometimes especially first Capacity maintenance rate deteriorates in stage phase.

Make the average grain diameter of the solid electrolyte in cathode become smaller (that is, specific surface area is made to become larger) when, from ionic conduction Viewpoint is set out excellent, but conductive material becomes easy the surface for being adsorbed in solid electrolyte.Therefore, the conduction material in cathode is generated The unevenness of material, electronics conduction path narrows in the few part of conductive material.

In this way, in the narrow part of electronics conduction path, due to repeated the alloy system active matter associated with charge and discharge The volume change of matter, electronics conduction path is cut off at leisure, therefore as a result, thinks that the capacity of lithium ion secondary battery maintains Rate deteriorates.

In the all-solid-state lithium-ion secondary battery of the disclosure, by using BET specific surface area in particular range in cathode Solid electrolyte particles, so as to maintain good ionic conductivity, while preventing the unevenness of conductive material, therefore, it is considered that Capacity maintenance rate can be kept higher in the case where using alloy system active material as negative electrode active material.

The all-solid-state lithium-ion secondary battery of the disclosure is explained in detail below.

1. all-solid-state lithium-ion secondary battery

As long as functioning as secondary cell, spy is had no to the composition of the all-solid-state lithium-ion secondary battery of the disclosure It does not limit.As illustrated in figure 1, typically, there is anode 2, cathode 3 and configure between the anode 2 and the cathode 3 Solid electrolyte layer 1 is constituted as anode-solid electrolyte layer-cathode aggregate 101.Anode-the solid electrolyte layer- Cathode aggregate 101 is the aggregate in each portion with following arrangement architecture: anode, solid electrolyte layer and cathode are successively arranged Column can engage directly or via the part that is made of other materials, in turn, can be existing for the solid electrolyte layer on anode Position existing for solid electrolyte layer in the opposite side (positive outside) and cathode of position opposite side (cathode it is outer Side) in one or both sides engage the part that is made of other materials.

It is installed on above-mentioned anode-solid electrolyte layer-cathode aggregate 101 by other components by collector etc., from And the element cell of the functional unit as all-solid-state battery is obtained, which can be directly used as to all-solid-state lithium-ion electricity Multiple element cells can also be integrated and be electrically connected by pond, so that element cell aggregate is made, the all-solid lithium as the disclosure Ion battery.

Anode-solid electrolyte layer-cathode aggregate anode and the respective thickness of cathode are usually the left side 0.1 μm~10mm The right side, the thickness of solid electrolyte layer are usually 0.01 μm~1mm or so.

1-1. cathode

The cathode of the all-solid-state lithium-ion battery of the disclosure contains negative electrode active material, conductive material and solid electrolyte.

(negative electrode active material)

Above-mentioned negative electrode active material include selected from can be formed with Li the metal of alloy, the oxide of the metal and the metal with The active material of at least one of the alloy of Li.

As long as can be with the Li metal for forming alloy and so-called electrochemical alloy shown in above-mentioned formula (2) and formula (3) Change reaction to accompany, Li ion can be inserted into the metal being detached from, then there is no particular restriction.As the gold that can form alloy with Li The example for belonging to element, can enumerate Mg, Ca, Al, Si, Ge, Sn, Pb, Sb and Bi etc., wherein it can be Si, Ge, Sn, it can also be with It is Si.It should be noted that " metal " term is as including " metal " used in general element classification and " half gold in the disclosure The concept of category " uses.

It can refer to that the charging with lithium ion secondary battery passes through together, in cathode with the oxide of the Li metal for forming alloy The electrochemical reaction of following formula (4) and the oxide for generating M.

Formula (4) xLi⁺+xe^-+yMO→Li_xO_y+yM

The M that oxide for forming the metal of alloy according to formula (4) You Keyu Li generates, can be according to above-mentioned formula (2) Or the electrochemical reaction of (3) carries out the insertion disengaging of Li, therefore, in general, the oxide of the metal of alloy can be formed with Li It is classified as the scope of alloy system active material.It is detached from the insertion of Li and react this big property of associated volume change and can be with The metal that Li forms alloy is same.

The example of oxide as the metal that can form alloy with Li, can enumerate SiO, SnO etc., can be SiO.

The ratio of negative electrode active material in cathode is not particularly limited, for example, 40 mass % or more, it can be 50 It, can be in the range of the 50 mass % of mass %~70 in the range of the mass of quality %~90 %.

Also simultaneously to the above-mentioned shape that can form the metal of alloy, the oxide of the metal and the metal and the alloy of Li with Li Be not particularly limited, such as particle shape, membranaceous shape can be enumerated etc..

(solid electrolyte)

Above-mentioned solid electrolyte is that BET specific surface area is 1.8~19.7m²The particle of/g.As described above, by using BET specific surface area is 1.8~19.7m²The particle of/g will can keep higher lithium ion as the solid electrolyte in cathode The capacity maintenance rate of secondary cell.

Wherein, so-called BET specific surface area refers to the unimolecule adsorbance using the gas to material surface, using BET method The specific surface area of calculating.

If BET specific surface area is more than 19.7m²/ g, then conductive material is adsorbed in the surface of solid electrolyte, leads in cathode Electric material is uneven, therefore locally electronics conduction path narrows, and as a result capacity maintenance rate reduces.If BET specific surface area less than 1.8m²/ g then tails off with the contact point of negative electrode active material, therefore cannot maintain ion conduction pathway.

In order to balancedly maintain ion conduction pathway and electronics conduction path, the BET specific surface area of solid electrolyte particles It can be 3.0~9.0m²/g。

In addition, the value A of above-mentioned solid electrolyte particles found out by following formula (1) can 12.4~56.7 range.

Formula (1) A=BET specific surface area (m²/ g) × median diameter D50 (μm) × density (g/cm³) in above-mentioned formula (1), it is so-called Median diameter is that the partial size of particle is become the one of total volume by the cumulative volume of particle in tactic situation from small to large Half (50%) diameter.

Value A is the parameter for indicating the shape of particle, and in the case where the shape of particle is sphere, value A is 6.0.Wherein, So-called shape in the disclosure refers to the shape of the also fine convex-concave comprising particle surface and the open pore existing for inside etc..

The BET specific surface area of solid electrolyte particles in cathode is in 1.8~19.7m²In the case where the range of/g, such as Fruit makes value A in 12.4~56.7 range, then capacity maintenance rate improves.It is difficult to manufacture solid electrolytic plasmid of the value A less than 12.4 Son, but the tendency that existence value A is more improved close to 6.0 capacity maintenance rates are led when therefore, it is considered that the shape of particle is closer to sphere Electric material is more difficult to exist on solid electrolyte particles surface.

For the raw material of above-mentioned solid electrolyte particles, as long as can be used in all-solid-state lithium-ion secondary battery, It is just not particularly limited, it is preferable to use the high oxide system amorphous solid electrolyte of the conductivity of Li ion, sulfide-based amorphous are solid Body electrolyte, crystalline oxides nitride etc..

As above-mentioned oxide system amorphous solid electrolyte, such as Li can be enumerated₂O-B₂O₃-P₂O₃、Li₂O-SiO₂Deng, As above-mentioned sulfide-based amorphous solid electrolyte, such as Li can be enumerated₂S-SiS₂、LiI-Li₂S-SiS₂、LiI-Li₂S- P₂S₅、LiI-Li₃PO₄-P₂S₅、Li₂S-P₂S₅Deng.In addition, as above-mentioned crystalline oxides nitride etc., can enumerate LiI, Li₃N、Li₅La₃Ta₂O₁₂、Li₇La₃Zr₂O₁₂、Li₆BaLa₂Ta₂O₁₂、Li₃PO_(4-3/2w)N_{W (w < 1)}、Li_3.6Si_0.6P_0.4O₄Deng.

The ratio of solid electrolyte in cathode is not particularly limited, for example, 10 mass % or more, it can be in 20 matter It, can be in the range of the 25 mass % of mass %~45 in the range of measuring the mass of %~50 %.

(conductive material)

As long as above-mentioned conductive material is able to use in all-solid-state lithium-ion secondary battery in cathode, special limit is had no System.For example, the raw material of above-mentioned conductive material can be selected from the carbon blacks such as acetylene black and furnace black, carbon nanotube and carbon Nanowire The carbon system raw material of at least one of dimension.

From the viewpoint of electronic conductivity, it can be selected from least one of carbon nanotube and carbon nano-fiber carbon system Raw material, the carbon nanotube and carbon nano-fiber can be VGCF (vapor phase method carbon fiber).

The ratio of conductive material in cathode is not particularly limited, for example, 1.0 mass % or more, it can be in 1.0 matter It, can be in the range of the 2.0 mass % of mass %~10.0 in the range of measuring the mass of %~12.0 %.

In cathode, in addition to the above ingredients, the other compositions such as binder can be contained.This is because viscous in cathode The presence or absence of other compositions such as knot agent do not influence following effects: being 1.8~19.7m by using BET specific surface area²The grain of/g Son is used as solid electrolyte, so that on solid electrolyte surface, conductive material is no longer uneven.

As above-mentioned binder, such as it is able to use polyvinylidene fluoride (PVdF), polytetrafluoroethylene (PTFE) (PTFE), butylene rubber Glue (BR), SBR styrene butadiene rubbers (SBR), polyvinyl butyral (PVB), acrylic resin etc., can be and gather inclined two Vinyl fluoride (PVdF).

From improving energy density, this disclosure relates to cathode can be few negative of the ingredient other than negative electrode active material Pole.

1-2. positive

As long as above-mentioned anode is functioned as the anode of all-solid-state lithium-ion secondary battery, there is no particular restriction, leads to It often include the positive active material containing Li, as needed comprising other compositions such as binder, solid electrolyte and conductive materials.

As long as active material of the positive active material containing Li element in the disclosure containing Li, then have no special limit System.As long as functioning, making as the positive active material in battery chemistries reaction according to the relationship with negative electrode active material With the substance that the battery chemistries reaction of the movement of Li ion carries out, then it can be used as positive active material with no particular limitation, Substance known to the positive active material as lithium ion battery can also use in the disclosure in the past.

Raw material as a positive electrode active material has no spy as long as can use in all-solid-state lithium-ion secondary battery It does not limit.Such as cobalt acid lithium (LiCoO can be enumerated₂), lithium nickelate (LiNiO₂), LiMn2O4 (LiMn₂O₄), by Li_1+xNi_{1/ 3}Mn_1/3Co_1/3O₂、Li_1+xMn_2-x-yM_yO₄The composition that (M is the element selected from one or more of Al, Mg, Co, Fe, Ni, Zn) indicates Xenogenesis element substitution Li-Mn spinelle, lithium titanate (Li_xTiO_y), phosphate metal lithium (LiMPO₄, M=Fe, Mn, Co, Ni etc.) Deng.

Above-mentioned positive active material can have coating, the coating have lithium-ion-conducting, even and if containing with Active material or solid electrolyte contact also immobilising substance.As the substance, such as LiNbO can be enumerated₃、Li₄Ti₅O₁₂、 Li₃PO₄。

Above-mentioned the shape of the positive electrode active material is not particularly limited, can be membranaceous, or particle shape.

The ratio of positive active material in anode is not particularly limited, for example, 60 mass % or more, it can be 70 It, can be in the range of the 80 mass % of mass %~90 in the range of the mass of quality %~95 %.

As long as the raw material of solid electrolyte used in anode can use in all-solid-state lithium-ion secondary battery, There is no particular restriction, it is preferable to use the conductivity of Li ion is high in the same manner as the raw material of solid electrolyte used in cathode Oxide system amorphous solid electrolyte, sulfide-based amorphous solid electrolyte, crystalline oxides nitride etc..

As conductive material, the raw material of binder, it is able to use material same as material used in cathode.

1-3. solid electrolyte layer

As long as above-mentioned solid electrolyte layer is functioned as the solid electrolyte of all-solid lithium secondary battery, also without spy It does not limit, generally comprises solid electrolyte raw material, as needed comprising other compositions such as binders.

As solid electrolyte, the raw material of binder, it is able to use material same as material used in anode.

The ratio of solid electrolyte raw material in solid electrolyte layer is not particularly limited, for example, 50 mass % with On, it can be in the range of 70 mass of mass %~99.99 %, it can be in the range of 90 mass of mass %~99.9 %.

2. the manufacturing method of all-solid-state lithium-ion secondary battery

As long as the manufacturing method of the all-solid-state lithium-ion secondary battery of the disclosure can manufacture the all-solid lithium of the disclosure The method of ion secondary battery, then there is no particular restriction.For example, can prepare that there is anode to close material, solid electrolyte material portion With the battery components of the negative electrode material together containing negative electrode active material, conductive material and solid electrolyte, which is carried out It is powered, to obtain the all-solid-state lithium-ion secondary battery of the disclosure.

The method that above-mentioned battery components are powered also is not particularly limited, in order to expeditiously carry out in above-mentioned formula (1) Shown in, electrochemically alloying reaction, can make current density become 0.1~6.0mA/cm²Range, can make voltage become 4.3 ~4.7V (vs Li/Li⁺) range.

The sequence of material, solid electrolyte material portion and battery components is closed to manufacturing process according to negative electrode material together, anode below Example be illustrated.

2-1. negative electrode material together

Negative electrode material together contains negative electrode active material, conductive material and solid electrolyte, as long as the negative electrode active material Containing the active material that can form at least one of the metal of alloy and the oxide of the metal with Li is selected from, as the solid Electrolyte is 1.8~19.7m containing BET specific surface area²The particle of/g, then there is no particular restriction.

As described above by being powered to battery components, cathode can be obtained by negative electrode material together.

Negative electrode material together is other than above-mentioned negative electrode active material, above-mentioned conductive material and above-mentioned solid electrolyte, as needed It may include the other compositions such as binder.

As long as this is because the use of BET specific surface area being 1.8~19.7m²Original of the particle of/g as solid electrolyte Material, is just able to maintain that the shape that conductive material equably disperses in above-mentioned negative electrode material together and the cathode manufactured by the negative electrode material together State.

Wherein, the BET specific surface area of the solid electrolyte particles in cathode is in 1.8~19.7m²The case where range of/g Under, although make the range of value A 12.4~56.7, capacity maintenance rate is improved, from the viewpoint of manufacture view, value A mistake Solid electrolyte particles are easy cohesion each other when low, therefore preferably make value A 17.5~22.0 (17.5~56.7).

As comprising living selected from the cathode that can form at least one of the metal of alloy and the oxide of the metal with Li Property substance, conductive material, solid electrolyte and binder contained as needed ingredient raw material, be able to use and 1- 1. the same raw material of the raw material illustrated in cathode.

Raw material, the i.e. negative electrode material together raw material for being used to form above-mentioned negative electrode material together may include negative electrode active material, conduction material Ingredient other than the raw material of material, solid electrolyte and binder contained as needed can also reside in form cathode in turn Close the ingredient being removed in the way of material.Although as the quilt included in negative electrode material together raw material but in the way for forming negative electrode material together The ingredient of removing can enumerate solvent and removable binder.As removable binder, it is able to use following bonding Agent: it is functioned when forming negative electrode material together as binder, but in the process for obtaining negative electrode material together and being burnt into Decompose or volatilization etc. and be removed, the negative electrode material together without binder can be made.

The method for forming negative electrode material together is also not particularly limited.As long as this is because using BET specific surface area be 1.8~ 19.7m²Raw material of the particle of/g as solid electrolyte is then being formed by negative electrode material together and is being manufactured by the negative electrode material together negative The state that conductive material equably disperses just is able to maintain that in extremely.

As the method for forming negative electrode material together, such as it can enumerate and compression forming is carried out to the powder of negative electrode material together raw material Method.In the case where carrying out compression forming to the powder of negative electrode material together raw material, usually 400~1000MPa's of load or so Moulding pressure.Further, it is possible to use roll squeezer carries out compression forming, line pressure can be set as 10~100kN/ in this case cm。

In addition, following methods can be used: the powder of the negative electrode material together raw material comprising removable binder is compressed By being burnt into the method for removing binder after molding；With the negative electrode material together original that will include solvent and removable binder The dispersion liquid of material is coated in solid electrolyte material portion or on other supporting masses, after shape that is dry and being formed as negative electrode material together The method etc. for being removed binder by firing.

2-2. anode closes material

In the manufacturing method of the disclosure, anode closes material for example comprising the positive active material raw material containing Li, according to need To include other raw materials such as binder, solid electrolyte and conductive material.

As described above by being powered to battery components, material can be closed by anode and obtain anode.

As other raw materials such as binder, conductive material, solid electrolyte, it is able to use and example in above-mentioned 1-2. anode The same raw material of the raw material shown.

It is used to form the raw material that anode closes material, i.e. anode conjunction material can further include with raw material and close the way of material in formation anode In the ingredient that is removed.The material ingredient being removed in raw material but in forming the positive way for closing material is closed as anode is included in, Ingredient same as the solvent that can contain in negative electrode material together raw material and removable binder can be enumerated.

As the method for forming anode conjunction material, method same as the method for forming negative electrode material together can be enumerated.

2-3. solid electrolyte material portion

In the manufacturing method of the disclosure, solid electrolyte material portion is for example comprising solid electrolyte raw material, as needed Include other compositions.

As described above by being powered to battery components, solid electrolyte can be obtained by solid electrolyte material portion Layer.

As solid electrolyte raw material, it is able to use raw material same as the raw material illustrated in 1-3. solid electrolyte layer.

The ratio of solid electrolyte raw material in solid electrolyte material portion is not particularly limited, for example, 50 mass % More than, it can be in the range of the 70 mass % of mass %~99.99, it can be in the range of the 90 mass % of weight %~99.9.

Other compositions contained in solid electrolyte material portion are also able to use and illustrate in 1-3. solid electrolyte layer The same material of material.

As the method for forming solid electrolyte material portion, can enumerate to comprising solid electrolyte raw material and as needed Other compositions solid electrolyte material powder carry out compression forming method.The powder of solid electrolyte material is carried out In the case where compression forming, in general, in the same manner as carrying out the situation of compression forming with the powder for closing material to cathode, load 400~ The moulding pressure of 1000MPa or so.Further, it is possible to use roll squeezer carries out compression forming, line pressure can be set in this case It is set to 10~100kN/cm.

In addition, as other methods, can using used containing solid electrolyte raw material and as needed other at Solution or the casting filming therapy of dispersion liquid of the solid electrolyte material divided etc..

2-4. battery components

In the manufacturing method of the disclosure, battery components are, for example, to have each portion of following arrangement architecture in the disclosure Aggregate (anode close material-solid electrolyte material portion-negative electrode material together aggregate): anode close material, solid electrolyte material portion and Negative electrode material together arranges in the order, directly or via the part being made of other materials engages, and in turn, can close on material in anode Solid electrolyte material portion existing for position the opposite side outside of material (anode close) and the solid electrolytic in negative electrode material together What the one or both sides engagement in the opposite side (outside of negative electrode material together) of position existing for material portion was made of other materials Part.

As long as above-mentioned battery components can close material side via solid electrolyte material portion to negative electrode material together side from anode It is powered on direction, then it can also the attached part being made of other materials.Example between material and solid electrolyte material portion is closed in anode Such as settable LiNbO₃、Li₄Ti₅O₁₂、Li₃PO₄Such coating.The outside of material and the outside of negative electrode material together are closed in anode Either side or two sides, for example, can attached collector, external packing body.

Above-mentioned battery components are typically to have the aggregate of following arrangement architecture: anode close material, negative electrode material together and Above-mentioned anode closes the solid electrolyte material portion configured between material and above-mentioned negative electrode material together and directly engages, and closes material in anode Outside and the outside of negative electrode material together are not engaged the part being made of other materials.

The method of production battery components is not particularly limited, for example, can be by the molding compression barrel of powder compression The powder of interior investment negative electrode material together raw material, is piled into uniform thickness, negative electrode material together raw material powder layer is formed, in the cathode Close the material solid electrolyte of investment comprising solid electrolyte powder and other compositions as needed on material powder stack layer With the powder of material, it is piled into uniform thickness, solid electrolyte material powder last layer is formed, in the solid electrolyte material Investment closes the powder of material raw material comprising the anode of the positive active material containing Li on powder bed, is piled into uniform thickness, It forms anode and closes material raw material powder layer, the powder accumulation body of the pile of grounds lamination to have three layers later to the tool formed in this way is simultaneously Compression forming is carried out, to make battery components.

In addition, the hand other than powder compression molding can also be used in solid electrolyte material portion, negative electrode material together and anode conjunction material Method production.Specific method is as aforementioned in this specification.For example, use, which can be used, in solid electrolyte material portion includes solid The casting filming therapy of the solution of the solid electrolyte material of electrolyte or dispersion liquid is carried out using the rubbing method of molding coating machine Molding.Negative electrode material together and anode close material and for example can be used by that will include negative electrode material together raw material or the positive powder for closing material raw material After the dispersion liquid of last and removable binder is coated in solid electrolyte material portion or collector and forms film, by this Film heats and the method that removes binder from film；Alternatively, it is former to close material comprising negative electrode material together raw material or anode The powder compression forming of material and removable binder and after the shape that anode closes material or negative electrode material together is made, by the formed body The method for heating and removing binder from film is formed.Material is closed for negative electrode material together and anode, in order to improve electrode density, Densification compacting can be carried out in advance before compression forming.

In addition, negative electrode material together and anode close material can also on the supporting mass other than solid electrolyte material portion or collector shape At.In this case, negative electrode material together and anode are closed material to remove from the support, the negative electrode material together of removing or anode is closed into material and existed Solid electrolyte material engages in portion.

Below pair this disclosure relates to all-solid-state lithium-ion secondary battery discharge capacity sustainment rate calculation method example Son is illustrated.

Firstly, carrying out the charging of constant current constant voltage until defined voltage.Next, being carried out for the battery after charging permanent The electric discharge of electric current constant voltage.By this from electric discharge is charged to as 1 circulation, repeatedly until X circulation.

Discharge capacity sustainment rate after calculating X circulation by following formula (5).

Formula (5) r=C_X/C_1st×100

Wherein, in above-mentioned formula (5), r refers to the discharge capacity sustainment rate (%) after X circulation, C_XRefer to X circulation Discharge capacity (mAh), C_1stRefer to the discharge capacity (mAh) of the 1st circulation.To the value of X, there is no particular restriction, due in cathode The unevenness of conductive material be easy to have an impact the discharge capacity sustainment rate at initial stage, therefore X can be for 10 hereinafter, can be 5.