WO2015118833A1 - Batterie secondaire à électrolyte non aqueux - Google Patents

Batterie secondaire à électrolyte non aqueux Download PDF

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WO2015118833A1
WO2015118833A1 PCT/JP2015/000340 JP2015000340W WO2015118833A1 WO 2015118833 A1 WO2015118833 A1 WO 2015118833A1 JP 2015000340 W JP2015000340 W JP 2015000340W WO 2015118833 A1 WO2015118833 A1 WO 2015118833A1
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negative electrode
aqueous electrolyte
graphite
particles
secondary battery
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PCT/JP2015/000340
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English (en)
Japanese (ja)
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泰典 渡邉
泰三 砂野
山本　諭
安展 岩見
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三洋電機株式会社
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0566—Liquid materials
    • H01M10/0569—Liquid materials characterised by the solvents
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/364—Composites as mixtures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/386—Silicon or alloys based on silicon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/621—Binders
    • H01M4/622—Binders being polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention relates to a non-aqueous electrolyte secondary battery.
  • Metal materials that can be alloyed with lithium such as silicon, germanium, tin and zinc instead of carbonaceous materials such as graphite as negative electrode active materials, and these metals for higher energy density and higher output of lithium ion batteries
  • silicon, germanium, tin and zinc instead of carbonaceous materials such as graphite as negative electrode active materials, and these metals for higher energy density and higher output of lithium ion batteries
  • carbonaceous materials such as graphite
  • Patent Document 1 proposes a composite of a material containing Si and O as a constituent element and a carbon material, and a negative electrode for a nonaqueous electrolyte secondary battery containing a graphitic carbon material as a negative electrode active material. .
  • the non-aqueous electrolyte secondary battery of Patent Document 1 has problems in that the cycle characteristics are not sufficiently improved and gas is generated during high-temperature storage.
  • a non-aqueous electrolyte secondary battery includes a positive electrode, a negative electrode, and a non-aqueous electrolyte
  • the negative electrode includes a negative electrode current collector and a negative electrode mixture layer
  • the negative electrode includes particles containing silicon and graphite particles whose surfaces are coated with a material containing cellulose.
  • the non-aqueous electrolyte includes a cyclic carbonate and a chain carbonate.
  • the cyclic carbonate is propylene. With carbonate.
  • the non-aqueous electrolyte secondary battery of the present invention has improved cycle characteristics and suppresses gas generation during high-temperature storage.
  • FIG. 2 is a schematic cross-sectional view along the line AA in FIG. 1. It is sectional drawing which shows the negative electrode which is an example of embodiment of this invention.
  • a nonaqueous electrolyte secondary battery which is an example of an embodiment includes a positive electrode, a negative electrode, and a nonaqueous electrolyte containing a nonaqueous solvent.
  • a separator is preferably provided between the positive electrode and the negative electrode.
  • As an example of the structure of the nonaqueous electrolyte secondary battery there is a structure in which an electrode body in which a positive electrode and a negative electrode are wound via a separator, and a nonaqueous electrolyte are housed in an exterior body.
  • other types of electrode bodies such as a stacked electrode body in which a positive electrode and a negative electrode are stacked via a separator may be applied.
  • the nonaqueous electrolyte secondary battery may have any form such as a cylindrical type, a square type, a coin type, a button type, and a laminate type.
  • the specific structure of the nonaqueous electrolyte secondary battery 11 is such that the positive electrode 1 and the negative electrode 2 are wound so as to face each other with a separator 3 therebetween.
  • a flat electrode body composed of the positive and negative electrodes 1 and 2 and the separator 3 is impregnated with a non-aqueous electrolyte.
  • a positive electrode current collecting tab 4 and a negative electrode current collecting tab 5 are connected to the positive electrode 1 and the negative electrode 2, respectively, so that a secondary battery can be charged and discharged.
  • the said electrode body is arrange
  • the positive electrode is preferably composed of a positive electrode current collector and a positive electrode active material layer formed on the positive electrode current collector.
  • a positive electrode current collector for example, a conductive thin film, particularly a metal foil or alloy foil that is stable in the potential range of the positive electrode such as aluminum, or a film having a metal surface layer such as aluminum is used.
  • the positive electrode active material layer preferably contains a conductive material and a binder in addition to the positive electrode active material.
  • the positive electrode active material includes an oxide including lithium and a metal element M, and the metal element M includes at least one selected from the group including cobalt and nickel.
  • Preferred is a lithium-containing transition metal oxide.
  • the lithium-containing transition metal oxide may contain non-transition metal elements such as Mg and Al. Specific examples include lithium-containing transition metal oxides such as lithium cobaltate, Ni—Co—Mn, Ni—Mn—Al, and Ni—Co—Al. These positive electrode active materials may be used alone or in combination of two or more.
  • the negative electrode 2 preferably includes a negative electrode current collector 21 and a negative electrode mixture layer 22 formed on the negative electrode current collector 21.
  • a conductive thin film particularly a metal foil or alloy foil that is stable in the potential range of the negative electrode such as copper, or a film having a metal surface layer such as copper is used.
  • the negative electrode mixture layer preferably contains a thickener and a binder in addition to the negative electrode active material.
  • the thickener it is preferable to use carboxymethylcellulose ammonium salt, ruboxymethylcellulose sodium salt, or the like.
  • the binder styrene-butadiene rubber (SBR), polyimide, or the like is preferably used.
  • the negative electrode active material 23 includes a negative electrode active material 23a which is a particle containing silicon and a negative electrode active material 23b which is a particle containing graphite.
  • the surface of graphite is preferably coated with a material containing cellulose.
  • a material containing cellulose By covering the surface with a material containing cellulose, the insertion of propylene carbonate between the graphite layers is suppressed, and the deterioration of the graphite due to the cycle is suppressed. Further, the adsorption of the thickener and the binder is promoted, the adhesion between the negative electrode current collector 21 and the negative electrode mixture layer 22 is improved, and the current collecting property is improved. That the surface of graphite is covered with a material containing cellulose includes the case where a material containing cellulose is adsorbed on the graphite surface.
  • the surface of graphite being coated with a material containing cellulose means that the outermost surface of graphite is coated with a material containing cellulose.
  • the material containing cellulose is preferably a water-soluble cellulose derivative having C 6 H 10 O 5 as a basic structure, and is preferably carboxyalkyl cellulose, hydroxyalkyl cellulose, or alkoxy cellulose. Examples thereof include carboxymethyl cellulose, methyl cellulose, hydroxyethyl cellulose, and hydroxypropyl cellulose. Of these, carboxymethylcellulose is preferable.
  • covers the graphite surface is not restricted to the material containing cellulose, It is possible to use as long as it is a polymer material which has ion permeability and does not react with lithium.
  • Polymer materials that do not react with lithium are starch derivatives having a basic structure of C 6 H 10 O 5 , such as starch acetate, phosphate starch, carboxymethyl starch, hydroxyethyl starch, and the like, C 6 H 10 O Viscous polysaccharides such as pullulan and dextrin having a basic structure of 5 , water-soluble acrylic resin, water-soluble epoxy resin, water-soluble polyester resin, water-soluble polyamide resin, vinylidene fluoride / hexafluoropropylene copolymer and polyvinylidene fluoride, Is mentioned.
  • the material containing cellulose relative to graphite is preferably 0.1 to 2.0% by mass, and more preferably 0.3 to 1.5% by mass. If the mass ratio is too small, the amount of gas generated during high-temperature storage tends to increase, and if the mass ratio is too large, the resistance of the negative electrode mixture layer tends to increase and cycle characteristics tend to decrease.
  • the surface of graphite 100% or less than 90% of a material containing cellulose, preferably, it is preferably covered approximately 100%. If the coverage is too small, the gas generated during high-temperature storage tends to increase. Note that the surface of graphite is covered with a material containing cellulose when the particle cross section is observed by SEM, the surface of the graphite is covered with a film made of a material containing cellulose at least 50 nm thick. It is.
  • Examples of the method of coating the graphite surface with a material containing cellulose include a spray dryer method and a stirring-drying method.
  • the negative electrode active material 23a preferably contains SiO x (preferably 0.5 ⁇ X ⁇ 1.5), Si or Si alloy.
  • Si alloys include solid solutions of silicon and one or more other elements, intermetallic compounds of silicon and one or more other elements, and eutectic alloys of silicon and one or more other elements. It is done. Among these, it is preferable to use SiO x particles.
  • the surface of the SiO x particles is covered with carbon at 50% or more and 100% or less, preferably 100%.
  • the SiO X particle surface is coated with carbon, when the particle cross sections were observed by SEM, SiO X particle surfaces, is that covered by at least 1nm thick or more carbon coating.
  • the SiO x surface is covered with carbon by 100%.
  • the carbon coating is preferably 1 to 200 nm, more preferably 5 to 100 nm. If the thickness of the carbon film becomes too thin, the conductivity decreases. On the other hand, if the thickness of the carbon film becomes too thick, the diffusion of Li + into SiO x tends to be inhibited and the capacity tends to decrease.
  • the carbon coating is preferably composed of amorphous carbon.
  • amorphous carbon By using amorphous carbon, it is possible to form a good and uniform film on the surface of SiO x , and it is possible to further promote the diffusion of Li + into SiO x .
  • the amorphous carbon film is produced, for example, by immersing SiO X particles to be coated in a solution such as coal tar and then performing a high temperature treatment under an inert atmosphere.
  • the heat treatment temperature at this time is preferably about 900 ° C. to 1100 ° C.
  • the surface of the negative electrode active material 23a may be coated with a material containing cellulose.
  • a material containing cellulose By covering the reaction active part of the surface of the particle
  • the negative electrode active material 23a is SiO x particles, it is preferable that the surface of the amorphous carbon coating on the surface of the SiO x particles is coated with a material containing cellulose.
  • the average particle diameter of the negative electrode active material particles 23a is preferably 1 to 15 ⁇ m and more preferably 4 to 10 ⁇ m from the viewpoint of increasing the capacity. If the particle size of the negative electrode active material particles 23a becomes too small, the particle surface area increases, and therefore the reaction amount with the electrolyte tends to increase and the capacity tends to decrease. On the other hand, if the particle size becomes too large, Li + cannot diffuse to the vicinity of the center of the particle, and the capacity tends to decrease and the load characteristics tend to deteriorate.
  • the average particle diameter of the negative electrode active material particles 23b is preferably 15 to 25 ⁇ m.
  • the mass ratio between the particles containing silicon and the graphite whose surface is coated with a material containing cellulose is preferably 1:99 to 50:50, more preferably 3:97 to 20:80. If mass ratio is in the said range, it will become easy to make high capacity
  • the mass of the thickener in the negative electrode mixture layer is preferably larger than the mass of the binder.
  • the mass ratio of the thickener to the binder is 98: 2 to less than 50:50, more preferably 80:20 to 60:40.
  • Non-aqueous electrolyte examples include LiClO 4 , LiBF 4 , LiPF 6 , LiAlCl 4 , LiSbF 6 , LiSCN, LiCF 3 SO 3 , LiCF 3 CO 2 , LiAsF 6 , LiB 10 Cl 10 , lower aliphatic carboxylic acid.
  • Lithium, LiCl, LiBr, Lii, chloroborane lithium, borates, imide salts, and the like can be used.
  • LiPF 6 is preferably used from the viewpoints of ion conductivity and electrochemical stability.
  • One electrolyte salt may be used alone, or two or more electrolyte salts may be used in combination. These electrolyte salts are preferably contained at a ratio of 0.8 to 1.5 mol with respect to 1 L of the nonaqueous electrolyte.
  • cyclic carbonates and chain carbonates are used as the solvent for the nonaqueous electrolyte.
  • cyclic carbonate examples include propylene carbonate (PC), ethylene carbonate (EC), and fluoroethylene carbonate (FEC).
  • chain carbonate examples include diethyl carbonate (DEC), ethyl methyl carbonate (EMC), and dimethyl carbonate (DMC).
  • the cyclic carbonate preferably contains propylene carbonate.
  • propylene carbonate When propylene carbonate is used, the reaction between the material containing cellulose and the electrolytic solution is less likely to occur during charge storage, and gas generation is suppressed.
  • Propylene carbonate is preferably contained in an amount of 1 to 40% by volume, more preferably 1 to 30% by volume, based on the entire non-aqueous solvent. If it is less than 1% by volume, the effect of suppressing gas generation tends to be reduced. When it exceeds 40 volume%, the viscosity of electrolyte solution will become high and there exists a tendency for charging / discharging capacity to fall.
  • the cyclic carbonate is preferably contained in an amount of 1 to 50% by volume based on the entire non-aqueous solvent. If the amount is less than 1% by volume, oxidative decomposition of the chain carbonate ester is likely to occur, which causes an increase in the generated gas. If it exceeds 50% by volume, the viscosity of the electrolytic solution tends to increase, and the charge / discharge capacity tends to decrease.
  • the ratio of propylene carbonate with respect to the cyclic carbonate in the non-aqueous solvent is preferably 1 to 100% by volume, more preferably 10 to 50% by volume.
  • the volume ratio of the cyclic carbonate and the chain carbonate in the non-aqueous solvent is preferably 1:90 to 70:30, more preferably 50:50.
  • cyclic carboxylic acid ester chain
  • the cyclic carboxylic acid ester include ⁇ -butyrolactone (GBL) and ⁇ -valerolactone (GVL).
  • chain carboxylic acid esters include methyl propionate (MP), fluoromethyl propionate (FMP), and methyl trimethyl acetate (MTMA).
  • fluoroarene include monofluorobenzene (FB).
  • separator a porous sheet having ion permeability and insulating properties is used.
  • the porous sheet include a microporous thin film, a woven fabric, and a nonwoven fabric.
  • material of the separator polyolefin such as polyethylene and polypropylene is suitable.
  • Example 1> (Preparation of positive electrode) Weigh and mix lithium cobaltate, acetylene black (manufactured by Denki Kagaku Kogyo Co., Ltd., HS100) and polyvinylidene fluoride (PVdF) so that the mass ratio is 95.0: 2.5: 2.5. Then, N-methyl-2-pyrrolidone (NMP) as a dispersion medium was added. Next, this was stirred using a mixer (Primix Co., Ltd., TK Hibismix) to prepare a positive electrode slurry.
  • NMP N-methyl-2-pyrrolidone
  • this positive electrode slurry is applied to both surfaces of a positive electrode current collector made of aluminum foil, dried, and then rolled by a rolling roller to produce a positive electrode in which a positive electrode mixture layer is formed on both surfaces of the positive electrode current collector. did.
  • the filling density in the positive electrode mixture layer was 3.60 g / ml.
  • the negative electrode active material, carboxymethyl cellulose, and styrene butadiene rubber were mixed at a mass ratio of 98: 1.5: 0.5 with a suitable amount of water with a mixer to prepare a negative electrode mixture slurry.
  • This negative electrode mixture slurry was applied to both sides of a negative electrode current collector sheet made of a copper foil having a thickness of 10 ⁇ m, dried and rolled.
  • the packing density of the negative electrode active material layer was 1.60 g / mL.
  • Ethylene carbonate (EC), propylene carbonate (PC), diethyl carbonate (DEC), monofluorobenzene (FB), and methyltrimethylacetate (MTMA) with a volume ratio of 30: 20: 40: 5: 5 1.2 mol / liter of lithium hexafluorophosphate (LiPF 6 ) is added to the mixed solvent, and 1% by volume each of vinylene carbonate (VC) and fluoroethylene carbonate (FEC) is added.
  • LiPF 6 lithium hexafluorophosphate
  • VC vinylene carbonate
  • FEC fluoroethylene carbonate
  • a tab was attached to each of the electrodes, and the positive electrode and the negative electrode were wound in a spiral shape through a separator so that the tab was positioned on the outermost periphery, thereby preparing a wound electrode body.
  • the electrode body is inserted into an exterior body made of an aluminum laminate sheet and vacuum-dried at 105 ° C. for 2 hours, and then the non-aqueous electrolyte is injected, and the opening of the exterior body is sealed to prepare the battery A1.
  • the design capacity of the battery A1 is 800 mAh.
  • Capacity maintenance rate (%) at the 100th cycle (discharge capacity at the 100th cycle / discharge capacity at the first cycle) ⁇ 100 (2)
  • the battery after the first charge / discharge is charged at a constant current of 1.0 it (800 mA) until the battery voltage becomes 4.2 V, and then the current value becomes 0.05 it (40 mA) at a voltage of 4.2 V. After performing constant voltage charging, it was stored at 60 ° C. for 2 days.
  • Battery swelling rate (%) ((Battery thickness after storage ⁇ Battery thickness before storage) / Battery thickness before storage) ⁇ 100 (3) The thickness of each battery was measured using a micrometer.
  • coated graphite particles When PC is not used for the cyclic carbonate in the non-aqueous solvent, the reaction between the material containing cellulose and the electrolytic solution is likely to occur during charge storage, and it is considered that the swelling of the battery due to gas generation increased.
  • CMC in the negative electrode mixture is easily adsorbed by graphite having the film containing cellulose. Therefore, in the negative electrode mixture, CMC is diffused as the graphite diffuses. Is easily diffused. Then, the diffused CMC is adsorbed by SiO x which is more easily adsorbed by CMC than graphite.
  • the charge potential differs between graphite and SiO x , so that selective charge / discharge to the SiO x is performed, in the cell A2 with the graphite particles and the SiO X particles as a negative electrode active material, since the charging potential of the SiO X is in the CMC coated-adsorption polarization increases it is close to graphite, selective charging of the SiO X It is thought that the discharge was suppressed. As described above, since the uneven charge / discharge reaction is alleviated, the suppression of the deterioration of the SiO x particles is one factor that did not decrease the capacity retention rate.
  • the thickener and the binder are easily adsorbed, the adhesion and the flexibility of the electrode plate are improved, and the destruction of the electrode plate structure due to charge / discharge is suppressed. This is also cited as one factor that did not decrease the capacity maintenance rate.
  • CMC When CMC is contained as a binder in the negative electrode mixture layer, CMC exists around the graphite particles without using the coated graphite particles. However, in this case, since a sufficient amount of CMC is not coated on the surface of graphite, it is considered that there are no effects such as suppression of deterioration of graphite particles and relaxation of non-uniform charging as described above.
  • the FB and MTMA used as the solvent for the battery A1 are used as regulators for the electrolyte viscosity equal to those of the batteries B1 and B2, and do not affect the capacity retention rate and the swelling rate.
  • a battery A2 was produced in the same manner as the battery A1, except that the negative electrode active material, carboxymethyl cellulose, and styrene butadiene rubber were mixed at a mass ratio of 98: 1: 1.
  • the swelling rate during high-temperature storage is particularly reduced when the thickener is contained in the negative electrode mixture in a larger amount than the binder.
  • the thickener is contained in a larger amount than the binder, a good pseudo film is easily formed on the surface of the coated graphite particles and the particles containing Si, and the decomposition reaction of the electrolytic solution due to the reaction between the active material and the electrolytic solution It is thought that it became difficult to occur.

Abstract

Selon l'invention, la génération de gaz lors d'une conservation à haute température d'une batterie secondaire à électrolyte non aqueux, est inhibée. La batterie secondaire à électrolyte non aqueux de l'invention, est équipée d'une électrode positive, d'une électrode négative et d'un électrolyte non aqueux. Ladite électrode négative est équipée d'un collecteur d'électrode négative et d'une couche de mélange d'électrode négative, ladite couche de mélange d'électrode négative étant à son tour équipée de particules contenant un silicium, et de particules de graphite dont la surface est revêtue d'un matériau contenant une cellulose. Ledit électrolyte non aqueux est équipé d'un ester de carbonate cyclique et d'un ester de carbonate à chaîne, ledit ester de carbonate cyclique étant à son tour équipé d'un carbonate de propylène. Ladite couche de mélange d'électrode négative est équipée d'un agent épaississant et d'un liant. De préférence, la quantité d'agent épaississant, est supérieure à celle de liant.
PCT/JP2015/000340 2014-02-04 2015-01-27 Batterie secondaire à électrolyte non aqueux WO2015118833A1 (fr)

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