WO2011102453A1 - ポリマー二次電池およびその製造方法 - Google Patents
ポリマー二次電池およびその製造方法 Download PDFInfo
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- WO2011102453A1 WO2011102453A1 PCT/JP2011/053480 JP2011053480W WO2011102453A1 WO 2011102453 A1 WO2011102453 A1 WO 2011102453A1 JP 2011053480 W JP2011053480 W JP 2011053480W WO 2011102453 A1 WO2011102453 A1 WO 2011102453A1
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- 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
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- H—ELECTRICITY
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- 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
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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
- H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
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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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/044—Activating, forming or electrochemical attack of the supporting material
- H01M4/0445—Forming after manufacture of the electrode, e.g. first charge, cycling
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- 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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- 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
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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
- 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
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- H—ELECTRICITY
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- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H—ELECTRICITY
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- 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
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0085—Immobilising or gelification of electrolyte
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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
- 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
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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
- 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
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T29/00—Metal working
- Y10T29/49—Method of mechanical manufacture
- Y10T29/49002—Electrical device making
- Y10T29/49108—Electric battery cell making
- Y10T29/4911—Electric battery cell making including sealing
Definitions
- the present embodiment relates to a polymer secondary battery including a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, a gel electrolyte, and an exterior member that encloses the positive electrode, the negative electrode, the separator, and the gel electrolyte, and its manufacture. Regarding the method.
- Carbon such as graphite and hard carbon is usually used for the negative electrode active material of the lithium ion secondary battery.
- carbon can repeat the charge / discharge cycle satisfactorily, it cannot be expected that the capacity will increase significantly in the future because the capacity has already been improved to near the theoretical capacity.
- the theoretical capacity of a graphite negative electrode is 372 mAh / g
- the theoretical capacity of a silicon negative electrode is 4200 mAh / g
- the silicon negative electrode has a theoretical capacity about 10 times that of the graphite negative electrode.
- Patent Document 2 discloses a specific aprotic organic solvent. It has been proposed a method of suppressing decomposition of non-aqueous electrolyte and gas generation by containing.
- Patent Document 3 discloses an example in which a gel electrolyte is used as an electrolyte when silicon (oxide) is used as a negative electrode active material.
- Patent Document 4 using a gel electrolyte an active material layer made of a silicon material and a binder provided on a current collector is sintered at a high temperature for a long time (10 to 30 hours) in a non-oxidizing atmosphere.
- a negative electrode in which an active material layer is closely attached to a current collector, and a gel electrolyte is embedded in a columnar crack generated in the thickness direction of the active material layer by temporary charging and discharging.
- Patent Document 4 can be expected to be effective for suppressing the peeling of the active material from the negative electrode, it requires high-temperature sintering for a long time (10 to 30 hours) and has low productivity. The effect of preventing deterioration due to the refinement of the material particles themselves cannot be expected.
- silicon and silicon oxide are used as the negative electrode active material, and a gel electrolyte is used as the electrolyte.
- the gas generated between the negative electrode active material and the gel electrolyte during charge / discharge enters the voids not in contact with the gel electrolyte inside the particles refined by charge / discharge, and the activity of silicon and silicon oxide as the negative electrode active material is Declined. Furthermore, it has been found that the polymer contained in the gel electrolyte is broken due to the expansion and contraction of the volume of the negative electrode active material. When the charge / discharge cycle was repeated, the capacity decreased.
- the present embodiment has been made in view of the above problems.
- a polymer secondary battery using silicon and silicon oxide as a negative electrode active material a polymer secondary battery exhibiting a high capacity retention rate even when charge and discharge cycles are repeated.
- An object is to provide a secondary battery.
- the polymer secondary battery according to the present embodiment includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a gel electrolyte containing a polymer, and the negative electrode includes silicon and silicon oxide as a negative electrode active material. And a gel electrolyte containing the polymer is present in the voids in which the particles of the negative electrode active material are miniaturized.
- the gel electrolyte containing the polymer is formed by polymerizing a polymerizable compound, includes a supporting salt that acts as a polymerization initiator for the polymerizable compound, and includes a polymerization initiator other than the supporting salt. It is characterized by not.
- the method for producing a polymer secondary battery according to the present embodiment includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, a gel electrolyte, and an exterior member containing the positive electrode, the negative electrode, the separator, and the gel electrolyte,
- the method for producing a polymer secondary battery comprising: a step in which the negative electrode contains silicon and silicon oxide as a negative electrode active material, and a gel electrolyte composition containing a positive electrode, a negative electrode, a separator, and a polymerizable compound is enclosed in an exterior member And at least one charge, a step of allowing the gel electrolyte composition containing the polymerizable compound to penetrate into the voids in which the negative electrode active material particles are refined by a large volume change accompanying the charge, and the polymerization And a step of polymerizing the active compound to form a gel electrolyte.
- the gel electrolyte composition includes a supporting salt that acts as a polymerization initiator for the polymerizable compound, and does not include a polymerization initiator other than the supporting salt.
- a polymer secondary battery using silicon and silicon oxide as a negative electrode active material a polymer secondary battery exhibiting a high capacity retention rate even when charge / discharge cycles are repeated can be provided. .
- the polymer secondary battery according to the present embodiment includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a gel electrolyte containing a polymer, and the negative electrode includes silicon and silicon oxide as a negative electrode active material.
- the gel electrolyte containing the polymer is present in the voids in which the particles of the negative electrode active material are refined.
- the gel electrolyte containing the polymer is formed by polymerizing a polymerizable compound, includes a supporting salt that acts as a polymerization initiator for the polymerizable compound, and includes a polymerization initiator other than the supporting salt. Preferably not.
- the method for producing a polymer secondary battery according to the present embodiment includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, a gel electrolyte, and an exterior member that includes the positive electrode, the negative electrode, the separator, and the gel electrolyte.
- a negative electrode contains silicon and silicon oxide as a negative electrode active material
- a gel electrolyte composition containing a positive electrode, a negative electrode, a separator, and a polymerizable compound is enclosed in an exterior member
- the gel electrolyte composition includes a supporting salt that acts as a polymerization initiator for the polymerizable compound and does not include a polymerization initiator other than the supporting salt.
- the negative electrode active material is obtained by charging at least once (hereinafter referred to as initial charge) before polymerizing the polymerizable compound contained in the gel electrolyte composition.
- initial charge at least once
- the silicon compound particles containing silicon and silicon oxide which are negative electrode active materials in the charge / discharge cycle of the manufactured secondary battery Further refinement, gas retention in the particles, and polymer breakage can be suppressed.
- the polymer secondary battery manufactured by the method according to the present embodiment exhibits a high capacity retention rate even when the charge / discharge cycle is repeated.
- the gel electrolyte composition containing the polymerizable compound contains a supporting salt that acts as a polymerization initiator, and if it does not contain a polymerization initiator other than the supporting salt, a polymerization initiator that reduces battery characteristics when remaining Since it is not necessary to add to a gel electrolyte composition separately, it is more preferable. Gas is likely to be generated particularly when the negative electrode active material particles containing silicon and silicon oxide are miniaturized, but if a polymerization initiator other than the supporting salt remains, the negative electrode active material particles are gelated in the micronized voids. Even in the presence of an electrolyte, the suppression of gas generation is not sufficient.
- FIG. 1 shows the behavior of the negative electrode active material particles during the initial charge in a conventional polymer secondary battery using silicon and silicon oxide as the negative electrode active material.
- a gel electrolyte composition containing a positive electrode, a negative electrode, a separator, and a polymerizable compound is enclosed in an exterior member, and then the polymerizable compound is polymerized, for example, by heating to obtain a gel electrolyte.
- the negative electrode active material particles in the polymer secondary battery include Si (2) and SiO 2 (1) as shown in FIG. 1, and the surface of the negative electrode active material particles has a conductive agent (4) such as polymer (3) and carbon. ) Exists.
- FIG. 2 shows the behavior of the negative electrode active material particles when the polymer secondary battery in the present embodiment is discharged from the fully charged state.
- the negative electrode active material particles are already finely divided by a large volume change accompanying the charge, and are in contact with the gel electrolyte. There are no voids (6), and instead the polymer (3) is present in the anode active material particles.
- the polymerizable compound is polymerized after the initial charge to produce a gel electrolyte.
- the polymerizable compound penetrates into the voids generated in the negative electrode active material particles, and the polymer (3) is also formed in the negative electrode active material particles in the polymerization step.
- the generation of gas is suppressed, and the destruction of the polymer is suppressed. Thereby, even if it repeats a charging / discharging cycle, the fall of a capacity
- the polymer secondary battery according to the present embodiment includes a positive electrode, a negative electrode, a separator interposed between the positive electrode and the negative electrode, and a gel electrolyte containing a polymer, and the negative electrode includes silicon and silicon oxide as a negative electrode active material.
- the gel electrolyte containing the polymer is present in the voids in which the particles of the negative electrode active material are refined.
- the gel electrolyte containing the polymer is formed by polymerizing a polymerizable compound, includes a supporting salt that acts as a polymerization initiator for the polymerizable compound, and includes a polymerization initiator other than the supporting salt. Preferably not.
- the configuration of the polymer secondary battery is not particularly limited as long as it includes a positive electrode, a negative electrode, a separator, and a gel electrolyte.
- the exterior member is a laminated laminate type secondary battery, which further suppresses a decrease in discharge capacity due to a charge / discharge cycle. This is preferable because it can be performed.
- An example of a method for producing a laminated laminate type secondary battery before gel electrolyte formation is shown in FIG. In the laminated laminate type secondary battery before gel electrolyte formation shown in FIG. 3, the flat positive electrode (10) and the negative electrode (8) are sandwiched between the positive electrode (10) and the negative electrode (8) inside the exterior member. Separator (9) and a gel electrolyte composition (not shown) are included.
- a positive electrode conductive tab (12) is attached to the positive electrode (10), and a negative electrode conductive tab (11) is attached to the negative electrode (8).
- the positive electrode (10), the separator (9) and the negative electrode (8) are accommodated in an exterior member (7), and the gel electrolyte composition is injected under reduced pressure. It is produced by sealing.
- the gel electrolyte composition is injected under reduced pressure. It is produced by sealing.
- at least one charge is performed, and a polymerizable compound contained in the gel electrolyte composition is polymerized to form a gel electrolyte, whereby a laminated laminate type secondary battery can be manufactured.
- the electrode element comprised by the positive electrode (10), the negative electrode (8), and the separator (9) is 1 set in FIG. 3, multiple sets may be laminated
- the material structure of the negative electrode is composed of a negative electrode active material composed of a composite of silicon (Si) and silicon oxide (SiO 2 ) capable of occluding and releasing lithium, carbon and a binder resin.
- a material layer is formed.
- a composite of silicon and silicon oxide coated with carbon may be used as the negative electrode active material.
- As a means for coating the negative electrode active material with carbon it is possible only to mix it, but examples thereof include a vapor deposition method, a CVD method, and a sputtering method. However, it is not limited to these.
- the finely divided negative electrode active material particles are finely pulverized negative electrode active material particles and negative electrode active materials having a large number of cracks (depth of 0.5 to 1 ⁇ m or more from the outermost surface of the active material particles). Including both particles.
- a thermosetting binder such as polyimide, polyamide, polyamideimide, polyacrylic acid resin, or polymethacrylic acid resin can be used.
- the mixture is well-known by methods such as a coated electrode plate obtained by rolling a paste obtained by kneading the mixture with a solvent on a metal foil such as copper foil and rolling, or by directly pressing into a pressure-formed electrode plate. Can be processed.
- the negative electrode is prepared by dispersing and kneading Si and SiO 2 composite powder, carbon powder, and a binder having a thermosetting property as a binder resin in a solvent such as N-methyl-2-pyrrolidone (NMP). It is formed by preparing a mixture, applying the negative electrode mixture on a negative electrode current collector made of a metal foil, and drying in a high temperature atmosphere.
- NMP N-methyl-2-pyrrolidone
- carbon black such as acetylene black may be mixed as necessary in order to impart conductivity in addition to the carbon powder.
- the electrode density of the produced negative electrode active material layer is preferably 0.5 g / cm 3 or more and 2.0 g / cm 3 or less.
- the thickness of the metal foil is preferably 4 to 100 ⁇ m because it is preferable to maintain the strength, and more preferably 5 to 30 ⁇ m for increasing the energy density.
- the gel electrolyte of the polymer secondary battery according to this embodiment includes an aprotic organic solvent, a supporting salt, and a polymer.
- aprotic organic solvent examples include propylene carbonate (PC), ethylene carbonate (EC), butylene carbonate (BC), cyclic carbonates such as vinylene carbonate (VC), dimethyl carbonate (DMC), diethyl carbonate (DEC), Chain carbonates such as ethyl methyl carbonate (EMC) and dipropyl carbonate (DPC), aliphatic carboxylic acid esters such as methyl formate, methyl acetate and ethyl propionate, ⁇ -lactones such as ⁇ -butyrolactone, Chain ethers such as 2-diethoxyethane (DEE) and ethoxymethoxyethane (EME), cyclic ethers such as tetrahydrofuran and 2-methyltetrahydrofuran, dimethyl sulfoxide, 1,3-dioxolane, formamide, aceto Amide, dimethylformamide, dioxolane, acetonitrile, propylnitrile,
- Examples of the supporting salt include LiPF 6 , LiAsF 6 , LiAlCl 4 , LiClO 4 , LiBF 4 , LiSbF 6 , LiCF 3 SO 3 , LiC 4 F 9 CO 3 , LiC (CF 3 SO 2 ) 3 , LiN (CF 3 SO 2) 2, LiN (C 2 F 5 SO 2) 2, LiB 10 Cl 10, lower aliphatic carboxylic acid lithium carboxylate, chloroborane lithium, lithium tetraphenylborate, LiCl, LiBr, LiI, LiSCN, LiCl, imide And the like. These may use only 1 type and may mix and use 2 or more types.
- the concentration of these supporting salts in the gel electrolyte is preferably 0.5 mol / l or more and 1.5 mol / l or less.
- concentration is higher than 1.5 mol / l, the properties of the gel electrolyte may be deteriorated.
- the concentration is less than 0.5 mol / l, the electrical conductivity may decrease.
- Examples of the polymerizable compound contained in the gel electrolyte composition that can be used as the raw material for the polymer include monomers and oligomers having one or more polymerizable functional groups per molecule.
- the gelling component methyl methacrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, propylene di ( (Meth) acrylate, dipropylene di (meth) acrylate, tripropylene di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, (3-ethyl-3-oxetanyl ) Methyl methacrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth)
- (meth) acrylate means the substance containing either an acrylate, a methacrylate, or both.
- the said polymeric compound may use only 1 type, and may mix and use 2 or more types. Further, other gelable components can be mixed and used.
- a polymer obtained by polymerizing the monomer to some extent as the polymerizable compound because the battery shape can be easily maintained when encapsulated in a laminate film.
- the degree of polymerization of the monomer is not particularly limited as long as the gel electrolyte composition to be prepared is liquid and is further polymerized in a subsequent polymerization step to become a solid gel electrolyte.
- the gel electrolyte composition containing the polymerizable compound contains a supporting salt that acts as a polymerization initiator for the polymerizable compound, and does not contain a polymerization initiator other than the supporting salt.
- a polymerization initiator that deteriorates battery characteristics does not need to be separately added to the gel electrolyte composition.
- LiPF 6 when LiPF 6 is used as the supporting salt, it is preferable to use a methacrylic acid ester polymer as the polymerizable compound. This is because LiPF 6 acts as a polymerization initiator for the methacrylic acid ester polymerized product, and it is not necessary to add a polymerization initiator separately.
- the gel electrolyte composition contains 5% by mass or less of the polymerizable compound from the viewpoint of suppressing battery resistance and suppressing peeling of the electrode active material. To preferred.
- the material composition of the positive electrode consists of a positive electrode active material made of an oxide capable of occluding and releasing lithium, a conductive agent for imparting conductivity, and a binder resin, and a mixture of these materials forms a positive electrode active material layer.
- the oxide capable of inserting and extracting lithium include lithium nickelate, lithium manganate, and lithium cobaltate.
- the conductive agent include carbon black and acetylene black.
- the binder resin include poly (vinylidene fluoride), bilinidene fluoride-hexafluoropropylene copolymer, bilinidene fluoride-tetrafluoroethylene copolymer, and polytetrafluoroethylene.
- the positive electrode mixture is prepared by dispersing and kneading an oxide powder capable of occluding and releasing lithium, a conductive agent powder, and a binder resin in a solvent such as N-methyl-2-pyrrolidone (NMP) and dehydrated toluene.
- NMP N-methyl-2-pyrrolidone
- the positive electrode material mixture is applied onto a positive electrode current collector made of a metal foil and dried in a high-temperature atmosphere.
- the electrode density of the active material layer of the formed positive electrode is preferably 2.0 g / cm 3 or more and 3.0 g / cm 3 or less. When the electrode density is lower than the above range, the absolute value of the discharge capacity may be small.
- the thickness of the metal foil is preferably 4 to 100 ⁇ m because it is preferable to maintain the strength, and more preferably 5 to 30 ⁇ m for increasing the energy density.
- separator As a separator of the polymer secondary battery according to the present embodiment, polyolefin such as polyethylene or polypropylene, a porous film of a fluororesin, a nonwoven fabric, or the like can be used. A separator having a laminated structure in which different kinds of porous films or nonwoven fabrics are laminated can also be used.
- the method for producing a polymer secondary battery according to the present embodiment includes a step of encapsulating a gel electrolyte composition containing a positive electrode, a negative electrode, a separator, and a polymerizable compound inside an exterior member, and at least charging once.
- this embodiment is not limited to these.
- a gel electrolyte composition containing a positive electrode, a negative electrode, a separator, and a polymerizable compound is sealed inside the exterior member.
- the exterior member is not particularly limited as long as it can enclose a gel electrolyte composition containing a positive electrode, a negative electrode, a separator, and a polymerizable compound.
- a laminate film or the like can be used.
- the exterior member is sealed in the order of the negative electrode (8) connected to the negative electrode conductive tab (11), the separator (9), and the positive electrode (10) connected to the positive electrode conductive tab (12).
- the active material layer so as to face the separator (9)
- injecting the gel electrolyte composition, and sealing under reduced pressure can be performed. .
- polymerization can be produced.
- the gel electrolyte composition containing the polymerizable compound penetrates into the voids in which the particles of the negative electrode active material are refined by the large volume change accompanying the charging.
- the gas is released to the outside of the negative electrode active material particles by this initial charge, the deactivation of the negative electrode active material and the destruction of the polymer are suppressed in the charge / discharge cycle of the completed battery, and the capacity retention rate is reduced. Can be suppressed.
- the initial charge is performed at least once. For example, only one charge may be performed as the initial charge, charge-discharge may be performed, charge-discharge-charge may be performed, or charge-discharge-charge-discharge may be performed. Thus, as long as the initial charge is performed at least once, the initial charge may be terminated in the discharged state or may be terminated in the charged state. Further, after the first charging, the charging and discharging may be performed any number of times.
- the end-of-charge voltage can be 4.2 to 3.8V. Further, the discharge end voltage can be set to 2.5 to 3.0V.
- the temperature for charging and discharging is not particularly limited as long as the polymerizable compound does not polymerize, but is preferably 20 to 30 ° C.
- the polymerization compound is polymerized to obtain a gel electrolyte.
- the polymerization method of the polymerizable compound is not particularly limited.
- the polymerizable compound can be polymerized by storing the battery for several days at a temperature at which the polymerizable compound can be polymerized.
- Example 1 As the negative electrode material, a composite of silicon and silicon oxide was used as the negative electrode active material, and carbon (acetylene black) was used as the conductive material. The molar ratio of silicon, silicon oxide and carbon used was 1: 1: 0.8.
- lithium nickelate which is an oxide capable of occluding and releasing lithium
- the lithium nickelate is commercially available as a powder reagent.
- the charge / discharge performance was confirmed (capacity characteristics were confirmed between 4.3 V and 3.0 V using a model cell with metallic lithium as a counter electrode), the lithium nickelate showed about 200 mAh / g, and the charge / discharge potential was It was around 3.8V.
- the negative active material layer was prepared by applying a negative electrode mixture prepared by mixing polyimide, as a binder, and NMP, as a solvent, onto the silicon, silicon oxide and carbon composite material particles on a 10 ⁇ m copper foil and drying at 125 ° C. for 5 minutes. After that, compression molding was performed with a roll press, and drying treatment was performed again in a drying furnace at 350 ° C. for 30 minutes in an N 2 atmosphere. Although the drying time at 350 ° C. is 30 minutes in this embodiment, it is not limited to this, and about 20 minutes to 2 hours is appropriate. If it is less than 20 minutes, there is a concern that the adhesiveness is lowered due to poor curing of the polyimide binder.
- the active material layer formed on this copper foil was punched out and used as a negative electrode, and a negative electrode lead tab made of nickel for charge extraction was fused by ultrasonic waves.
- the active material layer of the positive electrode the active material particles made of lithium nickelate, a positive electrode mixture in which polyvinylidene fluoride as a binder and NMP as a solvent are mixed are applied on a 20 ⁇ m aluminum foil and dried at 125 ° C. for 5 minutes. It processed and produced.
- the active material layer formed on the aluminum foil was punched into a positive electrode, and a positive electrode lead tab made of aluminum for charge extraction was fused by ultrasonic waves.
- EC ethylene carbonate
- DEC diethyl carbonate
- MEC methyl ethyl carbonate
- the initial charge was performed in the battery before polymerization of the polymerizable compound.
- the initial charging conditions were a constant current of 1.5 mA, a charge end voltage of 4.2 V, and a discharge end voltage of 2.5 V, which were performed at 20 ° C.
- the second fully charged state (4.2 V) after charge-discharge-charge the produced battery was stored at 60 ° C. for 1 day to polymerize the polymerizable compound.
- a laminated laminate type secondary battery was completed.
- a charge / discharge cycle test was performed on the battery produced as described above. This charge / discharge test was performed at 199 cycles at 60 ° C. with a constant current of 15 mA, a charge end voltage of 4.2 V, and a discharge end voltage of 2.5 V. The charge / discharge current was reduced to 15 mA (1 to 49 cycles), 7 mA (50 to 99 cycles), 3.5 mA (100 to 149 cycles), and 1.75 mA (150 to 199 cycles).
- Table 1 shows the discharge capacity per mass of the negative electrode active material after 199 cycles and the discharge capacity maintenance rate after 199 cycles relative to after 1 cycle.
- FIG. 4 is a graph showing the cycle number on the horizontal axis and the discharge capacity retention rate on the vertical axis.
- Example 2 In the battery before polymerization of the polymerizable compound according to Example 1, the charge-discharge-charge-discharge operation was performed as the initial charge under the same conditions as in Example 1, and in the second discharge state (2.5 V), The produced battery was stored at 60 ° C. for 1 day, and the polymerizable compound was polymerized to complete a laminated laminate type secondary battery. Using the battery, a charge / discharge cycle test was conducted in the same manner as in Example 1. The results are shown in Table 1 and FIG.
- Example 1 In the battery before polymerization of the polymerizable compound according to Example 1, the battery was stored at 60 ° C. for 1 day without performing initial charging, and the polymerizable compound was polymerized. Thus, a laminated laminate type secondary battery was completed. A charge / discharge cycle test was conducted in the same manner as in Example 1 on the battery thus fabricated. Table 1 shows the discharge capacity per mass of the negative electrode active material after 199 cycles and the discharge capacity maintenance rate after 199 cycles relative to after 1 cycle.
- FIG. 5 is a graph showing the cycle number on the horizontal axis and the discharge capacity retention rate on the vertical axis.
- Comparative Example 1 resulted in a lower capacity retention rate, which proved that the effect of this embodiment was great.
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Abstract
Description
本実施形態に係るポリマー二次電池は、正極と、負極と、正極と負極の間に介在するセパレータと、ポリマーを含むゲル電解質と、を備え、前記負極が負極活物質としてケイ素及びケイ素酸化物を含み、前記負極活物質の粒子が微細化した空隙内に、前記ポリマーを含むゲル電解質が存在する。また、前記ポリマーを含むゲル電解質は、重合性化合物が重合して形成されたものであり、前記重合性化合物の重合開始剤として作用する支持塩を含み、該支持塩以外の重合開始剤を含まない方が好ましい。
負極の材料構成は、リチウムを吸蔵放出可能なケイ素(Si)とケイ素酸化物(SiO2)の複合物からなる負極活物質、炭素及びバインダ樹脂からなり、これらを混合した合剤によって負極の活物質層が形成される。ケイ素とケイ素酸化物の複合物に炭素を被覆したものを用いて負極活物質としてもよい。負極活物質に炭素を被覆する手段としては、混合するのみでも可能だが、蒸着法、CVD法、スパッタリング法等も挙げられる。しかし、これらに限定されるものではない。なお、微細化した負極活物質の粒子とは、微細に粉砕された負極活物質の粒子、及び多数の亀裂(活物質粒子最表面から深さ0.5~1μm以上)の入った負極活物質の粒子の両方を含む。バインダ樹脂には、ポリイミド、ポリアミド、ポリアミドイミド、ポリアクリル酸系樹脂、ポリメタクリル酸系樹脂等の熱硬化性を有する結着剤を用いることができる。前記合剤は、該合剤を溶剤と混練したペーストを銅箔等の金属箔上に塗布して圧延加工した塗布型極板や直接プレスして加圧成形極板にするなどの方法で周知の形態に加工することができる。負極は、例えば、SiとSiO2複合粉末と、炭素粉末と、バインダ樹脂として熱硬化性を有する結着剤とをN-メチル-2-ピロリドン(NMP)等の溶剤に分散させ混練して負極合剤を調製し、金属箔からなる負極集電体の上にこの負極合剤を塗布し、高温雰囲気で乾燥することにより形成される。負極の活物質層中には必要に応じて前記炭素粉末以外に導電性を付与するため、アセチレンブラック等のカーボンブラックを混合してもよい。生成した負極活物質層の電極密度は0.5g/cm3以上、2.0g/cm3以下であることが好ましい。電極密度が前記範囲より低い場合は放電容量の絶対値が小さく、従来の炭素材料に対するメリットが得られない場合がある。また、電極密度が前記範囲より高い場合には、電極に電解液を含浸させることが難しいことがあり、やはり放電容量が低下する場合がある。金属箔の厚みは強度を保てるような厚みとすることが好ましいことから、4~100μmであることが好ましく、エネルギー密度を高めるためには、5~30μmであることがより好ましい。
本実施形態に係るポリマー二次電池のゲル電解質は、非プロトン性有機溶媒、支持塩及びポリマーを含む。
正極の材料構成は、リチウムを吸蔵放出可能な酸化物からなる正極活物質、導電性を付与するための導電剤及びバインダ樹脂からなり、これらを混合した合剤によって正極の活物質層が形成される。リチウムを吸蔵放出可能な酸化物としては、ニッケル酸リチウム、マンガン酸リチウム、コバルト酸リチウム等が挙げられる。導電剤としては、カーボンブラック、アセチレンブラック等が挙げられる。バインダ樹脂としては、ポリフッ化ビリニデン、ビリニデンフルオライド-ヘキサフルオロプロピレン共重合体、ビリニデンフルオライド-テトラフルオロチレン共重合体、ポリテトラフルオロチレン等が挙げられる。正極は、例えば、リチウムを吸蔵放出可能な酸化物粉末と、導電剤粉末と、バインダ樹脂とをN‐メチル‐2‐ピロリドン(NMP)、脱水トルエン等の溶剤に分散させ混練して正極合剤を調製し、金属箔からなる正極集電体の上にこの正極合剤を塗布し、高温雰囲気で乾燥することにより形成される。形成した正極の活物質層の電極密度は2.0g/cm3以上、3.0g/cm3以下であることが好ましい。電極密度が前記範囲より低い場合には放電容量の絶対値が小さくなる場合がある。また、電極密度が前記範囲より高い場合には電極に電解液を含浸させることが難しいことがあり、やはり放電容量が低下する場合がある。金属箔の厚みは強度を保てるような厚みとすることが好ましいことから、4~100μmであることが好ましく、エネルギー密度を高めるためには、5~30μmであることがより好ましい。
本実施形態に係るポリマー二次電池のセパレータとしては、ポリエチレン、ポリプロピレン等のポリオレフィン、あるいはフッ素樹脂の多孔性フィルム、不織布等を使用することができる。また、異種の多孔性フィルムあるいは不織布を積層した積層構造のセパレータを使用することもできる。
本実施形態に係るポリマー二次電池の製造方法は、正極、負極、セパレータ及び重合性化合物を含むゲル電解質組成物を外装部材の内部に封入する工程と、少なくとも充電を1回行い、該充電に伴う大きな体積変化によって前記負極活物質の粒子が微細化された空隙内に、前記重合性化合物を含むゲル電解質組成物を浸透させる工程と、前記重合性化合物を重合させてゲル電解質とする工程と、をこの順序で含む。以下、各工程の詳細について説明するが本実施形態はこれらに限定されない。
まず、正極、負極、セパレータ及び重合性化合物を含むゲル電解質組成物を外装部材の内部に封入する。外装部材としては正極、負極、セパレータ及び重合性化合物を含むゲル電解質組成物を内部に封入することができるものであれば特に限定されない。例えば、ラミネートフィルム等を用いることができる。
次に、前記重合性化合物重合前の電池に対し少なくとも1回充電を行う。該充電に伴う大きな体積変化によって負極活物質の粒子が微細化された空隙内に、重合性化合物を含むゲル電解質組成物が浸透する。前述したように、この初期充電により負極活物質粒子外部にガスが放出されるため、完成した電池の充放電サイクルにおいて負極活物質の失活、ポリマーの破壊を抑制し、容量維持率の低下を抑制することができる。
次に、前記初期充電を行った重合性化合物重合前の電池において、重合性化合物を重合させてゲル電解質とする。この工程により本実施形態に係るポリマー二次電池が完成する。重合性化合物の重合方法は特に限定されないが、例えば重合性化合物が重合可能な温度下で該電池を数日保存することで重合性化合物を重合することができる。
負極材料には、負極活物質としてケイ素とケイ素酸化物の複合物を、導電材として炭素(アセチレンブラック)を用いた。用いるケイ素、ケイ素酸化物及び炭素のモル比は1:1:0.8とした。
実施例1に係る重合性化合物重合前の電池において、実施例1と同様の条件で初期充電として充電-放電-充電-放電の操作を行い、2回目の放電状態(2.5V)にて、作製した電池を60℃で1日保存し、重合性化合物の重合を行い、積層ラミネート型二次電池を完成させた。該電池を用いて実施例1と同様にして充放電サイクル試験を行った。結果を表1、図4に示す。
実施例1に係る重合性化合物重合前の電池において、初期充電を行わずに該電池を60℃で1日保存し重合性化合物の重合を行った。これにより積層ラミネート型二次電池を完成させた。このように作製した電池にて、実施例1と同様に充放電サイクル試験を行った。199サイクル後の負極活物質の質量あたりの放電容量と1サイクル後に対する199サイクル後の放電容量維持率を表1に示す。また、横軸にサイクル数、縦軸に放電容量維持率を示したグラフを図5に示す。
2 Si
3 ポリマー
4 導電剤(炭素)
5 LixSi(Liと合金化したSi)
6 空隙
7 外装部材
8 負極
9 セパレータ
10 正極
11 負極導電タブ
12 正極導電タブ
Claims (6)
- 正極と、負極と、正極と負極の間に介在するセパレータと、ポリマーを含むゲル電解質と、を備え、
前記負極が負極活物質としてケイ素及びケイ素酸化物を含み、
前記負極活物質の粒子が微細化した空隙内に、前記ポリマーを含むゲル電解質が存在するポリマー二次電池。 - 前記ポリマーを含むゲル電解質は、重合性化合物が重合して形成されたものであり、
前記重合性化合物の重合開始剤として作用する支持塩を含み、該支持塩以外の重合開始剤を含まない請求項1に記載のポリマー二次電池。 - 前記ポリマー二次電池が積層ラミネート型二次電池である請求項1又は2に記載のポリマー二次電池。
- 正極と、負極と、
正極と負極の間に介在するセパレータと、
ゲル電解質と、
正極、負極、セパレータ及びゲル電解質を内包する外装部材と、
を備えるポリマー二次電池の製造方法において、
前記負極が負極活物質としてケイ素及びケイ素酸化物を含み、
正極、負極、セパレータ及び重合性化合物を含むゲル電解質組成物を外装部材の内部に封入する工程と、
少なくとも充電を1回行い、該充電に伴う大きな体積変化によって前記負極活物質の粒子を微細化した空隙内に、前記重合性化合物を含むゲル電解質組成物を浸透させる工程と、
前記重合性化合物を重合させてゲル電解質とする工程と、
をこの順序で含むポリマー二次電池の製造方法。 - 前記ゲル電解質組成物が、前記重合性化合物の重合開始剤として作用する支持塩を含み、該支持塩以外の重合開始剤を含まない請求項4に記載のポリマー二次電池の製造方法。
- 前記ポリマー二次電池が積層ラミネート型二次電池である請求項4又は5に記載のポリマー二次電池の製造方法。
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US20120321962A1 (en) | 2012-12-20 |
JPWO2011102453A1 (ja) | 2013-06-17 |
EP2538485A4 (en) | 2014-07-09 |
EP2538485A1 (en) | 2012-12-26 |
CN102771002A (zh) | 2012-11-07 |
EP2538485B1 (en) | 2016-08-31 |
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