阅读说明：本技术 负极和用于制备负极的方法 (Negative electrode and method for producing a negative electrode ) 是由 李秀民 申善英 李秀娟 金银卿 于 2017-10-26 设计创作，主要内容包括：本发明涉及负极和用于制备负极的方法。所述负极包含：集电器；和布置在所述集电器上的负极活性材料层,其中所述负极活性材料层包含第一粒子、第二粒子和第三粒子；所述第一粒子包含含有人造石墨的第一核；和布置在所述第一核上且含有所述人造石墨的氧化物的第一壳；所述第二粒子为通过所述粒形分析仪测量的球度为0.70至0.92的人造石墨；所述第三粒子包含含有天然石墨的第二核；和布置在所述第二核上且包含所述天然石墨的氧化物的第二壳,其中所述第一粒子、所述第二粒子和所述第三粒子的重量比为10～30:40～80:10～30。所述负极能够改善负极活性材料层和集电器之间的粘附强度。(The invention relates to an anode and a method for producing an anode. The negative electrode includes: a current collector; and an anode active material layer disposed on the current collector, wherein the anode active material layer includes first particles, second particles, and third particles; the first particles comprise a first core comprising artificial graphite; and a first shell disposed on the first core and containing an oxide of the artificial graphite; the second particles are artificial graphite having a sphericity of 0.70 to 0.92 as measured by the particle shape analyzer; the third particles comprise a second core comprising natural graphite; and a second shell disposed on the second core and comprising an oxide of the natural graphite, wherein a weight ratio of the first particles, the second particles, and the third particles is 10-30: 40-80: 10-30. The anode can improve adhesion strength between an anode active material layer and a current collector.)

1. An anode, comprising:

a current collector; and

a negative electrode active material layer disposed on the current collector,

wherein the anode active material layer includes first particles, second particles, and third particles;

the first particles comprise a first core comprising artificial graphite; and a first shell disposed on the first core and containing an oxide of the artificial graphite, the first particle having a sphericity of 0.94 to 0.98 as measured by a particle shape analyzer;

the second particles are artificial graphite having a sphericity of 0.70 to 0.92 as measured by the particle shape analyzer;

the third particles comprise a second core comprising natural graphite; and a second shell disposed on the second core and comprising an oxide of the natural graphite, and having a sphericity of 0.94 to 0.98 as measured by the particle shape analyzer,

wherein the weight ratio of the first particles to the second particles to the third particles is 10-30: 40-80: 10-30.

2. The anode of claim 1, wherein the first particles have an average particle diameter D of 10 to 25 μm₅₀。

3. The negative electrode according to claim 1, wherein the first core has an average particle diameter D of 10 μm to 20 μm₅₀。

4. The anode of claim 1, wherein the first shell has a thickness of 1nm to 200 nm.

5. The anode of claim 1, wherein the first particles have 0.95g/cm³To 1.3g/cm³The tap density of (1).

6. The anode of claim 1, wherein the second particles have an average particle diameter D of 10 to 25 μm₅₀。

7. The anode according to claim 1, wherein an oxygen atom content is 1200mg/kg to 2500mg/kg with respect to a total weight of the first particles.

8. The anode according to claim 1, wherein the third particles have an average particle diameter D of 7 μm to 25 μm₅₀。

9. The negative electrode according to claim 1, wherein the second core has an average particle diameter D of 5 μm to 25 μm₅₀。

10. The anode of claim 1, wherein the second shell has a thickness of 1nm to 200 nm.

11. The anode of claim 1, wherein the third particles have 1.0g/cm³To 1.2g/cm³The tap density of (1).

12. A method for preparing an anode, comprising:

preparing anode slurry; and

coating the anode slurry on a current collector, and then drying the resultant,

wherein the anode slurry comprises first particles, second particles, and third particles;

the first particles comprise a first core comprising artificial graphite; and a first shell disposed on the first core and comprising an oxide of the artificial graphite, the first particle having a sphericity of 0.94 to 0.98 as measured by a particle shape analyzer;

the second particles are artificial graphite having a sphericity of 0.70 to 0.92 as measured by the particle shape analyzer;

the third particles comprise a second core comprising natural graphite; and a second shell disposed on the second core and comprising an oxide of the natural graphite, and having a sphericity of 0.94 to 0.98 as measured by the particle shape analyzer,

wherein the weight ratio of the first particles to the second particles to the third particles is 10-30: 40-80: 10-30.

Technical Field

The present invention relates to an anode and a method for preparing the anode, specifically, the anode includes first particles having a sphericity of 0.94 to 0.98 and second particles having a sphericity of 0.70 to 0.92.

Background

As the use of fossil fuels has rapidly increased, the demand for the use of alternative energy or clean energy has increased, and the field most actively studied for this is the field of power generation and storage using electrochemical reactions.

Typical examples of electrochemical devices using such electrochemical energy at present may include secondary batteries, and the application range tends to be further expanded. As the technology develops and the demand for portable devices such as portable computers, portable phones, or cameras has recently increased, the demand for secondary batteries as an energy source, among which lithium secondary batteries having high energy density, i.e., high capacity, have been widely studied, commercialized, and widely used.

A secondary battery is generally formed with a positive electrode, a negative electrode, an electrolyte, and a separator. Lithium ions coming out of the positive electrode active material by the first charge are intercalated into the negative electrode active material such as carbon particles and deintercalated again at the time of discharge, and it becomes possible to charge and discharge because the lithium ions function to transfer energy while moving back and forth between the two electrodes. The electrode includes a current collector and an active material layer, and a binding agent such as a binder is generally used to increase the adhesive strength between the active material and the current collector.

In order to further increase the adhesive strength, techniques of adding a separate additive to the electrode paste or increasing the binder ratio have been introduced in the prior art. However, when the additive is added or the content of the binder is increased, the content of the active material particles is decreased, resulting in a problem of decreasing the capacity.

Therefore, it is required to develop an electrode capable of securing adhesive strength between an active material and a current collector while maintaining high capacity of a battery.

[ Prior art documents ]

(patent document)

(patent document 1) Korean patent application laid-open No. 10-2004-0053492

Disclosure of Invention

Technical problem

An aspect of the present invention provides an anode capable of improving adhesion strength (electrode adhesion strength) between an anode active material layer and a current collector, and a method for preparing the anode.

Technical scheme

According to an aspect of the present invention, there is provided an anode comprising a current collector and an anode active material layer disposed on the current collector, wherein the anode active material layer comprises first particles comprising a first core comprising artificial graphite and second particles; and a first shell disposed on the first core and comprising an oxide of the artificial graphite, the first particles having a sphericity of 0.94 to 0.98 as measured by a particle shape analyzer, the second particles being the artificial graphite having a sphericity of 0.70 to 0.92 as measured by a particle shape analyzer, and the first particles and the second particles being in a weight ratio of 1:1 to 1: 9.

According to another aspect of the present invention, there is provided a method for preparing an anode, the method including: preparing anode slurry (step 1); and coating the anode slurry on a current collector and then drying the resultant (step 2), wherein the anode slurry comprises first particles comprising a first core comprising artificial graphite and second particles; and a first shell disposed on the first core and comprising an oxide of the artificial graphite, the first particles having a sphericity of 0.94 to 0.98 as measured by a particle shape analyzer, the second particles being artificial graphite having a sphericity of 0.70 to 0.92 as measured by the particle shape analyzer, and the first particles and the second particles being in a weight ratio of 1:1 to 1: 9.

Advantageous effects

In the anode according to one embodiment of the present invention, by using the first particles having a relatively high sphericity and a high oxygen content and the second particles having a relatively low sphericity at an appropriate weight ratio, the particles can be smoothly accumulated in the anode active material layer, and the electrode adhesion strength can be improved. Therefore, the particles of the anode active material layer are prevented from falling off from the current collector, with the result that the electrode preparation process is easily performed and the performance of the manufactured battery can be improved.

Detailed Description

Hereinafter, the present invention will be described in more detail to explain the present invention.

The terms or words used in the present specification and claims should not be construed as limited to general or dictionary meanings, but interpreted as meanings and concepts corresponding to technical ideas of the present disclosure on the basis of the principle that the inventor can appropriately define the concept of the terms in order to describe the invention in the best possible manner.

The terms used in the present specification are used only to describe exemplary embodiments, and are not intended to limit the present invention. As used herein, the singular forms also include the plural forms unless the context clearly dictates otherwise.

In this specification, terms such as "comprising," "setting" or "having" indicate the presence of stated features, numbers, steps, constituents or combinations thereof, and should be interpreted as not excluding the possibility of the presence or addition of one or more other features, numbers, steps, constituents or combinations thereof.

An anode according to one embodiment of the present invention includes a current collector and an anode active material layer disposed on the current collector, wherein the anode active material layer includes first particles including a first core including artificial graphite and second particles; and a first shell disposed on the first core and containing an oxide of the artificial graphite, the first particles having a sphericity of 0.94 to 0.98 as measured by a particle shape analyzer, the second particles being artificial graphite having a sphericity of 0.70 to 0.92 as measured by the particle shape analyzer, and the first particles and the second particles being in a weight ratio of 1:1 to 1: 9.

The first particle may include a first core and a first shell.

The first core may be artificial graphite. The artificial graphite has excellent lithium absorption capacity, and when the first core is the artificial graphite, the charge and discharge characteristics of the battery can be improved.

The first core may have an average particle diameter (D) of 10 to 20 μm, specifically 14 to 18 μm₅₀). When the first core has an average particle diameter (D) of less than 10 μm₅₀) When the amount of the negative electrode active material layer is increased, a side reaction between the liquid electrolyte and the negative electrode active material layer is increased, causing a problem of lowering the adhesion strength of the electrode due to an increase in the specific surface area of the negative electrode active material layer. Further, the average particle diameter (D)₅₀) The first core larger than 20 μm has a problem of lowering the output performance of the anode.

With respect to the average particle diameter (D) of the first core₅₀) Average particle diameter (D) in the present specification₅₀) May be defined as the particle size at 50% basis of the particle size distribution. The average particle diameter (D) can be measured, for example, using a laser diffraction method₅₀). Laser diffraction methods can typically measure particle sizes from the submicron range to several mm and can obtain highly reproducible and high resolution results.

The first shell may be disposed on the first core. In particular, the first shell may cover a part or all of the surface of the first core.

The first shell may comprise an oxide of artificial graphite. The oxide of the artificial graphite may be a compound resulting from oxidation of the artificial graphite, and the oxygen content of the oxide of the artificial graphite may be higher than that of the artificial graphite.

The first shell may have a thickness of 1nm to 200nm, specifically 20nm to 100 nm. The first shell having a thickness of less than 1nm has a problem of low adhesion strength of the electrode. In addition, the first case having a thickness of more than 200nm has a problem of degradation of battery performance due to an excessive increase in resistance.

Average particle diameter (D) of first core₅₀) And the thickness of the first shell may be measured using a Transmission Electron Microscope (TEM), however, the measurement is not limited thereto.

The sphericity of the first particles measured by a particle shape analyzer may be 0.94 to 0.98, specifically 0.95 to 0.96. Sphericity may refer to the major axis versus the minor axis of the first particle. Sphericity can be measured by a particle analyzer (QICPIC-LIXELL, Simpatec Gmbh). Specifically, after the sphericity cumulative distribution of the first particles is obtained by the particle shape analyzer, the sphericity corresponding to 50% of the distribution ratio from the particles having a large sphericity may be determined as the sphericity of the first particles. The measurement method may be the same as the method of measuring the sphericity of the second particle and the sphericity of the third particle described below.

The sphericity may be obtained from a spheroidizing process in the preparation process of the first particles. The first particles having a sphericity of less than 0.94 may cause a problem of low adhesion strength of the electrode due to the excessively curved surface of the first particles. In addition, the first particles having a sphericity of more than 0.98 may cause a problem of lowering the production yield because a large amount of the first particles is required to obtain a high sphericity.

The first particles may have an average particle diameter (D) of 10 to 25 μm, specifically 15 to 20 μm₅₀). When the average particle diameter (D) of the first particles₅₀) Less than 10 μm, side reactions between the liquid electrolyte and the anode active material layer increase, and are due to the anode active materialThe specific surface area of the material layer increases and a problem of a decrease in the adhesive strength of the electrode may occur. Further, the average particle diameter (D)₅₀) The first particles larger than 25 μm may cause a problem of lowering the output performance of the anode.

The first particles may have a density of 0.95g/cm³To 1.3g/cm³Specifically 1.0g/cm³To 1.2g/cm³The tap density of (1). Tap density of less than 0.95g/cm³May cause a problem of low adhesion strength of the electrode due to the excessively curved surface of the first particles. In addition, the tap density is more than 1.3g/cm³May cause a problem of lowering the production yield because a large amount of the first particles is required to obtain a high tap density. The tap density can be obtained, for example, as follows: 40g of the first particles were introduced into a 100ml cylinder and the powder bulk density was measured after 1000 taps. However, the method is not limited thereto.

The oxygen atom content of the first particles may be 1200mg/kg to 2500mg/kg, specifically 1500mg/kg to 2000mg/kg, relative to the total weight. An oxygen atom content of less than 1200mg/kg may cause a problem of low adhesion strength of the electrode. In addition, an oxygen atom content of more than 2500mg/kg may cause a problem of degradation of battery performance due to an increase in electrical resistance. The oxygen atom content can be measured using an elemental analysis method, and specifically, can be measured by an oxynitridosiometer or a TPO-MS apparatus. However, the method is not limited thereto.

The second particles may be artificial graphite. The artificial graphite has excellent lithium absorption capacity, and when the second particles are artificial graphite, the charge and discharge performance of the battery can be improved.

Meanwhile, the sphericity of the second particles measured by the sphericity analyzer may be 0.70 to 0.92, specifically 0.8 to 0.9. The second particles having a sphericity of less than 0.70 may cause a problem of a decrease in electrode adhesive strength due to the second particles having a surface with an excessively curved shape, making it difficult to prepare an electrode. In addition, the second particles having a sphericity of more than 0.92 may cause a problem of lowering the production yield because a large amount of the second particles is required to obtain a high sphericity.

The second particles may have a particle size of 10 to 25 μm,Specifically, an average particle diameter (D) of 15 to 20 μm₅₀). When the average particle diameter (D) of the second particles₅₀) Less than 10 μm, side reactions between the liquid electrolyte and the anode active material layer increase, and a problem of a decrease in electrode adhesion strength may occur due to an increase in the specific surface area of the anode active material layer. Further, the average particle diameter (D)₅₀) The second particles larger than 25 μm may cause a problem of lowering the output performance of the negative electrode. Measuring the average particle diameter (D) of the second particles₅₀) And measuring the average particle diameter (D) of the first particles₅₀) The same method is used.

In the anode active material, the first particles and the second particles may have a weight ratio of 1:1 to 1:9, specifically 1:1 to 1:4, more specifically 1:1 to 1: 3. Satisfying the above weight ratio can improve the electrode adhesion strength.

Specifically, when the first particles or the second particles are excessively used in an amount other than the above weight ratio, too many voids are present in the anode active material layer by the respective morphologies of the first particles and the second particles. In addition, the accumulation between the first particles and the second particles is not smooth, which may cause a difference in adhesive strength between the particles in the anode active material layer, and a difference in adhesive strength between the anode active material layer and the current collector. On the other hand, when the first particles and the second particles are appropriately mixed and used as in the above-described weight ratio, the amounts of the first particles having a shape relatively closer to a sphere and the second particles having a relatively curved surface are controlled, voids in the anode active material layer are reduced, and the first particles and the second particles may exist in a form smoothly meshing with each other. As a result, the electrode adhesion strength can be improved.

The total weight of the first particles and the second particles may be 95 wt% to 99 wt%, specifically 97 wt% to 98 wt%, relative to the total weight of the anode active material layer.

In the negative electrode, the electrode adhesion strength may be 40gf/cm to 90gf/cm, specifically 44gf/cm to 65 gf/cm. Electrode adhesion strength can be measured using the following method. The negative electrode was punched to 10mm × 150mm and fixed on the center of a 26mm × 76mm glass slide using an adhesive tape, and 180-degree peel strength was measured while peeling the current collector using UTM. The electrode adhesion strength can be obtained from the average of the measured values by performing 5 or more measurements.

The negative active material layer may further include a conductive agent. The conductive agent is not particularly limited as long as it has conductivity without causing chemical changes to the corresponding battery, and examples thereof may include: graphite such as natural graphite or artificial graphite; carbon black-based materials such as carbon black, acetylene black, ketjen black, channel black, furnace black, lamp black, or thermal black; conductive fibers such as carbon fibers or metal fibers; conductive tubes such as carbon nanotubes; fluorocarbon powders, aluminum and metal powders such as nickel powders; conductive whiskers such as zinc oxide and potassium titanate; conductive metal oxides such as titanium oxide; conductive materials such as polyphenylene derivatives, and the like.

The negative active material layer may further include a binder. The binder may include at least any one selected from the group consisting of: polyvinylidene fluoride-hexafluoropropylene copolymer (PVDF-co-HFP), polyvinylidene fluoride, polyacrylonitrile, polymethyl methacrylate, polyvinyl alcohol, carboxymethyl cellulose (CMC), starch, hydroxypropyl cellulose, regenerated cellulose, polyvinylpyrrolidone, tetrafluoroethylene, polyethylene, polypropylene, polyacrylic acid, ethylene-propylene-diene monomer (EPDM), sulfonated EPDM, styrene-butadiene rubber (SBR), fluororubber, a polymer whose hydrogen is substituted with Li, Na, Ca, or the like, or various copolymers that may contain them.

An anode according to another embodiment of the present invention is similar to the anode of the above-described one embodiment, but differs from the above-described one example in that the anode active material layer may further include third particles. This difference will be described below.

The third particles may comprise a second core and a second shell.

The second core may be natural graphite. Natural graphite has a high lithium binding amount, and thus, when the second core is natural graphite, the battery capacity can be improved.

The second core may have an average particle diameter (D) of 5 to 25 μm, specifically 9 to 20 μm₅₀). When the average particle diameter (D) of the second core₅₀) When the particle diameter is less than 5 μm,side reactions between the liquid electrolyte and the anode active material layer increase, and a problem of a decrease in electrode adhesion strength may occur due to an increase in the specific surface area of the anode active material layer. Further, the average particle diameter (D)₅₀) The second core larger than 25 μm has a problem that the output performance of the negative electrode is lowered.

The second shell may be disposed on the second core. In particular, the second shell may cover a part or all of the surface of the second core.

The second shell may comprise an oxide of natural graphite. The oxide of natural graphite may be a compound resulting from oxidation of natural graphite, and the oxygen content of the oxide of natural graphite may be higher than that of artificial graphite.

The second shell may have a thickness of 1nm to 200nm, specifically 20nm to 100 nm. The second shell having a thickness of less than 1nm may have a problem that the electrode adhesion strength is excessively low. In addition, the second case having a thickness of more than 200nm has a problem of degradation of battery performance due to an excessive increase in resistance.

Meanwhile, the sphericity of the third particles measured by the particle shape analyzer may be 0.94 to 0.98, specifically 0.96 to 0.97. When the sphericity of the third particles is less than 0.94, the effect of improving the adhesion strength of the electrode may not be significant. In addition, the third particles having a sphericity of more than 0.98 may cause a problem of lowering the production yield because a large amount of the third particles is required to obtain a high sphericity.

The third particles may have an average particle diameter (D) of 7 to 25 μm, specifically 12 to 20 μm₅₀). When the average particle diameter (D) of the third particles₅₀) Less than 7 μm, side reactions between the liquid electrolyte and the anode active material layer increase, and a problem of a decrease in electrode adhesion strength may occur due to an increase in the specific surface area of the anode active material layer. Further, the average particle diameter (D)₅₀) The third particles larger than 25 μm may cause a problem of lowering the output performance of the negative electrode.

The third particles may have a density of 1.0g/cm³To 1.2g/cm³Specifically 1.05g/cm³To 1.15g/cm³The tap density of (1). Tap density of less than 1.0g/cm³Third particles due to third particlesMay cause a problem of poor adhesion strength of the electrode. In addition, the tap density is more than 1.2g/cm³May cause a problem of lowering the production yield because a large amount of the third particles is required to obtain a high tap density. The tap density may be measured using the same method as the method of measuring the tap density of the first particles.

The weight ratio of the first particles, the second particles, and the third particles may be 10 to 30:40 to 80:10 to 30, specifically 20 to 25:50 to 60:20 to 25. Satisfying the above weight ratio can further improve the electrode adhesion strength since the particles in the active material layer are smoothly accumulated.

A method for preparing an anode according to another embodiment of the present invention includes: preparing anode slurry (step 1); and coating the anode slurry on a current collector and then drying the resultant (step 2), wherein the anode slurry comprises first particles comprising a first core comprising artificial graphite and second particles; and a first shell disposed on the first core and comprising an oxide of the artificial graphite, the first particles having a sphericity of 0.94 to 0.98 as measured by a particle shape analyzer, the second particles being artificial graphite having a sphericity of 0.70 to 0.92 as measured by the particle shape analyzer, and the first particles and the second particles being in a weight ratio of 1:1 to 1: 9. Herein, the first particles and the second particles included in the anode slurry may be the same as the first particles and the second particles included in the anode active material layer described above.

Step 1 may include adding the first particles and the second particles to a solvent, and mixing the resultant (step 1-1). The solvent may be a solvent generally used in the art, and may be, specifically, distilled water. In step 1-1, a binder may be further added and mixed with the first particles and the second particles. Alternatively, in step 1-1, a conductive agent and a binder may be further added and mixed with the first particles and the second particles. The conductive agent and the binder may be the same as those that may be contained in the above-described anode active material layer.

The anode slurry may further include third particles. Specifically, in step 1-1, the third particles may be added to the solvent together with the first particles and the second particles and mixed. Herein, the third particles included in the anode slurry may be the same as the third particles included in the anode active material layer described above.

A secondary battery according to another embodiment of the present invention may include an anode, a cathode, a separator disposed between the cathode and the anode, and an electrolyte, and the anode may be the anode according to any one of the above embodiments.

A separator may be used without particular limitation as long as it separates the negative electrode and the positive electrode, provides a migration path of lithium ions, and is generally used as a separator in a secondary battery, and in particular, those having excellent liquid electrolyte moisture-containing ability while having low resistance to ion migration of an electrolyte are preferred. Specifically, a porous polymer film, such as one prepared from a polyolefin-based polymer, such as an ethylene homopolymer, a propylene homopolymer, an ethylene/butene copolymer, an ethylene/hexene copolymer, and an ethylene/methacrylate copolymer, or a laminated structure of two or more layers thereof, may be used. It is also possible to use a common porous nonwoven fabric such as a nonwoven fabric made of high-melting glass fibers, polyethylene terephthalate fibers, or the like. In addition, in order to secure heat resistance or mechanical strength, a coated separator including a ceramic component or a polymer material may also be used, and may be selectively used in a single layer or a multi-layer structure.

As the electrolyte, an organic-based liquid electrolyte, an inorganic-based liquid electrolyte, a solid polymer electrolyte, a gel-type polymer electrolyte, a solid inorganic electrolyte, a molten inorganic electrolyte, and the like, which can be used in manufacturing a lithium secondary battery, may be included, however, the electrolyte is not limited thereto.

Specifically, the electrolyte may include a non-aqueous organic solvent and a metal salt.

Examples of the non-aqueous organic solvent may include aprotic organic solvents such as N-methyl-2-pyrrolidone, propylene carbonate, ethylene carbonate, butylene carbonate, dimethyl carbonate, diethyl carbonate, γ -butyrolactone, 1, 2-dimethoxyethane, tetrahydrofuran, 2-methyltetrahydrofuran, dimethylsulfoxide, 1, 3-dioxolane, formamide, dimethylformamide, dioxolane, acetonitrile, nitromethane, methyl formate, methyl acetate, phosphoric acid triester, trimethoxymethane, dioxolane derivatives, sulfolane, methylsulfolane, 1, 3-dimethyl-2-imidazolidinone, propylene carbonate derivatives, tetrahydrofuran derivatives, ether, methyl propionate, or ethyl propionate.

In particular, among carbonate-based organic solvents, ethylene carbonate and propylene carbonate, which are cyclic carbonates, may be more preferably used because they are high-viscosity organic solvents and have high dielectric constants, thereby more advantageously dissociating lithium salts in the electrolyte. It is more preferable to mix a linear carbonate having a low viscosity and a low dielectric constant such as dimethyl carbonate and diethyl carbonate in an appropriate ratio to such a cyclic carbonate and use it because an electrolyte having a higher conductivity can be prepared.

As the metal salt, a lithium salt, which is a material to be favorably dissolved in the nonaqueous liquid electrolyte, may be used, and for example, one type selected from the group consisting of: f^-、Cl^-、I^-、NO₃ ^-、N(CN)₂ ^-、BF₄ ^-、ClO₄ ^-、PF₆ ^-、(CF₃)₂PF₄ ^-、(CF₃)₃PF₃ ^-、(CF₃)₄PF₂ ^-、(CF₃)₅PF^-、(CF₃)₆P^-、CF₃SO₃ ^-、CF₃CF₂SO₃ ^-、(CF₃SO₂)₂N^-、(FSO₂)₂N^-、CF₃CF₂(CF₃)₂CO^-、(CF₃SO₂)₂CH^-、(SF₅)₃C^-、(CF₃SO₂)₃C^-、CF₃(CF₂)₇SO₃ ^-、CF₃CO₂ ^-、CH₃CO₂ ^-、SCN^-And (CF)₃CF₂SO₂)₂N^-。

In order to improve the life performance of the battery, suppress the decrease in the capacity of the battery, improve the discharge capacity of the battery, etc., one or more types of additives, for example, halogenated alkylene carbonate compounds such as difluoroethylene carbonate, pyridine, triethyl phosphite, triethanolamine, cyclic ether, ethylenediamine, N-glyme, hexamethylphosphoric triamide, nitrobenzene derivatives, sulfur, quinoneimine dyes, N-substituted compounds, may be further included in the electrolyte in addition to the above-mentioned electrolyte componentsOxazolidinones, N-substituted imidazolines, ethylene glycol dialkyl ethers, ammonium salts, pyrroles, 2-methoxyethanol or aluminum trichloride.

According to another embodiment of the present invention, there are provided a battery module including the lithium secondary battery as a unit cell, and a battery pack including the same. The battery module and the battery pack include a secondary battery having high capacity, high rate determining performance, and cycle performance, and thus may be used as a power source for a middle-to large-sized device selected from the group consisting of: an electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, and an electrical storage system.

Hereinafter, preferred embodiments will be provided to illustrate the present invention, however, the embodiments are only for illustrative purposes, and it is apparent to those skilled in the art that various changes and modifications may be made within the scope and technical concept of the present disclosure and such changes and modifications also fall within the scope of the appended claims.

Examples and comparative examples

Preparation example 1: preparation of first particles

The average particle diameter (D)₅₀) 7 μm artificial graphite bonded to pitchAfter mixing the agents, the resultant was heat-treated at 3000 ℃ for 2 hours to prepare an average particle diameter (D)₅₀) Artificial graphite having a secondary particle structure of 17 μm. Thereafter, the artificial graphite is spheroidized using a rotary spheroidizing apparatus to prepare preliminary particles.

Subjecting the prepared particles to an oxygen atmosphere at 400 deg.C under a pressure of 0.1MPa and 60m³Oxidizing under a gas flow per hour to produce first particles comprising a first core and a first shell.

In the first particles prepared, the first cores had an average particle diameter (D) of 16.86 μm₅₀) The first shell has a thickness of 70 nm. Measuring the average particle diameter (D) of the first core using a particle size analyzer (PSD)₅₀) The thickness of the first shell was measured using a Transmission Electron Microscope (TEM). Further, the sphericity of the prepared first particles measured by a particle shape analyzer was 0.96.

Preparation example 2: preparation of the second particles

The average particle diameter (D)₅₀) After artificial graphite of 7 μm was mixed with a pitch binder, the resultant was heat-treated at 3000 ℃ for 2 hours to prepare an average particle diameter (D)₅₀) And second particles having a secondary particle structure of 19 μm. Further, the prepared second particles had a sphericity of 0.89 as measured by a particle shape analyzer.

Preparation example 3: preparation of third particles

The average particle diameter (D)₅₀) After mixing natural graphite of 7 μm with a pitch binder, the resultant was heat-treated at 3000 ℃ for 2 hours to prepare an average particle diameter (D)₅₀) Natural graphite having a secondary particle structure of 16 μm. Thereafter, the natural graphite is spheroidized using a rotary spheroidizing apparatus to prepare preliminary particles.

Subjecting the prepared particles to an oxygen atmosphere at 400 deg.C under a pressure of 0.1MPa and 60m³Oxidizing under a gas flow per hour to produce third particles comprising a second core and a second shell.

In the prepared third particles, the second core had an average particle diameter (D) of 15.80 μm₅₀) The second shell has a thickness of 100 nm. Measuring the average particle diameter (D) of the second core using a particle size analyzer (PSD)₅₀) The thickness of the second shell was measured using a Transmission Electron Microscope (TEM). Further, the sphericity of the prepared third particles measured by a particle shape analyzer was 0.97.

For each of the first, second, and third particles prepared in preparation examples 1 to 3, tap density and oxygen atom content were measured, and the results are shown in table 1 below. The respective measurement methods are as follows.

Tap density

The first, second and third particles were each introduced into a 100ml cylinder at 40g each and the powder bulk density was measured after tapping 1000 times.

Oxygen atom content

The oxygen atom content was measured for a 2mg sample of each of the first, second, and third particles using an ONH835 analyzer apparatus.

TABLE 1

Example 1: preparation of the negative electrode

Active material particles formed with 1g of the first particles prepared in preparation example 1 and 9g of the second particles prepared in preparation example 2, carbon black as a conductive agent, and carboxymethyl cellulose and Styrene Butadiene Rubber (SBR) as a binder were added to distilled water in a weight ratio of 95.3:1.0:1.2:2.5, and mixed to prepare negative electrode slurry having 45% of mixture solids. The slurry of the negative electrode was mixed at 260mg/25cm²Was coated on a copper current collector having a thickness of 20 μm, and the resultant was dried to prepare a preliminary electrode. In this context, the temperature of the circulating air is 70 ℃. Subsequently, the pre-electrode was rolled, dried in a vacuum oven at 130 ℃ for 12 hours, and then pressed to 1.4875cm²The coin cell size of (1) to prepare a negative electrode.

Example 2: preparation of the negative electrode

An anode was prepared in the same manner as in example 1 except that active material particles formed of 3g of the first particles prepared in preparation example 1 and 7g of the second particles prepared in preparation example 2 were used instead of the active material particles of example 1.

Example 3: preparation of the negative electrode

An anode was prepared in the same manner as in example 1 except that active material particles formed with 2g of the first particles prepared in preparation example 1, 6g of the second particles prepared in preparation example 2, and 2g of the third particles prepared in preparation example 3 were used instead of the active material particles in example 1.

Comparative example 1: preparation of the negative electrode

An anode was prepared in the same manner as in example 1, except that active material particles formed of only 10g of the first particles prepared in preparation example 1 were used instead of the active material particles of example 1.

Comparative example 2: preparation of the negative electrode

An anode was prepared in the same manner as in example 1 except that active material particles formed of only 10g of the second particles prepared in preparation example 2 were used instead of the active material particles of example 1.

Comparative example 3: preparation of the negative electrode

An anode was prepared in the same manner as in example 1, except that active material particles formed with 7g of the first particles prepared in preparation example 1 and 3g of the second particles prepared in preparation example 2 were used instead of the active material particles of example 1.

Comparative example 4: preparation of the negative electrode

An anode was prepared in the same manner as in example 1 except that active material particles formed with 0.2g of the first particles prepared in preparation example 1 and 9.8g of the second particles prepared in preparation example 2 were used instead of the active material particles of example 1.

Experimental example 1: evaluation of electrode adhesion Strength

For each of the anodes of examples 1 to 3 and comparative examples 1 to 4, the anode was punched to 10mm × 150mm and fixed at the center of a 26mm × 76mm glass slide using a tape, and 180 degree peel strength was measured while peeling the anode current collector using UTM. For evaluation, the peel strength was measured 5 times or more, and the average value was determined. The results are shown in table 2 below.

Experimental example 2: evaluation of cycle Performance

Each of the negative electrodes of examples 1 to 3 and comparative examples 1 to 4 was charged with a Constant Current (CC) of 0.8C at 25 ℃ up to 4.25V, and then charged with a Constant Voltage (CV) until the charging current became 0.005C (off current), which was used as the first charge. After that, the anode was left to stand for 20 minutes, and discharged to 2.5V with a Constant Current (CC) of 0.8C. This was repeated for 1 to 50 cycles to evaluate the capacity retention rate, and the results are shown in table 2 below.

The results of experimental examples 1 and 2 are shown in table 2 below.

TABLE 2

Based on the above results, it was seen that the negative electrodes of examples 1 and 2 using the first particles and the second particles at 1:9 and 1:2.33, respectively, and the negative electrode of example 3 using the first particles, the second particles, and the third particles at 1:3:1 were higher in electrode adhesion strength than the negative electrodes of comparative examples 1 to 4 satisfying the weight ratio outside the range of 1:1 to 1: 9. In addition, it was confirmed that the capacity retention rates of examples 1 to 3 were also higher than those of comparative examples 1 to 4.

Further, it was confirmed that example 3 including the third particles at an appropriate content has higher electrode adhesive strength and capacity retention rate compared to examples 1 and 2.