WO2014192652A1 - 電気化学素子電極用バインダー、電気化学素子電極用粒子複合体、電気化学素子電極、電気化学素子及び電気化学素子電極の製造方法 - Google Patents
電気化学素子電極用バインダー、電気化学素子電極用粒子複合体、電気化学素子電極、電気化学素子及び電気化学素子電極の製造方法 Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000004760 aramid Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910021387 carbon allotrope Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- GTBGXKPAKVYEKJ-UHFFFAOYSA-N decyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C(C)=C GTBGXKPAKVYEKJ-UHFFFAOYSA-N 0.000 description 1
- FWLDHHJLVGRRHD-UHFFFAOYSA-N decyl prop-2-enoate Chemical compound CCCCCCCCCCOC(=O)C=C FWLDHHJLVGRRHD-UHFFFAOYSA-N 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 125000001153 fluoro group Chemical group F* 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- MDNFYIAABKQDML-UHFFFAOYSA-N heptyl 2-methylprop-2-enoate Chemical compound CCCCCCCOC(=O)C(C)=C MDNFYIAABKQDML-UHFFFAOYSA-N 0.000 description 1
- SCFQUKBBGYTJNC-UHFFFAOYSA-N heptyl prop-2-enoate Chemical compound CCCCCCCOC(=O)C=C SCFQUKBBGYTJNC-UHFFFAOYSA-N 0.000 description 1
- LNCPIMCVTKXXOY-UHFFFAOYSA-N hexyl 2-methylprop-2-enoate Chemical compound CCCCCCOC(=O)C(C)=C LNCPIMCVTKXXOY-UHFFFAOYSA-N 0.000 description 1
- LNMQRPPRQDGUDR-UHFFFAOYSA-N hexyl prop-2-enoate Chemical compound CCCCCCOC(=O)C=C LNMQRPPRQDGUDR-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- PBOSTUDLECTMNL-UHFFFAOYSA-N lauryl acrylate Chemical compound CCCCCCCCCCCCOC(=O)C=C PBOSTUDLECTMNL-UHFFFAOYSA-N 0.000 description 1
- 239000001989 lithium alloy Substances 0.000 description 1
- 229910001386 lithium phosphate Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
- 239000011976 maleic acid Substances 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000002931 mesocarbon microbead Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- LKEDKQWWISEKSW-UHFFFAOYSA-N nonyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCOC(=O)C(C)=C LKEDKQWWISEKSW-UHFFFAOYSA-N 0.000 description 1
- MDYPDLBFDATSCF-UHFFFAOYSA-N nonyl prop-2-enoate Chemical compound CCCCCCCCCOC(=O)C=C MDYPDLBFDATSCF-UHFFFAOYSA-N 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- HMZGPNHSPWNGEP-UHFFFAOYSA-N octadecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)C(C)=C HMZGPNHSPWNGEP-UHFFFAOYSA-N 0.000 description 1
- NZIDBRBFGPQCRY-UHFFFAOYSA-N octyl 2-methylprop-2-enoate Chemical compound CCCCCCCCOC(=O)C(C)=C NZIDBRBFGPQCRY-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- GYDSPAVLTMAXHT-UHFFFAOYSA-N pentyl 2-methylprop-2-enoate Chemical compound CCCCCOC(=O)C(C)=C GYDSPAVLTMAXHT-UHFFFAOYSA-N 0.000 description 1
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- PMJHHCWVYXUKFD-UHFFFAOYSA-N piperylene Natural products CC=CC=C PMJHHCWVYXUKFD-UHFFFAOYSA-N 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920001197 polyacetylene Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001083 polybutene Polymers 0.000 description 1
- 229920006393 polyether sulfone Polymers 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000098 polyolefin Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BOQSSGDQNWEFSX-UHFFFAOYSA-N propan-2-yl 2-methylprop-2-enoate Chemical compound CC(C)OC(=O)C(C)=C BOQSSGDQNWEFSX-UHFFFAOYSA-N 0.000 description 1
- LYBIZMNPXTXVMV-UHFFFAOYSA-N propan-2-yl prop-2-enoate Chemical compound CC(C)OC(=O)C=C LYBIZMNPXTXVMV-UHFFFAOYSA-N 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- PNXMTCDJUBJHQJ-UHFFFAOYSA-N propyl prop-2-enoate Chemical compound CCCOC(=O)C=C PNXMTCDJUBJHQJ-UHFFFAOYSA-N 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 description 1
- 238000001694 spray drying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 description 1
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 1
- ATZHWSYYKQKSSY-UHFFFAOYSA-N tetradecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C(C)=C ATZHWSYYKQKSSY-UHFFFAOYSA-N 0.000 description 1
- XZHNPVKXBNDGJD-UHFFFAOYSA-N tetradecyl prop-2-enoate Chemical compound CCCCCCCCCCCCCCOC(=O)C=C XZHNPVKXBNDGJD-UHFFFAOYSA-N 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/38—Carbon pastes or blends; Binders or additives therein
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
-
- 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
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/60—Other road transportation technologies with climate change mitigation effect
- Y02T10/70—Energy storage systems for electromobility, e.g. batteries
Definitions
- the present invention relates to a binder for an electrochemical element electrode, a particle composite for an electrochemical element electrode, an electrochemical element electrode, an electrochemical element, and a method for producing an electrochemical element electrode.
- Lithium ion secondary batteries have a relatively high energy density and are used in mobile fields such as mobile phones and notebook personal computers.
- the electric double layer capacitor can be rapidly charged and discharged, the electric double layer capacitor is expected to be used as an auxiliary power source for an electric vehicle or the like in addition to being used as a memory backup small power source for a personal computer or the like.
- the lithium ion capacitor that takes advantage of the lithium ion secondary battery and the electric double layer capacitor has higher energy density and output density than the electric double layer capacitor.
- Application to applications that could not meet the specifications for capacitor performance is being considered.
- lithium ion secondary batteries have been studied for application not only to in-vehicle applications such as hybrid electric vehicles and electric vehicles, but also to power storage applications.
- An electrode for an electrochemical element is usually formed by laminating an electrode active material layer formed by binding an electrode active material and a conductive agent used as necessary with a binder on a current collector. is there.
- An electrode for an electrochemical element includes a coated electrode manufactured by a method of applying a slurry for a coated electrode containing an electrode active material, a binder, a conductive agent and the like on a current collector and removing the solvent by heat or the like.
- Patent Document 1 polymer particles obtained by extruding a polymer into a film and pulverizing are used as a binder, and the binder, electrode active material, conductive agent and solvent are mixed to obtain a slurry for a coated electrode.
- a coated electrode is obtained by coating on a current collector.
- the polymer particles used in Patent Document 1 are a dried binder, that is, a dry binder.
- Patent Document 2 a dry binder or binder dispersed in a solvent, an electrode active material, and a conductive agent containing a carbon material are mixed and dried to form an electrode active material layer using a powdery mixture. is doing. Further, in Patent Document 3, a coating is formed on the negative electrode surface of a lithium primary battery using a mixed powder obtained by mixing carbon powder and a binder in a wet manner and then drying and grinding.
- an electrode active material layer is formed using a mixed powder obtained by mixing binder particles combined with a conductive agent by a suspension polymerization method performed in the presence of a conductive agent and an electrode active material. Forming.
- PVDF polyvinylidene fluoride
- Patent Document 1 when using a dry binder as a binder and forming an electrode active material layer using an electrode material obtained by mixing a dry binder and an electrode active material by a dry method, using the binder described in Patent Document 1, Since the glass transition temperature was too high, an electrode having sufficient flexibility could not be obtained. Moreover, when the binder of patent document 2 or 5 was used, since the glass transition temperature of the binder was too low, formation of the uniform electrode active material layer was difficult. Patent Documents 3 and 4 did not describe the use of a dry binder.
- the object of the present invention is to produce a slurry at the time of electrode layer formation, so that the productivity of the electrode is excellent, and since a water-soluble polymer component is not required as a dispersant, the resistance can be reduced, and the thickness accuracy of the obtained electrode
- Electrochemical element electrode binder excellent in flexibility, electrochemical element electrode particle composite using the electrochemical element electrode binder, electrochemical element electrode and electrochemical using the electrochemical element electrode particle composite It is to provide an element. Furthermore, the objective of this invention is providing the manufacturing method of the electrochemical element electrode which is excellent in productivity, and excellent in thickness precision and a softness
- the present inventor has found that the above object can be achieved by setting the glass transition temperature and the average particle diameter within a predetermined range, thereby completing the present invention.
- (1) It is composed of a polymer having a glass transition temperature of 35 to 80 ° C. and a primary particle volume-based D50 average particle size of 80 to 1000 nm, and has a volatile content at 120 ° C. of less than 1% by weight, and is powdered composite Electrochemical element electrode binder characterized by being a particle, (2) The electrochemical element according to (1), which is obtained by drying an aqueous dispersion of a particulate polymer in which the polymer is dispersed at a temperature lower than the minimum film-forming temperature of the particulate polymer.
- Electrode binder (3) Conjugated diene monomer unit, acrylate ester monomer unit, methacrylate ester monomer unit, aromatic vinyl compound monomer unit, ethylenically unsaturated nitrile monomer unit, ethylenically unsaturated carboxylic acid (1) or (2), comprising at least one monomer unit selected from an acid monomer unit, an ethylenically unsaturated amide monomer unit, and a polyfunctional ethylene monomer unit
- Electrochemical element electrode binder (4) A particle composite for an electrochemical element electrode obtained by dry-mixing an electrochemical element electrode binder according to any one of (1) to (3) and an electrode active material, (5) The ratio (Da / Db) of the volume-based D50 average particle diameter (Da) of the particle composite for electrochemical element electrodes according to (4) and the volume-based D50 average particle diameter (Db) of the electrode active material ) Is 0.5 to 2, a particle composite for an electrochemical element electrode, (6) An electrochemical element electrode comprising
- An electrochemical device comprising the electrochemical device electrode according to (6) or (7), (9) An aqueous dispersion in which a spherical particulate polymer having a glass transition temperature of 35 to 80 ° C. and a primary particle volume-based D50 average particle diameter of 80 to 1000 nm is dispersed is prepared as a minimum product of the particulate polymer.
- a drying step of obtaining powdered composite particles by drying at a temperature lower than the membrane temperature, a mixing step of dry-mixing the powdered composite particles and the electrode active material to obtain a particle composite, and the particle composite And an electrode manufacturing process for manufacturing the electrode using the method.
- the productivity of the electrode is excellent, and since no water-soluble polymer is required as a dispersant, the resistance can be reduced, and the thickness accuracy of the obtained electrode and Electrochemical element electrode binder having excellent flexibility, electrochemical element electrode particle composite using the electrochemical element electrode binder, electrochemical element electrode and electrochemical element using the electrochemical element electrode particle composite Can be provided. Furthermore, according to this invention, the manufacturing method of the electrochemical element electrode which is excellent in productivity and excellent in thickness precision and a softness
- the binder for an electrochemical element electrode of the present invention (hereinafter sometimes referred to as “binder for electrode”) has a glass transition temperature of 35 to 80 ° C. and a primary particle volume-based D50 average particle diameter of 80 to 1000 nm.
- the volatile matter at 120 ° C. is less than 1% by weight and is a powdered composite particle.
- positive electrode active material means an electrode active material for positive electrode
- negative electrode active material means an electrode active material for negative electrode
- the “positive electrode active material layer” means an electrode active material layer provided on the positive electrode
- the “negative electrode active material layer” means an electrode active material layer provided on the negative electrode.
- the glass transition temperature (Tg) of the electrode binder of the present invention is 35 to 80 ° C., preferably 40 to 75 ° C., more preferably 40 to 70 ° C., still more preferably 40 to 60 ° C., and particularly preferably 45 to 55 ° C. It is.
- Tg glass transition temperature
- the glass transition temperature of the binder for electrodes is within this range, a flexible and sufficiently strong electrode can be obtained.
- the glass transition temperature of the binder for electrodes is too high, it becomes difficult to obtain an electrode having sufficient flexibility.
- liquidity of the particle composite mentioned later is not enough when the glass transition temperature of the binder for electrodes is too low, the thickness precision of the electrode obtained will worsen. That is, thickness unevenness occurs in the electrode.
- the volume-based D50 average particle diameter of the primary particles of the binder for an electrode of the present invention (hereinafter sometimes referred to as “primary particle diameter”) is 80 to 1000 nm, preferably 80 to 800 nm, more preferably 100 to 500 nm, More preferably, it is 130 to 400 nm.
- primary particle diameter of the binder for electrodes is within this range, the adhesive strength between the current collector and the electrode active material can be sufficiently maintained.
- the adhesiveness will fall when the primary particle diameter of the binder for electrodes is too large, when the below-mentioned electrode flexibility test is performed, powder falling occurs.
- the primary particle diameter of the electrode binder is too small, the electrode binder is difficult to disperse, and the adhesiveness is lowered.
- an electrode binder is obtained by drying an aqueous dispersion of a particulate polymer obtained by a polymerization method.
- the primary particle diameter of the particulate polymer in the aqueous dispersion is in the above range. It is.
- the shape of the particulate polymer is preferably spherical.
- the short axis diameter is Ls
- the long axis diameter is Ll
- La (Ls + Ll) / 2
- the value of (1 ⁇ (Ll ⁇ Ls) / La) ⁇ 100 is the degree of sphericity. (%) Means that the sphericity is 80% or more.
- the minor axis diameter Ls and the major axis diameter Ll are measured by observing a photographic image of a transmission or scanning electron microscope, for example, the major axis diameter of a predetermined number of polymer particles such as 10 to 30 particles ( L1) and the average value of the minor axis diameter (Ls).
- the volatile content of the electrode binder of the present invention at 120 ° C. is less than 1% by weight.
- the volatile content of the electrode binder at 120 ° C. is within this range, the electrode binder is uniformly dispersed and an electrode having sufficient strength can be obtained.
- the fluidity of the particle composite described later is improved, an electrode with good thickness accuracy can be obtained.
- the volatile content of the electrode binder at 120 ° C. is too large, the electrode binder does not disperse during the production of the particle composite, so that an electrode having sufficient strength cannot be obtained, and the flow of the particle composite Since the property is not sufficient, the thickness accuracy of the obtained electrode is deteriorated.
- the electrode binder of the present invention exists in the form of a powder having a spherical shape or a shape in which a plurality of spheres are combined (aggregate of spheres), that is, powdered composite particles.
- the primary particles of the electrode binder may exist as individual particles, but usually, a plurality of primary particles are formed by binding with intermolecular force while maintaining the shape. ing.
- grains formed with the several primary particle may exist as an independent particle
- the binder for electrodes of the present invention comprises a conjugated diene monomer unit, a (meth) acrylate monomer unit, an aromatic vinyl compound monomer unit, an ethylenically unsaturated nitrile monomer unit, and an ethylenically unsaturated carboxylic acid. It is preferable to include at least one monomer unit selected from an acid monomer unit, an ethylenically unsaturated amide monomer unit, and a polyfunctional ethylene monomer unit.
- (meth) acryl means “acryl” and “methacryl”.
- conjugated diene monomer forming the conjugated diene monomer unit examples include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene and the like having 4 or more carbon atoms. Conjugated dienes are mentioned. Of these, 1,3-butadiene is preferred.
- (Meth) acrylate monomers that form (meth) acrylate monomer units include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, t-butyl acrylate, pentyl Acrylic acid alkyl esters such as acrylate, hexyl acrylate, heptyl acrylate, octyl acrylate, 2-ethylhexyl acrylate, nonyl acrylate, decyl acrylate, lauryl acrylate, n-tetradecyl acrylate, stearyl acrylate; methyl methacrylate, ethyl methacrylate, n-propyl methacrylate , Isopropyl methacrylate, n-butyl methacrylate, t-butyl methacrylate, pentyl methacrylate Over DOO, hex
- an alkyl acrylate or methacrylic acid alkyl ester having 4 or more carbon atoms in the alkyl group bonded to the carbonyl oxygen atom is preferred, and an alkyl acrylate having an alkyl group bonded to the non-carbonyl oxygen atom having 6 to 20 carbon atoms. More preferred are esters or alkyl methacrylates.
- aromatic vinyl compound monomer forming the aromatic vinyl compound monomer unit examples include styrene, ⁇ -methylstyrene, vinyltoluene and the like.
- the monomer forming the ⁇ , ⁇ -ethylenically unsaturated nitrile monomer unit is not limited as long as it is an ⁇ , ⁇ -ethylenically unsaturated compound having a nitrile group, and acrylonitrile; ⁇ -chloroacrylonitrile, ⁇ - ⁇ -halogenoacrylonitrile such as bromoacrylonitrile; ⁇ -alkylacrylonitrile such as methacrylonitrile; and the like. Acrylonitrile and methacrylonitrile are preferred. These ⁇ , ⁇ -ethylenically unsaturated nitrile monomers may be used in combination.
- Examples of the ethylenically unsaturated carboxylic acid monomer that forms the ethylenically unsaturated carboxylic acid monomer unit include acrylic acid, methacrylic acid, maleic acid, fumaric acid, and itaconic acid.
- Examples of the ethylenically unsaturated amide monomer forming the ethylenically unsaturated amide monomer unit include (meth) acrylamide, N-methylol (meth) acrylamide, N, N′-dimethylol (meth) acrylamide and the like. .
- polyfunctional ethylenically unsaturated monomer having two or more olefinic double bonds that form a polyfunctional ethylenically unsaturated monomer unit examples include divinyl compounds such as divinylbenzene; ethylene di (meth) acrylate, diethylene glycol Di (meth) acrylates such as di (meth) acrylate and ethylene glycol di (meth) acrylate; trimethacrylates such as trimethylolpropane tri (meth) acrylate; and the like.
- a suspension polymerization method (including a fine suspension polymerization method) in which an aqueous dispersion of a particulate polymer is obtained using the above dispersant can be suitably used.
- the emulsion polymerization method is more preferable because the polymerization reaction can be easily controlled.
- the electrode binder of the present invention can be obtained by drying a polymer obtained by polymerizing each monomer. That is, by drying the polymer, an electrode binder (powder binder) which is powdery composite particles can be obtained.
- the drying method is not particularly limited as long as it can be dried in a redispersible state without excessively adhering the primary particles of the particulate polymer, but for example, an aqueous dispersion of the particulate polymer is spray-dried. And a method of drying with a rotary evaporator. Moreover, it is more preferable to dry on a vacuum condition after drying by spray drying or a rotary evaporator.
- the drying temperature is lower than the minimum film-forming temperature of the particulate polymer from the viewpoint of removing moisture in a redispersible state without excessively adhering the primary particles of the particulate polymer. It is preferable. If the drying temperature is too high, it becomes difficult to redisperse because the particulate polymer forms a film.
- the minimum film-forming temperature of the particulate polymer can be dried in a state where the particulate polymer can be redispersed, and both the fluidity of the particle composite described later and the flexibility of the electrode after electrode formation can be achieved. From a possible viewpoint, it is preferably 35 to 100 ° C. When the minimum film-forming temperature of the particulate polymer is too high, the flexibility of the obtained electrode is lowered. Moreover, when the minimum film forming temperature of a particulate polymer is too low, it will become difficult to dry so that the primary particle of a particulate polymer may not adhere too much. That is, it becomes difficult to dry the particulate polymer in a redispersible state.
- the minimum film-forming temperature is the minimum temperature at which the particulate polymer film is formed.
- the minimum film forming temperature can be measured according to, for example, JIS K6828-2 (2003) or ISO 2115. Specifically, an aqueous dispersion of a particulate polymer is applied and dried to a thickness of about 100 ⁇ m on a flat plate such as an iron plate having an appropriate temperature gradient, and a filmed portion and a non-filmed portion Measure the boundary temperature.
- the filmed portion becomes transparent, and the non-filmed portion becomes cloudy. Therefore, the boundary between the filmed portion and the non-filmed portion can be visually confirmed.
- the part that is not filmed will fall off, so the part that is filmed and the part that is not filmed depending on the presence or absence of powdering Can be confirmed.
- the particle composite for electrochemical device electrodes of the present invention (hereinafter sometimes referred to as “particle composite”) comprises the above-mentioned binder for electrodes and an electrode active material.
- the particle composite may include a conductive agent as necessary.
- each of the electrode binder and the electrode active material may exist as independent particles, but usually a plurality of electrode binders are attached to the surface of the electrode active material. Particles are formed. A plurality of individual particles of the electrode binder and the electrode active material and the one particle are bonded together to form secondary particles in a state where the shape is substantially maintained.
- the primary particles may exist as independent particles.
- Electrode active material As the positive electrode active material when the electrochemical device of the present invention is a lithium ion secondary battery, an active material capable of doping and dedoping lithium ions is used, and the positive electrode active material is composed of an inorganic compound and an organic compound. Broadly divided.
- Examples of the positive electrode active material made of an inorganic compound include transition metal oxides, transition metal sulfides, lithium-containing composite metal oxides of lithium and transition metals, and the like.
- Examples of the transition metal include Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Mo.
- Transition metal oxides include MnO, MnO 2 , V 2 O 5 , V 6 O 13 , TiO 2 , Cu 2 V 2 O 3 , amorphous V 2 O—P 2 O 5 , MoO 3 , V 2 O. 5 , V 6 O 13 and the like. Among them, MnO, V 2 O 5 , V 6 O 13 and TiO 2 are preferable from the viewpoint of cycle stability and capacity.
- the lithium-containing composite metal oxide include a lithium-containing composite metal oxide having a layered structure, a lithium-containing composite metal oxide having a spinel structure, and a lithium-containing composite metal oxide having an olivine structure.
- lithium-containing composite metal oxide having a layered structure examples include lithium-containing cobalt oxide (LiCoO 2 ), lithium-containing nickel oxide (LiNiO 2 ), Co—Ni—Mn lithium composite oxide, and Ni—Mn—Al lithium. Examples thereof include composite oxides and lithium composite oxides of Ni—Co—Al. Examples of the lithium-containing composite metal oxide having a spinel structure include lithium manganate (LiMn 2 O 4 ) and Li [Mn 3/2 M 1/2 ] O 4 in which a part of Mn is substituted with another transition metal (here, M may be Cr, Fe, Co, Ni, Cu or the like.
- Li x MPO 4 (wherein, M is Mn, Fe, Co, Ni, Cu, Mg, Zn, V, Ca, Sr, Ba, Ti, Al, and the like) is a lithium-containing composite metal oxide having an olivine structure.
- An olivine type lithium phosphate compound represented by at least one selected from Si, B, and Mo, 0 ⁇ X ⁇ 2) may be mentioned.
- a conductive polymer such as polyacetylene or poly-p-phenylene can be used.
- An iron-based oxide having poor electrical conductivity may be used as a positive electrode active material covered with a carbon material by allowing a carbon source material to be present during reduction firing. These compounds may be partially element-substituted.
- the positive electrode active material may be a mixture of the above inorganic compound and organic compound.
- the positive electrode active material may be any material that can reversibly carry lithium ions and anions such as tetrafluoroborate.
- carbon allotropes can be preferably used, and electrode active materials used in electric double layer capacitors can be widely used.
- Specific examples of the allotrope of carbon include activated carbon, polyacene (PAS), carbon whisker, carbon nanotube, and graphite.
- Examples of the negative electrode active material when the electrochemical device of the present invention is a lithium ion secondary battery include carbonaceous materials such as amorphous carbon, graphite, natural graphite, mesocarbon microbeads, pitch-based carbon fibers; Conductive polymers; metals such as silicon, tin, zinc, manganese, iron, nickel or alloys thereof; oxides or sulfates of the metals or alloys; metal lithium; Li—Al, Li—Bi—Cd, Li— Examples thereof include lithium alloys such as Sn—Cd; lithium transition metal nitrides; silicon and the like.
- a material obtained by attaching a conductive agent to the surface of the negative electrode active material particles by, for example, a mechanical modification method may be used.
- a negative electrode active material may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.
- examples of the negative electrode active material preferably used when the electrochemical element is a lithium ion capacitor include the negative electrode active material formed of carbon.
- the particle diameter of the electrode active material particles is usually selected as appropriate in consideration of other components of the electrochemical element. Among these, from the viewpoint of improving battery characteristics such as initial efficiency, load characteristics, and cycle characteristics, the volume-based D50 average particle diameter of the electrode active material particles is preferably 1 to 50 ⁇ m, more preferably 15 to 30 ⁇ m.
- the content of the electrode active material in the electrode active material layer can increase the capacity of the lithium ion secondary battery, and improve the flexibility of the electrode and the binding property between the current collector and the electrode active material layer. From the viewpoint of achieving the above, it is preferably 90 to 99.9% by weight, more preferably 95 to 99% by weight.
- the conductive agent used as necessary in the present invention furnace black, acetylene black (hereinafter sometimes abbreviated as “AB”), and ketjen black (Akzo Nobel Chemicals Bethloten Fennaut Shap Co., Ltd.) (Registered trademark), carbon nanotubes, carbon nanohorns, graphene and other conductive carbons are preferably used. Among these, acetylene black is more preferable.
- the average particle diameter of the conductive agent is not particularly limited, but is preferably smaller than the average particle diameter of the electrode active material, preferably 0.001 to 10 ⁇ m, from the viewpoint of expressing sufficient conductivity with a smaller amount of use. More preferably, the thickness is 0.005 to 5 ⁇ m, and still more preferably 0.01 to 1 ⁇ m.
- the amount of the conductive agent used is preferably 1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the electrode active material.
- the particle composite can be obtained by dry-mixing an electrode binder, an electrode active material, and a conductive agent used as necessary.
- dry mixing refers to mixing an electrode binder, an electrode active material, and a conductive agent used as necessary using a mixer. Specifically, the solid content concentration during mixing is 99. It means mixing at weight% or more.
- a container stirring method using a rocking mixer, a tumbler mixer or the like that is mixed by shaking, rotating, or vibrating the container itself;
- Horizontal cylindrical mixer, V-type mixer, ribbon-type mixer, conical-type screw mixer, high-speed flow-type mixer, rotation which is a mixer equipped with blades, rotating disk or screw for stirring And mechanical stirring using a disk-type mixer and a high-speed rotating blade mixer; and airflow stirring using a swirling airflow by compressed gas to mix powder in a fluidized bed.
- the ratio (Da / Db) between the volume-based D50 average particle diameter (Da) of the particle composite of the present invention and the volume-based D50 average particle diameter (Db) of the electrode active material is preferably 0.5-2. More preferably, it is 0.8-2. That is, it is preferable that a plurality of electrode active materials are not combined.
- the electrochemical element electrode of the present invention is an electrode formed by laminating an electrode active material layer containing the above-described particle composite on a current collector.
- a material for the current collector for example, metal, carbon, conductive polymer, and the like can be used, and metal is preferably used.
- metal copper, aluminum, platinum, nickel, tantalum, titanium, stainless steel, other alloys and the like are usually used. Among these, it is preferable to use copper, aluminum, or an aluminum alloy in terms of conductivity and voltage resistance. In addition, when high voltage resistance is required, high-purity aluminum disclosed in JP 2001-176757 A can be suitably used.
- the current collector is in the form of a film or a sheet, and the thickness thereof is appropriately selected depending on the purpose of use, but is preferably 1 to 200 ⁇ m, more preferably 5 to 100 ⁇ m, and still more preferably 10 to 50 ⁇ m.
- the particle composite When the electrode active material layer is laminated on the current collector, the particle composite may be formed into a sheet and then laminated on the current collector. However, the particle composite may be directly applied on the current collector.
- a pressure forming method is preferred. As a method for pressure molding, for example, a roll type pressure molding apparatus having a pair of rolls is used, and a particle complex is rolled by pressure molding with a supply device such as a screw feeder while feeding a current collector with the roll.
- roll press molding method for forming the electrode active material layer on the current collector or by dispersing the particle composite on the current collector
- examples thereof include a method of adjusting and then forming with a pressurizing apparatus, a method of filling a particle composite into a mold, and pressing the mold to form.
- the roll pressure molding method is preferable.
- the particle composite of the present invention since the particle composite of the present invention has high fluidity, it can be molded by roll pressure molding after the powder layer is made uniform by supplying with a quantitative feeder or a blade, etc. Thereby, productivity can be improved.
- the roll temperature at the time of roll press molding is preferably 25 to 200 ° C., more preferably 50 to 150 ° C., from the viewpoint of ensuring sufficient adhesion between the electrode active material layer and the current collector. More preferably, it is 80 to 120 ° C.
- the press linear pressure between the rolls during roll pressing is preferably 10 to 1000 kN / m, more preferably 200 to 900 kN / m, from the viewpoint of improving the uniformity of the thickness of the electrode active material layer. More preferably, it is 300 to 600 kN / m.
- the molding speed at the time of roll press molding is preferably 0.1 to 20 m / min, more preferably 4 to 10 m / min.
- post-pressurization may be further performed as necessary in order to eliminate variations in the thickness of the formed electrochemical element electrode and increase the density of the electrode active material layer to increase the capacity.
- the post-pressing method is preferably a pressing process using a roll.
- the roll pressing step two cylindrical rolls are arranged vertically in parallel with a narrow interval, each is rotated in the opposite direction, and pressure is applied by interposing an electrode therebetween.
- the temperature of the roll may be adjusted as necessary, such as heating or cooling.
- the electrochemical device of the present invention uses the electrochemical device electrode obtained as described above as at least one of a positive electrode and a negative electrode, and further includes a separator and an electrolytic solution.
- the electrochemical element include a lithium ion secondary battery and a lithium ion capacitor.
- separator for example, a polyolefin resin such as polyethylene or polypropylene, or a microporous film or nonwoven fabric containing an aromatic polyamide resin; a porous resin coat containing an inorganic ceramic powder; Specific examples include microporous membranes made of polyolefin resins (polyethylene, polypropylene, polybutene, polyvinyl chloride), and resins such as mixtures or copolymers thereof; polyethylene terephthalate, polycycloolefin, polyether sulfone, polyamide, Examples thereof include a microporous film made of a resin such as polyimide, polyimide amide, polyaramid, polycycloolefin, nylon, and polytetrafluoroethylene; a polyolefin fiber woven or non-woven fabric thereof; an aggregate of insulating substance particles, and the like.
- a polyolefin resin such as polyethylene or polypropylene, or a microporous film or nonwoven fabric containing
- the thickness of the separator is preferably 0.5 to 40 ⁇ m from the viewpoint of reducing the internal resistance due to the separator in the lithium ion secondary battery and from the viewpoint of excellent workability when manufacturing the lithium ion secondary battery. More preferably, the thickness is 1 to 30 ⁇ m, still more preferably 1 to 25 ⁇ m.
- Electrode As an electrolytic solution for a lithium ion secondary battery, for example, a nonaqueous electrolytic solution in which a supporting electrolyte is dissolved in a nonaqueous solvent is used.
- a lithium salt is preferably used.
- the lithium salt include LiPF 6 , LiAsF 6 , LiBF 4 , LiSbF 6 , LiAlCl 4 , LiClO 4 , CF 3 SO 3 Li, C 4 F 9 SO 3 Li, CF 3 COOLi, (CF 3 CO) 2 NLi , (CF 3 SO 2 ) 2 NLi, (C 2 F 5 SO 2 ) NLi, and the like.
- LiPF 6 , LiClO 4 , and CF 3 SO 3 Li that are easily soluble in a solvent and exhibit a high degree of dissociation are preferable.
- One of these may be used alone, or two or more of these may be used in combination at any ratio. Since the lithium ion conductivity increases as the supporting electrolyte having a higher degree of dissociation is used, the lithium ion conductivity can be adjusted depending on the type of the supporting electrolyte.
- the concentration of the supporting electrolyte in the electrolytic solution is preferably used at a concentration of 0.5 to 2.5 mol / L depending on the type of the supporting electrolyte. If the concentration of the supporting electrolyte is too low or too high, the ionic conductivity may decrease.
- the non-aqueous solvent is not particularly limited as long as it can dissolve the supporting electrolyte.
- non-aqueous solvents include carbonates such as dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC), propylene carbonate (PC), butylene carbonate (BC), methyl ethyl carbonate (MEC);
- DMC dimethyl carbonate
- EC ethylene carbonate
- DEC diethyl carbonate
- PC propylene carbonate
- BC butylene carbonate
- MEC methyl ethyl carbonate
- esters such as ⁇ -butyrolactone and methyl formate
- ethers such as 1,2-dimethoxyethane and tetrahydrofuran
- sulfur-containing compounds such as sulfolane and dimethyl sulfoxide
- ionic liquids used also as supporting electrolytes used also as supporting electrolytes.
- a non-aqueous solvent may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. In general, the lower the viscosity of the non-aqueous solvent, the higher the lithium ion conductivity, and the higher the dielectric constant, the higher the solubility of the supporting electrolyte, but since both are in a trade-off relationship, the lithium ion conductivity depends on the type of solvent and the mixing ratio. It is recommended to adjust the conductivity.
- the nonaqueous solvent may be used in combination or in whole or in a form in which all or part of hydrogen is replaced with fluorine.
- the electrolyte solution may contain an additive.
- the additive include carbonates such as vinylene carbonate (VC); sulfur-containing compounds such as ethylene sulfite (ES); and fluorine-containing compounds such as fluoroethylene carbonate (FEC).
- An additive may be used individually by 1 type and may be used combining two or more types by arbitrary ratios.
- an electrolyte solution for lithium ion capacitors the same electrolyte solution that can be used for the above-described lithium ion secondary battery can be used.
- Method for producing electrochemical element As a specific method for producing an electrochemical element such as a lithium ion secondary battery or a lithium ion capacitor, for example, a positive electrode and a negative electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery. Examples of the method include putting the battery in a battery container, injecting an electrolyte into the battery container, and sealing the battery. Further, if necessary, an expanded metal; an overcurrent prevention element such as a fuse or a PTC element; a lead plate or the like may be inserted to prevent an increase in pressure inside the battery or overcharge / discharge.
- an electrochemical element such as a lithium ion secondary battery or a lithium ion capacitor
- a positive electrode and a negative electrode are overlapped via a separator, and this is wound or folded according to the shape of the battery. Examples of the method include putting the battery in a battery container, injecting an electrolyte into the battery container, and sealing the battery. Further, if necessary, an
- the shape of the lithium ion secondary battery may be any of a coin type, a button type, a sheet type, a cylindrical type, a square type, a flat type, and the like.
- the material of the battery container is not particularly limited as long as it inhibits the penetration of moisture into the battery, and is not particularly limited, such as a metal or a laminate such as aluminum.
- the electrochemical element electrode binder according to the present embodiment has excellent electrode productivity and good thickness accuracy and flexibility of the obtained electrode. Moreover, since the electrochemical element electrode of the present invention does not use a dispersant such as carboxymethylcellulose, the resistance of the obtained electrochemical element can be lowered.
- the glass transition temperature of the binder for an electrode within a predetermined range, fluidity can be ensured even if the obtained particle composite has a small particle size, so that the thickness accuracy of the electrode can be ensured. it can. Furthermore, the strength and flexibility of the obtained electrode can be ensured by setting the glass transition temperature of the binder for electrochemical element electrodes within a predetermined range.
- Tg glass transition temperature
- primary particle diameter primary particle diameter
- particle composite Measurement of volume-based D50 average particle diameter (Da) and electrode active material volume-based D50 average particle diameter (Db)
- measurement of 120 ° C. volatile content of electrode binder measurement of minimum film-forming temperature of electrode binder, and The shape measurement of the electrode binder was performed as follows.
- the glass transition temperature (Tg) of the binder for electrodes was measured based on JIS K 7121: 1987 using a differential scanning calorimeter (DSC6220SII manufactured by Nanotechnology).
- binders for electrodes (negative electrode binders 1 to 12 and positive electrode binders 1 to 13) prepared in Examples and Comparative Examples were added to 1% aqueous sodium alkylbenzene sulfonate solutions and dispersed by ultrasonic waves. Then, the particle size corresponding to the 50% integral value was measured by an integrated particle size distribution using a Coulter Counter LS230 (Coulter particle size measuring device), and the volume-based D50 average particle size (primary particle size) of the electrode binder. It was.
- Da volume-based D50 average particle diameter of particle composites produced in Examples and Comparative Examples by dry-type integral particle size distribution using a laser diffraction / scattering type particle size distribution measuring device (Microtrac MT3200II; Nikkiso), and Examples
- Db volume-based D50 average particle diameter of the electrode active material used in the comparative example was measured, and the ratio (Da / Db) was determined.
- ⁇ Minimum film forming temperature> A test was conducted in accordance with ISO 2115 using a minimum film forming temperature measuring device (MFFTB90; manufactured by RHOPOINT).
- ⁇ Shape measurement> The powder electrode binder was observed with an SEM, and 30 particles visible in the image were randomly taken out, and the average minor axis diameter and average major axis diameter of each particle were determined to calculate the average sphericity. At this time, when the average sphericity was 80% or more, it was spherical, and when the average sphericity was less than 80%, it was non-spherical.
- the electrode accuracy, electrode flexibility, and rate characteristics were evaluated as follows.
- Electrode thickness unevenness accuracy (
- the laminated cell type lithium ion secondary batteries produced in the examples and comparative examples were allowed to stand for 5 hours after injecting the electrolyte, and the cell voltage was 3.65 V by a constant current method of 0.2 C in an atmosphere at 25 ° C. Then, the temperature was raised to 60 ° C., an aging treatment was performed for 12 hours, and a cell voltage was discharged to 3.00 V by a constant current method of 0.2 C in an atmosphere at 25 ° C.
- Example 1 (Production of particulate polymer 1 for negative electrode)
- ST styrene
- BD 1,3-butadiene
- IA itaconic acid
- ST styrene
- IA itaconic acid
- IA alkyldiphenyl oxide disulfonate
- TDM t-dodecyl mercaptan
- particulate polymer 1 for negative electrode styrene / butadiene copolymer; hereinafter sometimes abbreviated as “SBR”).
- SBR styrene / butadiene copolymer
- the particle composite obtained above is subjected to a press roll (roll) using a quantitative feeder (“Nicker Spray K-V” manufactured by Nikka Co., Ltd.) and a roll press machine (“Press-Roughened Surface Heat Roll” manufactured by Hiran Giken Co., Ltd.).
- the temperature was 100 ° C. and the press linear pressure was 500 kN / m.
- a copper foil having a thickness of 20 ⁇ m is inserted between press rolls, the particle composite supplied from the quantitative feeder is adhered onto the copper foil, and pressure-molded at a molding speed of 1.5 m / min.
- the negative electrode which has this was obtained.
- a single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 ⁇ m, manufactured by dry method, porosity 55%) was cut into a square of 5 ⁇ 5 cm 2 .
- An aluminum packaging exterior was prepared as the battery exterior.
- the positive electrode obtained above was cut into a 4 ⁇ 4 cm 2 square and placed so that the current collector-side surface was in contact with the aluminum packaging exterior.
- the square separator obtained above was arrange
- the negative electrode obtained above was cut into a square of 4.2 ⁇ 4.2 cm 2 and arranged on the separator so that the surface on the negative electrode active material layer side faced the separator.
- a LiPF 6 solution having a concentration of 1.0 mol / L and containing 2.0% of vinylene carbonate was charged.
- Example 2 (Production of particulate polymer 2 for negative electrode)
- 74.5 parts of styrene, 22.5 parts of 1,3-butadiene, 3 parts of itaconic acid, alkyldiphenyl oxide disulfonate as an emulsifier (Dowfax (registered trademark) 2A1, manufactured by Dow Chemical Company) was added in an amount of 0.4 part in terms of solid content, 150 parts of ion-exchanged water, 0.3 part of t-dodecyl mercaptan as a chain transfer agent and 0.5 part of potassium persulfate as a polymerization initiator, and after sufficient stirring, The polymerization was started by heating to 75 ° C.
- the reaction was stopped by cooling to obtain an aqueous dispersion of particulate polymer 2 for negative electrode.
- the minimum film-forming temperature of the particulate polymer 2 was 40 ° C.
- the glass transition temperature (Tg) was 40 ° C.
- the primary particle diameter was 135 nm.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 2 was used.
- Example 3> (Production of particulate polymer 3 for negative electrode)
- the reaction was stopped by cooling to obtain an aqueous dispersion of the particulate polymer 3 for negative electrode.
- the minimum film-forming temperature of the particulate polymer 3 for negative electrode was 88 ° C.
- the glass transition temperature (Tg) was 70 ° C.
- the primary particle size was 134 nm.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 3 was used.
- Example 4 (Production of particulate polymer 4 for negative electrode)
- a 5 MPa pressure vessel with a stirrer 78 parts of styrene, 19 parts of 1,3-butadiene, 3 parts of itaconic acid, and alkyldiphenyl oxide disulfonate (Dowfax (registered trademark) 2A1, manufactured by Dow Chemical Co., Ltd.) as an emulsifier 2.0 parts by weight, 150 parts of ion-exchanged water, 0.3 part of t-dodecyl mercaptan as a chain transfer agent and 0.5 part of potassium persulfate as a polymerization initiator were stirred sufficiently, and then heated to 75 ° C.
- the polymerization was started by warming. When the polymerization conversion rate reached 96%, the reaction was stopped by cooling to obtain an aqueous dispersion of the particulate polymer 4 for negative electrode.
- the minimum film forming temperature of the particulate polymer 4 for the negative electrode was 53 ° C.
- the glass transition temperature (Tg) was 50 ° C.
- the primary particle diameter was 80 nm.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 4 was used.
- Example 5 (Production of particulate polymer 5 for negative electrode) In a 5 MPa pressure vessel equipped with a stirrer, 210 parts of ion-exchanged water was charged, heated to 75 ° C. with stirring, and 25.5 parts of a 1.96% aqueous potassium persulfate solution was added to the reactor.
- an aqueous dispersion of the particulate polymer 5 for negative electrode was obtained.
- the minimum film forming temperature of the particulate polymer 5 for negative electrode was 56 ° C.
- the glass transition temperature (Tg) was 50 ° C.
- the primary particle diameter was 304 nm.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 5 was used.
- Example 6 (Production of particulate polymer 6 for negative electrode) In a 5 MPa pressure vessel equipped with a stirrer, 210 parts of ion-exchanged water was charged, heated to 75 ° C. with stirring, and 25.5 parts of a 1.96% aqueous potassium persulfate solution was added to the reactor.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 6 was used.
- Example 7 Water was removed from the aqueous dispersion of the particulate polymer 1 for negative electrode at 40 ° C. using a rotary evaporator. Thereafter, the particulate polymer was dried and crushed in the same manner as in Example 1 except that drying under conditions of 40 ° C. and 0.6 kPa was not performed in a vacuum dryer, and the powdered negative electrode binder 7 Got. The 120 ° C. volatile content of the powdered negative electrode binder 7 was 0.8%.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 7 was used.
- the reaction was stopped by cooling to obtain an aqueous dispersion of the particulate polymer 7 for negative electrode.
- the minimum film-forming temperature of the particulate polymer 7 for negative electrode was 27 ° C.
- the glass transition temperature (Tg) was 30 ° C.
- the primary particle diameter was 130 nm.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 8 was used.
- the reaction was stopped by cooling to obtain an aqueous dispersion of the particulate polymer 8 for negative electrode.
- the minimum film-forming temperature of the particulate polymer 8 for negative electrode was 120 ° C.
- the glass transition temperature (Tg) was 100 ° C.
- the primary particle size was 135 nm.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 9 was used.
- ⁇ Comparative Example 3> (Production of particulate polymer 9 for negative electrode) Toluene was added at a weight ratio of 100 parts with respect to 10 parts by weight of polymer to the aqueous dispersion of particulate polymer 1 for negative electrode, and emulsified at 15000 rpm with an emulsifying dispersion device (Milder MDN303V; manufactured by Taiheiyo Kiko Co., Ltd.). did. Thereafter, the solvent was removed from the emulsion using a rotary evaporator to obtain an aqueous dispersion of the particulate polymer 9 for negative electrode.
- the minimum film-forming temperature of the particulate polymer 9 for the negative electrode was 53 ° C.
- the glass transition temperature (Tg) was 50 ° C.
- the primary particle size was 3020 nm.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 10 was used.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 11 was used.
- the negative electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 1 except that the negative electrode binder 12 was used.
- Example 8> (Production of particulate polymer 1 for positive electrode) A reactor equipped with a mechanical stirrer and a condenser was charged with 210 parts of ion-exchanged water in a nitrogen atmosphere, heated to 70 ° C. with stirring, and 25.5 parts of a 1.96% aqueous potassium persulfate solution was added to the reactor. . Next, 20 parts of butyl acrylate (hereinafter sometimes abbreviated as “BA”) and ethyl methacrylate (hereinafter abbreviated as “EMA”) in a container different from the above equipped with a mechanical stirrer under a nitrogen atmosphere.
- BA butyl acrylate
- EMA ethyl methacrylate
- MAA methacrylic acid
- AMA allyl methacrylate
- emulsifier 1.0 part in terms of solid content, and 22.7 parts of ion-exchanged water
- the polymerization conversion rate was obtained until an aqueous dispersion of the particulate polymer 1 for positive electrode (acrylic polymer; hereinafter sometimes abbreviated as “acrylic”) was obtained.
- the minimum film forming temperature of the particulate polymer 1 for positive electrodes was 45 degreeC
- the glass transition temperature (Tg) was 40 degreeC
- the primary particle diameter was 310 nm.
- the aqueous dispersion of the particulate polymer 1 for positive electrode is sprayed using a rotating disk type atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed, and the obtained particles were dried under the conditions of 30 ° C. and 0.6 kPa in a vacuum dryer to obtain a powdered positive electrode binder 1.
- the 120 ° C. volatile content of the powdered positive electrode binder 1 was 0.1%.
- the particle composite obtained above is subjected to a press roll (roll) using a quantitative feeder (“Nicker Spray K-V” manufactured by Nikka Co., Ltd.) and a roll press machine (“Press-Roughened Surface Heat Roll” manufactured by Hiran Giken Co., Ltd.).
- the temperature was 100 ° C. and the press linear pressure was 500 kN / m.
- An aluminum foil having a thickness of 20 ⁇ m is inserted between press rolls, the above-mentioned particle composite supplied from a quantitative feeder is adhered onto the aluminum foil, and press-molded at a molding speed of 1.5 m / min.
- a single-layer polypropylene separator (width 65 mm, length 500 mm, thickness 25 ⁇ m, manufactured by dry method, porosity 55%) was cut into a square of 5 ⁇ 5 cm 2 .
- An aluminum packaging exterior was prepared as the battery exterior.
- the positive electrode obtained above was cut into a 4 ⁇ 4 cm 2 square and placed so that the current collector-side surface was in contact with the aluminum packaging exterior.
- the square separator obtained above was arrange
- the negative electrode obtained above was cut into a square of 4.2 ⁇ 4.2 cm 2 and arranged on the separator so that the surface on the negative electrode active material layer side faced the separator.
- a LiPF 6 solution having a concentration of 1.0 mol / L and containing 2.0% of vinylene carbonate was charged.
- Example 9 (Production of particulate polymer 2 for positive electrode) A reactor equipped with a mechanical stirrer and a condenser was charged with 210 parts of ion-exchanged water in a nitrogen atmosphere, heated to 70 ° C. with stirring, and 25.5 parts of a 1.96% aqueous potassium persulfate solution was added to the reactor. .
- the polymerization conversion rate was reacted until the water content became 95% to obtain an aqueous dispersion of the particulate polymer 2 for positive electrode.
- the minimum film forming temperature of the particulate polymer 2 for positive electrodes was 52 degreeC
- the glass transition temperature (Tg) was 50 degreeC
- the primary particle diameter was 319 nm.
- the aqueous dispersion of the above-mentioned positive electrode particulate polymer 2 is sprayed using a rotating disk type atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed, and the obtained particles were dried in a vacuum dryer under the conditions of 40 ° C. and 0.6 kPa to obtain a powdered positive electrode binder 2.
- the 120 ° C. volatile content of the powdered positive electrode binder 2 was 0.1%.
- the production of the positive electrode and the production of the lithium ion secondary battery were carried out in the same manner as in Example 8 except that the positive electrode binder 2 was used.
- Example 10> (Production of particulate polymer 3 for positive electrode) A reactor equipped with a mechanical stirrer and a condenser was charged with 210 parts of ion-exchanged water in a nitrogen atmosphere, heated to 70 ° C. with stirring, and 25.5 parts of a 1.96% aqueous potassium persulfate solution was added to the reactor. .
- the polymerization conversion rate was reacted until the water content became 95% to obtain an aqueous dispersion of the particulate polymer 3 for positive electrode.
- the minimum film forming temperature of the particulate polymer 3 for positive electrodes was 65 degreeC
- the glass transition temperature (Tg) was 60 degreeC
- the primary particle diameter was 331 nm.
- the aqueous dispersion of the positive electrode particulate polymer 3 is sprayed in a spray dryer (Okawara Chemical Co., Ltd.) using a rotating disk atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed, and the obtained particles were dried in a vacuum dryer under the conditions of 40 ° C. and 0.6 kPa to obtain a powdered positive electrode binder 3.
- the 120 ° C. volatile content of the powdered positive electrode binder 3 was 0.1%.
- the positive electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 8 except that the positive electrode binder 3 was used.
- Example 11 (Production of particulate polymer 4 for positive electrode)
- a reactor equipped with a mechanical stirrer and a condenser 210 parts of ion-exchanged water and a 30% concentration of alkyldiphenyl oxide disulfonate (Dowfax (registered trademark) 2A1, manufactured by Dow Chemical Co., Ltd.) as a solid content in a nitrogen atmosphere
- Dowfax (registered trademark) 2A1 manufactured by Dow Chemical Co., Ltd.
- the polymerization conversion rate was reacted until the water content became 95% to obtain an aqueous dispersion of the particulate polymer 4 for positive electrode.
- the minimum film forming temperature of the particulate polymer 4 for positive electrodes was 43 degreeC
- the glass transition temperature (Tg) was 40 degreeC
- the primary particle diameter was 139 nm.
- the aqueous dispersion of the particulate polymer 4 for positive electrode is sprayed in a spray dryer (Okawara Chemical Co., Ltd.) using a rotating disk type atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed, and the obtained particles were dried in a vacuum dryer at 30 ° C. and 0.6 kPa, thereby obtaining a powdery positive electrode binder 4.
- the 120 ° C. volatile content of the powdered positive electrode binder 4 was 0.1%.
- the positive electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 8 except that the positive electrode binder 4 was used.
- Example 12 (Production of particulate polymer 5 for positive electrode)
- a reactor equipped with a mechanical stirrer and a condenser 210 parts of ion-exchanged water and a 30% concentration of alkyldiphenyl oxide disulfonate (Dowfax (registered trademark) 2A1, manufactured by Dow Chemical Co., Ltd.) as a solid content in a nitrogen atmosphere
- An appropriate amount of 0.8 parts was charged, heated to 70 ° C. with stirring, and 25.5 parts of a 1.96% aqueous potassium persulfate solution was added to the reactor.
- the monomer mixture in a state of stirring and emulsifying the monomer mixture, it was added to a reactor charged with 210 parts of ion exchange water and an aqueous potassium persulfate solution at a constant rate over 2.5 hours, and the polymerization conversion rate To 95%, an aqueous dispersion of the particulate polymer 5 for positive electrode was obtained.
- the minimum film forming temperature of the particulate polymer 5 for positive electrodes was 43 degreeC
- the glass transition temperature (Tg) was 40 degreeC
- the primary particle diameter was 100 nm.
- the aqueous dispersion of the above-mentioned positive electrode particulate polymer 5 is sprayed in a spray dryer (made by Okawahara Chemical Co., Ltd.) using a rotating disk type atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed, and the obtained particles were dried under the conditions of 30 ° C. and 0.6 kPa in a vacuum dryer to obtain a powdered positive electrode binder 5.
- the 120 ° C. volatile content of the powdered positive electrode binder 5 was 0.1%.
- the positive electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 8, except that the positive electrode binder 5 was used.
- Example 13> (Production of particulate polymer 6 for positive electrode) A reactor equipped with a mechanical stirrer and a condenser was charged with 210 parts of ion-exchanged water in a nitrogen atmosphere, heated to 70 ° C. with stirring, and 25.5 parts of a 1.96% aqueous potassium persulfate solution was added to the reactor. .
- the polymerization conversion rate was reacted until the water content became 95% to obtain an aqueous dispersion of the particulate polymer 6 for positive electrode.
- the minimum film forming temperature of the particulate polymer 6 for positive electrodes was 48 degreeC
- the glass transition temperature (Tg) was 40 degreeC
- the primary particle diameter was 625 nm.
- the aqueous dispersion of the above-mentioned positive electrode particulate polymer 6 is sprayed in a spray dryer (Okawara Chemical Co., Ltd.) using a rotating disk type atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed, and the obtained particles were dried under the conditions of 30 ° C. and 0.6 kPa in a vacuum dryer to obtain a powdery positive electrode binder 6.
- the 120 ° C. volatile content of the powdered positive electrode binder 6 was 0.1%.
- the positive electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 8 except that the positive electrode binder 6 was used.
- Example 14 In the spray dryer (made by Okawahara Kako Co., Ltd.), the aqueous dispersion of the particulate polymer 1 for positive electrode is sprayed using a rotating disk type atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed to obtain particles. Thereafter, the particulate polymer was dried in the same manner as in Example 8 except that the obtained particles were not dried under the conditions of 30 ° C. and 0.6 kPa in a vacuum dryer. Binder 7 was obtained. The 120 ° C. volatile content of the powdered positive electrode binder 7 was 0.8%.
- the positive electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 8 except that the positive electrode binder 7 was used.
- the polymerization conversion rate was reacted until the water content became 95% to obtain an aqueous dispersion of the particulate polymer 7 for positive electrode.
- the minimum film forming temperature of the particulate polymer 7 for positive electrodes was 27 degreeC
- the glass transition temperature (Tg) was 30 degreeC
- the primary particle diameter was 307 nm.
- the aqueous dispersion of the above-mentioned positive electrode particulate polymer 7 is sprayed in a spray dryer (made by Okawahara Chemical Co., Ltd.) using a rotating disk type atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed, and the obtained particles were dried under the conditions of 25 ° C. and 0.6 kPa in a vacuum dryer to obtain a powdered positive electrode binder 8.
- the 120 ° C. volatile content of the powdered positive electrode binder 8 was 0.1%.
- the positive electrode and the lithium ion secondary battery were manufactured in the same manner as in Example 8 except that the positive electrode binder 8 was used.
- the polymerization conversion rate was reacted until the water content became 95% to obtain an aqueous dispersion of the particulate polymer 8 for positive electrode.
- the minimum film forming temperature of the particulate polymer 8 for positive electrodes was 115 degreeC
- the glass transition temperature (Tg) was 100 degreeC
- the primary particle diameter was 280 nm.
- the aqueous dispersion of the positive electrode particulate polymer 8 is sprayed in a spray dryer (Okawara Chemical Co., Ltd.) using a rotating disk type atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed, and the obtained particles were dried under the conditions of 80 ° C. and 0.6 kPa in a vacuum dryer to obtain a powdered positive electrode binder 9.
- the 120 degreeC volatile matter of the binder 9 for powdery positive electrodes was 0.1%.
- the positive electrode and lithium ion secondary battery were manufactured in the same manner as in Example 8 except that the positive electrode binder 9 was used.
- ⁇ Comparative Example 8> (Production of particulate polymer 9 for positive electrode)
- a reactor equipped with a mechanical stirrer and a condenser 831 parts of ion-exchanged water and 30% alkyldiphenyl oxide disulfonate (Dowfax (registered trademark) 2A1, manufactured by Dow Chemical Co., Ltd.) as an emulsifier in a nitrogen atmosphere
- Add 10 parts in a substantial amount add 6 parts butyl acrylate, 91.5 parts ethyl methacrylate, 2.4 parts methacrylic acid, 0.1 parts allyl methacrylate, and stir emulsify the monomer mixture. It was. This was heated to 60 ° C.
- the minimum film forming temperature of the particulate polymer 9 for positive electrodes was 42 degreeC
- the glass transition temperature (Tg) was 60 degreeC
- the primary particle diameter was 50 nm.
- the aqueous dispersion of the above-mentioned positive electrode particulate polymer 9 is sprayed in a spray dryer (made by Okawahara Chemical Co., Ltd.) using a rotating disk type atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed, and the obtained particles were dried by a vacuum dryer under the conditions of 40 ° C. and 0.6 kPa to obtain a powdered positive electrode binder 10.
- the 120 ° C. volatile content of the powdered positive electrode binder 10 was 0.1%.
- the positive electrode and lithium ion secondary battery were manufactured in the same manner as in Example 8 except that the positive electrode binder 10 was used.
- ⁇ Comparative Example 9> (Production of particulate polymer 10 for positive electrode) Toluene was added at a weight ratio of 100 parts with respect to 10 parts by weight of polymer to the aqueous dispersion of particulate polymer 1 for positive electrode, and emulsified at 15000 rpm with an emulsifying dispersion device (Milder MDN303V; manufactured by Taiheiyo Kiko Co., Ltd.). did. Thereafter, the solvent was removed from the emulsion using a rotary evaporator to obtain an aqueous dispersion of the particulate polymer 10 for positive electrode.
- the minimum film forming temperature of the particulate polymer for positive electrode 10 was 53 ° C.
- the glass transition temperature (Tg) was 40 ° C.
- the primary particle diameter was 3050 nm.
- the aqueous dispersion of the above-mentioned positive electrode particulate polymer 10 is sprayed in a spray dryer (Okawara Chemical Co., Ltd.) using a rotating disk type atomizer (diameter 65 mm) at a rotational speed of 25,000 rpm and a hot air temperature of 40 ° C. Dry granulation was performed, and the obtained particles were dried in a vacuum dryer under the conditions of 40 ° C. and 0.6 kPa to obtain a powdered positive electrode binder 11.
- the 120 ° C. volatile content of the powdered positive electrode binder 11 was 0.1%.
- the positive electrode and lithium ion secondary battery were manufactured in the same manner as in Example 8 except that the positive electrode binder 11 was used.
- the positive electrode and lithium ion secondary battery were manufactured in the same manner as in Example 8 except that the positive electrode binder 12 was used.
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Abstract
Description
(1) ガラス転移温度が35~80℃、一次粒子の体積基準のD50平均粒子径が80~1000nmである重合体からなり、120℃における揮発分が1重量%未満であり、粉末状複合化粒子であることを特徴とする電気化学素子電極用バインダー、
(2) 前記重合体が分散された粒子状重合体の水分散体を前記粒子状重合体の最低製膜温度未満で乾燥することにより得られることを特徴とする(1)記載の電気化学素子電極用バインダー、
(3) 共役ジエン単量体単位、アクリル酸エステル単量体単位、メタクリル酸エステル単量体単位、芳香族ビニル化合物単量体単位、エチレン性不飽和ニトリル単量体単位、エチレン性不飽和カルボン酸単量体単位、エチレン性不飽和アミド単量体単位、多官能エチレン単量体単位のうちから選ばれる少なくとも一種の単量体単位を含むことを特徴とする(1)または(2)記載の電気化学素子電極用バインダー、
(4) (1)~(3)の何れかに記載の電気化学素子電極用バインダーと、電極活物質とを乾式混合することにより得られることを特徴とする電気化学素子電極用粒子複合体、
(5) (4)記載の電気化学素子電極用粒子複合体の体積基準のD50平均粒子径(Da)と前記電極活物質の体積基準のD50平均粒子径(Db)との比(Da/Db)が0.5~2であることを特徴とする電気化学素子電極用粒子複合体、
(6) (5)に記載の電気化学素子電極用粒子複合体を含む電極活物質層を集電体上に積層してなることを特徴とする電気化学素子電極、
(7) 前記電極活物質層は、前記電気化学素子電極用粒子複合体を含む電極材料を前記集電体上に加圧成形することにより得られることを特徴とする(6)記載の電気化学素子電極、
(8) (6)または(7)に記載の電気化学素子電極を備えることを特徴とする電気化学素子、
(9) ガラス転移温度が35~80℃、一次粒子の体積基準のD50平均粒子径が80~1000nmの球形である粒子状重合体が分散された水分散体を前記粒子状重合体の最低製膜温度未満で乾燥することにより粉末状複合化粒子を得る乾燥工程と、前記粉末状複合化粒子と、電極活物質とを乾式混合して粒子複合体を得る混合工程と、前記粒子複合体を用いて電極を製造する電極製造工程とを含むことを特徴とする電気化学素子電極の製造方法が提供される。
本発明の電極用バインダーのガラス転移温度(Tg)は、35~80℃、好ましくは40~75℃、より好ましくは40~70℃、さらに好ましくは40~60℃、特に好ましくは45~55℃である。電極用バインダーのガラス転移温度がこの範囲にあると、柔軟で十分な強度の電極を得ることができる。また、電極用バインダーのガラス転移温度が高すぎると、十分な柔軟性を有する電極を得ることが困難となる。また、電極用バインダーのガラス転移温度が低すぎると、後述する粒子複合体の流動性が十分でないため、得られる電極の厚み精度が悪くなる。即ち、電極に厚みムラが発生する。
本発明の電気化学素子電極用粒子複合体(以下、「粒子複合体」と記載することがある。)は、上記電極用バインダーと、電極活物質とを含んでなる。粒子複合体は、必要に応じて導電剤を含んでもよい。ここで、粒子複合体においては、電極用バインダーおよび電極活物質のそれぞれが個別に独立した粒子として存在してもよいが、通常、電極活物質の表面に複数の電極用バインダーが付着して一粒子を形成している。そして、電極用バインダーおよび電極活物質のそれぞれの個別粒子や前記一粒子が、実質的に形状を維持した状態で複数個が結合して二次粒子を形成している。また、この二次粒子は、外力を受けた場合に一次粒子が個別に独立した粒子として存在することがある。
本発明の電気化学素子がリチウムイオン二次電池である場合の正極活物質としては、リチウムイオンをドープ及び脱ドープ可能な活物質が用いられ、無機化合物からなるものと有機化合物からなるものとに大別される。
また、本発明において必要に応じて用いられる導電剤としては、ファーネスブラック、アセチレンブラック(以下、「AB」と略記することがある。)、及びケッチェンブラック(アクゾノーベル ケミカルズ ベスローテン フェンノートシャップ社の登録商標)、カーボンナノチューブ、カーボンナノホーン、グラフェンなどの導電性カーボンが好ましく用いられる。これらの中でも、アセチレンブラックがより好ましい。導電剤の平均粒子径は、特に限定されないが、より少ない使用量で十分な導電性を発現させる観点から、電極活物質の平均粒子径よりも小さいものが好ましく、好ましくは0.001~10μm、より好ましくは0.005~5μm、さらに好ましくは0.01~1μmである。
粒子複合体は、電極用バインダー、電極活物質および必要に応じて用いられる導電剤を乾式混合することにより得られる。ここでいう「乾式混合」とは、電極用バインダー、電極活物質および必要に応じて用いられる導電剤を混合機を用いて混合することをいい、具体的には混合時の固形分濃度が99重量%以上で混合することをいう。具体的な混合方法としては、容器自体が振とう、回転、または振動することで混合される、ロッキングミキサー、タンブラーミキサー等を用いた容器攪拌法;容器内に対し水平、または垂直の回転軸に撹拌のための羽根、回転盤、またはスクリュー等が取り付けられた混合機である、水平円筒型混合機、V型混合機、リボン型混合機、円錐型スクリュー混合機、高速流動型混合機、回転円盤型混合機および高速回転羽根混合機等を用いた機械式撹拌;圧縮気体による旋回気流を利用する、流動層の中で粉体を混合する気流攪拌;等が挙げられる。また、これらの機構は単独あるいは併用して用いられた混合機を使用することもできる。また、乾式混合を行った後に、乳鉢等により凝集をほぐす程度に解砕を行ってもよい。乾式混合することにより、電気化学素子電極用粒子複合体の分散が良好に保たれ、ひいては塗布精度等の諸物性が向上する。
本発明の電気化学素子電極は、上述の粒子複合体を含む電極活物質層を集電体上に積層してなる電極である。集電体の材料としては、たとえば、金属、炭素、導電性高分子などを用いることができ、好適には金属が用いられる。金属としては、通常、銅、アルミニウム、白金、ニッケル、タンタル、チタン、ステンレス鋼、その他の合金等が使用される。これらの中で導電性、耐電圧性の面から、銅、アルミニウム又はアルミニウム合金を使用するのが好ましい。また、高い耐電圧性が要求される場合には特開2001-176757号公報等で開示される高純度のアルミニウムを好適に用いることができる。集電体は、フィルム又はシート状であり、その厚みは、使用目的に応じて適宜選択されるが、好ましくは1~200μm、より好ましくは5~100μm、さらに好ましくは10~50μmである。
本発明の電気化学素子は、上述のようにして得られる電気化学素子電極を正極および負極の少なくとも一方に用い、さらにセパレーターおよび電解液を備える。電気化学素子としては、例えば、リチウムイオン二次電池、リチウムイオンキャパシタ等が挙げられる。
セパレーターとしては、例えば、ポリエチレン、ポリプロピレンなどのポリオレフィン樹脂や、芳香族ポリアミド樹脂を含んでなる微孔膜または不織布;無機セラミック粉末を含む多孔質の樹脂コート;などを用いることができる。具体例を挙げると、ポリオレフィン系(ポリエチレン、ポリプロピレン、ポリブテン、ポリ塩化ビニル)、及びこれらの混合物あるいは共重合体等の樹脂からなる微多孔膜;ポリエチレンテレフタレート、ポリシクロオレフィン、ポリエーテルスルフォン、ポリアミド、ポリイミド、ポリイミドアミド、ポリアラミド、ポリシクロオレフィン、ナイロン、ポリテトラフルオロエチレン等の樹脂からなる微多孔膜;ポリオレフィン系の繊維を織ったもの又はその不織布;絶縁性物質粒子の集合体等が挙げられる。これらの中でも、セパレーター全体の膜厚を薄くすることができ、リチウムイオン二次電池内の活物質比率を上げて体積あたりの容量を上げることができるため、ポリオレフィン系の樹脂からなる微多孔膜が好ましい。
リチウムイオン二次電池用の電解液としては、例えば、非水溶媒に支持電解質を溶解した非水電解液が用いられる。支持電解質としては、リチウム塩が好ましく用いられる。リチウム塩としては、例えば、LiPF6、LiAsF6、LiBF4、LiSbF6、LiAlCl4、LiClO4、CF3SO3Li、C4F9SO3Li、CF3COOLi、(CF3CO)2NLi、(CF3SO2)2NLi、(C2F5SO2)NLiなどが挙げられる。中でも、溶媒に溶けやすく高い解離度を示すLiPF6、LiClO4、CF3SO3Liが好ましい。これらは1種類を単独で用いてもよく、2種類以上を任意の比率で組み合わせて用いてもよい。解離度の高い支持電解質を用いるほど、リチウムイオン伝導度が高くなるので、支持電解質の種類によりリチウムイオン伝導度を調節することができる。
なお、リチウムイオンキャパシタ用の電解液としては、上述のリチウムイオン二次電池に用いることができる電解液と同様のものを用いることができる。
リチウムイオン二次電池やリチウムイオンキャパシタ等の電気化学素子の具体的な製造方法としては、例えば、正極と負極とをセパレーターを介して重ね合わせ、これを電池形状に応じて巻く、折るなどして電池容器に入れ、電池容器に電解液を注入して封口する方法が挙げられる。さらに、必要に応じてエキスパンドメタル;ヒューズ、PTC素子などの過電流防止素子;リード板などを入れ、電池内部の圧力上昇、過充放電を防止してもよい。リチウムイオン二次電池の形状は、コイン型、ボタン型、シート型、円筒型、角形、扁平型など、何れであってもよい。電池容器の材質は、電池内部への水分の侵入を阻害するものであればよく、金属製、アルミニウムなどのラミネート製など特に限定されない。
電極用バインダーのガラス転移温度(Tg)は、示差走査熱量分析計(ナノテクノロジー社製 DSC6220SII)を用いて、JIS K 7121:1987に基づいて測定した。
直鎖アルキルベンゼンスルホン酸ナトリウムの1%水溶液中に実施例及び比較例で製造した電極用バインダー(負極用バインダー1~12、正極用バインダー1~13)をそれぞれ添加し、超音波にて分散化した後、コールターカウンターLS230(コールター社製粒子径測定器)による積分粒子径分布によって測定し、その50%積分値に相当する粒子径を電極用バインダーの体積基準のD50平均粒子径(一次粒子径)とした。
レーザー回折・散乱式粒度分布測定装置(マイクロトラックMT3200II;日機装)による乾式の積分粒子径分布によって実施例及び比較例で製造した粒子複合体の体積基準のD50平均粒子径(Da)と、実施例及び比較例で用いた電極活物質の体積基準のD50平均粒子径(Db)とを測定し、比(Da/Db)を求めた。
120℃に設定したオーブン内に実施例及び比較例で製造した粉末状負極用バインダー1~12、粉末状正極用バインダー1~13をそれぞれ入れ、10分ごとにバインダー重量の測定を行い、重量変化が0.1%未満になった時点で終了とした。この時の初期重量から測定終了時までの重量変化率(減少分)を120℃揮発分とした。
最低製膜温度測定装置(MFFTB90;RHOPOINT社製)を使用しISO2115に準じて試験を行った。
粉末状電極用バインダーをSEMで観察し画像中に見える粒子30個をランダムに取り出し、各々の粒子の平均短軸径、平均長軸径を求め平均球形度を算出した。このとき平均球形度が80%以上である場合を球状、平均球形度が80%未満のものを非球状とした。
実施例及び比較例で作製した電極活物質層のTD方向(横方向)10cm、MD方向(縦方向)10cmについて、TD方向に均等に3点、MD方向に均等に3点の計9点の膜厚を測定した。この膜厚の平均値をA、平均値から最も離れている厚みをBとするとき、下記の式で電極厚みムラを計算した。
電極厚みムラ精度(%)=(|A-B|)×100/A
これを電極精度とし、以下の基準で評価した。結果を表1及び表2に示す。この値が小さいほど成形性に優れることを示す。
A:4%未満
B:4%以上9%未満
C:9%以上15%未満
D:15%以上
E:電極に穴が開いている
実施例及び比較例で作製した電気化学素子電極を、1cm×8cmに切り出し、直径3mm、4mm、5mmの金属棒にそれぞれ巻きつけ、生じた割れを下記のように評価した。結果を表1及び表2に示す。割れが少ないほど柔軟性に優れる、すなわち電極強度に優れることを示す。
A:直径3mmの金属棒で割れがない
B:直径4mmの金属棒で割れはないが、直径3mmの金属棒で割れがある
C:直径5mmで割れがある
実施例及び比較例で作製したラミネートセル型のリチウムイオン二次電池を、電解液注液後、5時間静置させ、25℃雰囲気下で0.2Cの定電流法によって、セル電圧3.65Vまで充電し、その後60℃に昇温し、12時間エージング処理を行い、25℃雰囲気下で0.2Cの定電流法によってセル電圧3.00Vまで放電を行った。
A:ΔCが83%以上
B:ΔCが82%以上83%未満
C:ΔCが80%以上82%未満
D:ΔCが80%未満
(負極用粒子状重合体1の製造)
攪拌機付き5MPa耐圧容器に、スチレン(以下、「ST」と略記することがある。)78部、1,3-ブタジエン(以下、「BD」と略記することがある。)19部、イタコン酸(以下、「IA」と略記することがある。)3部、乳化剤としてアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.4部、イオン交換水150部、連鎖移動剤としてt-ドデシルメルカプタン(以下、「TDM」と略記することがある。)0.3部および重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、75℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、負極用粒子状重合体1(スチレン・ブタジエン共重合体;以下、「SBR」と略記することがある。)の水分散体を得た。負極用粒子状重合体1の最低製膜温度は55℃であり、ガラス転移温度(Tg)は50℃、一次粒子径は132nmであった。
上記負極用粒子状重合体1の水分散体からロータリーエバポレーターにて40℃で水分を除去したのち、真空乾燥機にて40℃、0.6kPaの条件で乾燥させた。その後、乾燥させた負極用粒子状重合体1を乳鉢で解砕し、粉末状の負極用バインダー1を得た。粉末状の負極用バインダー1の120℃揮発分は0.1%であった。
負極活物質として人造黒鉛(平均粒子径:24.5μm、黒鉛層間距離(X線回折法による(002)面の面間隔(d値)):0.354nm)98.8部および上記負極用バインダーを固形分換算量で1.2部、ヘンシェルミキサー(三井三池社製)を用いて10分間混合し、負極活物質に負極用バインダーを付着させ、粒子複合体を得た。
上記で得られた粒子複合体を、定量フィーダ(ニッカ社製「ニッカスプレーK-V))を用いてロールプレス機(ヒラノ技研工業社製「押し切り粗面熱ロール」)のプレス用ロール(ロール温度100℃、プレス線圧500kN/m)に供給した。プレス用ロール間に、厚さ20μmの銅箔を挿入し、定量フィーダから供給された上記粒子複合体を銅箔上に付着させ、成形速度1.5m/分で加圧成形し、負極活物質を有する負極を得た。
正極活物質としてLiCoO292部に、正極用バインダーとしてポリフッ化ビニリデン(PVDF;クレハ化学社製「KF-1100」)を固形分量が2部となるように加え、さらに、アセチレンブラック(電気化学工業社製「HS-100」)を6部、N-メチルピロリドン20部を加えて、プラネタリーミキサーで混合して正極用スラリーを得た。この正極用スラリーを厚さ18μmのアルミニウム箔に塗布し、120℃で30分乾燥した後、ロールプレスして厚さ60μmの正極を得た。
単層のポリプロピレン製セパレーター(幅65mm、長さ500mm、厚さ25μm、乾式法により製造、気孔率55%)を、5×5cm2の正方形に切り抜いた。
電池の外装として、アルミ包材外装を用意した。上記で得られた正極を、4×4cm2の正方形に切り出し、集電体側の表面がアルミ包材外装に接するように配置した。また、上記で得られた正極の正極活物質層の面上に、上記で得られた正方形のセパレーターを配置した。さらに、上記で得られた負極を、4.2×4.2cm2の正方形に切り出し、負極活物質層側の表面がセパレーターに向かい合うように、セパレーター上に配置した。更に、ビニレンカーボネートを2.0%含有する、濃度1.0モル/LのLiPF6溶液を充填した。このLiPF6溶液の溶媒はエチレンカーボネート(EC)とエチルメチルカーボネート(EMC)との混合溶媒(EC/EMC=3/7(体積比))である。さらに、アルミニウム包材の開口を密封するために、150℃でヒートシールをしてアルミニウム外装を閉口し、ラミネート型のリチウムイオン二次電池(ラミネート型セル)を製造した。
(負極用粒子状重合体2の製造)
攪拌機付き5MPa耐圧容器に、スチレン74.5部、1,3-ブタジエン22.5部、イタコン酸3部、乳化剤としてアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.4部、イオン交換水150部、連鎖移動剤としてt-ドデシルメルカプタン0.3部および重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、75℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、負極用粒子状重合体2の水分散体を得た。粒子状重合体2の最低製膜温度は40℃であり、ガラス転移温度(Tg)は40℃、一次粒子径は135nmであった。
上記負極用粒子状重合体2の水分散体からロータリーエバポレーターにて25℃で水分を除去したのち、真空乾燥機にて25℃、0.6kPaの条件で乾燥させた。その後、乾燥させた負極用粒子状重合体2を乳鉢で解砕し、粉末状の負極用バインダー2を得た。粉末状の負極用バインダー2の120℃揮発分は0.1%であった。
(負極用粒子状重合体3の製造)
攪拌機付き5MPa耐圧容器に、スチレン85部、1,3-ブタジエン12部、イタコン酸3部、乳化剤としてアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.4部、イオン交換水150部、連鎖移動剤としてt-ドデシルメルカプタン0.3部および重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、75℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、負極用粒子状重合体3の水分散体を得た。負極用粒子状重合体3の最低製膜温度は88℃であり、ガラス転移温度(Tg)は70℃、一次粒子径は134nmであった。
上記負極用粒子状重合体3の水分散体からロータリーエバポレーターにて60℃で水分を除去したのち、真空乾燥機にて60℃、0.6kPaの条件で乾燥させた。その後、乾燥させた負極用粒子状重合体3を乳鉢で解砕し、粉末状の負極用バインダー3を得た。粉末状の負極用バインダー3の120℃揮発分は0.1%であった。
(負極用粒子状重合体4の製造)
攪拌機付き5MPa耐圧容器に、スチレン78部、1,3-ブタジエン19部、イタコン酸3部、乳化剤としてアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で2.0部、イオン交換水150部、連鎖移動剤としてt-ドデシルメルカプタン0.3部および重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、75℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、負極用粒子状重合体4の水分散体を得た。負極用粒子状重合体4の最低製膜温度は53℃であり、ガラス転移温度(Tg)は50℃、一次粒子径は80nmであった。
上記負極用粒子状重合体4の水分散体からロータリーエバポレーターにて40℃で水分を除去したのち、真空乾燥機にて40℃、0.6kPaの条件で乾燥させた。その後、乾燥させた負極用粒子状重合体4を乳鉢で解砕し、粉末状の負極用バインダー4を得た。粉末状の負極用バインダー4の120℃揮発分は0.4%であった。
(負極用粒子状重合体5の製造)
攪拌機付き5MPa耐圧容器に、イオン交換水210部を仕込み、撹拌しながら75℃に加熱し、1.96%過硫酸カリウム水溶液25.5部を反応器に添加した。次いで、上記とは別の攪拌機付き5MPa耐圧容器に、スチレン78部、1,3-ブタジエン19部、イタコン酸3部、乳化剤としてアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.4部、連鎖移動剤としてt-ドデシルメルカプタン0.3部、及びイオン交換水26部を添加し、これを攪拌乳化させて単量体混合液を調製した。そして、この単量体混合液を攪拌乳化させた状態にて、3.5時間かけて一定の速度で、イオン交換水210部及び過硫酸カリウム水溶液を仕込んだ反応器に添加し、重合転化率が95%になるまで反応させて、負極用粒子状重合体5の水分散体を得た。負極用粒子状重合体5の最低製膜温度は56℃であり、ガラス転移温度(Tg)は50℃、一次粒子径は304nmであった。
上記負極用粒子状重合体5の水分散体からロータリーエバポレーターにて40℃で水分を除去したのち、真空乾燥機にて40℃、0.6kPaの条件で乾燥させた。その後、乾燥させた負極用粒子状重合体5を乳鉢で解砕し、粉末状の負極用バインダー5を得た。粉末状の負極用バインダー5の120℃揮発分は0.1%であった。
(負極用粒子状重合体6の製造)
攪拌機付き5MPa耐圧容器に、イオン交換水210部を仕込み、撹拌しながら75℃に加熱し、1.96%過硫酸カリウム水溶液25.5部を反応器に添加した。次いで、上記とは別の攪拌機付き5MPa耐圧容器に、スチレン78部、1,3-ブタジエン19部、イタコン酸3部、乳化剤としてアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.2部、連鎖移動剤としてt-ドデシルメルカプタン0.3部、及びイオン交換水26部を添加し、これを攪拌乳化させて単量体混合液を調製した。そして、この単量体混合液を攪拌乳化させた状態にて、3.5時間かけて一定の速度で、イオン交換水210部及び過硫酸カリウム水溶液を仕込んだ反応器に添加し、重合転化率が95%になるまで反応させて、負極用粒子状重合体6の水分散体を得た。負極用粒子状重合体6の最低製膜温度は56℃であり、ガラス転移温度(Tg)は50℃、一次粒子径は625nmであった。
上記負極用粒子状重合体6の水分散体からロータリーエバポレーターにて40℃で水分を除去したのち、真空乾燥機にて40℃、0.6kPaの条件で乾燥させた。その後、乾燥させた負極用粒子状重合体6を乳鉢で解砕し、粉末状の負極用バインダー6を得た。粉末状の負極用バインダー6の120℃揮発分は0.1%であった。
上記負極用粒子状重合体1の水分散体からロータリーエバポレーターにて40℃で水分を除去した。その後、真空乾燥機にて40℃、0.6kPaの条件での乾燥を行わなかった以外は、実施例1と同様に粒子状重合体の乾燥と解砕を行い、粉末状の負極用バインダー7を得た。粉末状の負極用バインダー7の120℃揮発分は0.8%であった。
(負極用粒子状重合体7の製造)
攪拌機付き5MPa耐圧容器に、スチレン70部、1,3-ブタジエン27部、イタコン酸3部、乳化剤としてアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.4部、イオン交換水150部、連鎖移動剤としてt-ドデシルメルカプタン0.3部および重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、75℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、負極用粒子状重合体7の水分散体を得た。負極用粒子状重合体7の最低製膜温度は27℃であり、ガラス転移温度(Tg)は30℃、一次粒子径は130nmであった。
上記負極用粒子状重合体7の水分散体からロータリーエバポレーターにて20℃で水分を除去したのち、真空乾燥機にて20℃、0.6kPaの条件で乾燥させた。その後、乾燥させた負極用粒子状重合体7を乳鉢で解砕し、若干凝集性の高い粉末状の負極用バインダー8を得た。粉末状の負極用バインダー8の120℃揮発分は0.1%であった。
(負極用粒子状重合体8の製造)
攪拌機付き5MPa耐圧容器に、スチレン94部、1,3-ブタジエン3部、イタコン酸3部、乳化剤としてアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.4部、イオン交換水150部および重合開始剤として過硫酸カリウム0.5部を入れ、十分に攪拌した後、75℃に加温して重合を開始した。重合転化率が96%になった時点で冷却し反応を停止して、負極用粒子状重合体8の水分散体を得た。負極用粒子状重合体8の最低製膜温度は120℃であり、ガラス転移温度(Tg)は100℃、一次粒子径は135nmであった。
上記負極用粒子状重合体8の水分散体からロータリーエバポレーターにて80℃で水分を除去したのち、真空乾燥機にて80℃、0.6kPaの条件で乾燥させた。その後、乾燥させた負極用粒子状重合体8を乳鉢で解砕し、粉末状の負極用バインダー9を得た。
(負極用粒子状重合体9の製造)
負極用粒子状重合体1の水分散体に対して重合体重量10部に対してトルエンを100部の重量比で添加し、乳化分散装置(マイルダーMDN303V;太平洋機工社製)にて15000rpmで乳化した。その後、その乳化液をロータリーエバポレーターを用いて溶剤を除去し、負極用粒子状重合体9の水分散体を得た。負極用粒子状重合体9の最低製膜温度は53℃であり、ガラス転移温度(Tg)は50℃、一次粒子径は3020nmであった。
上記粒子状重合体9の水分散体からロータリーエバポレーターにて40℃で水分を除去したのち、真空乾燥機にて40℃、0.6kPaの条件で乾燥させた。その後、乾燥させた負極用粒子状重合体9を乳鉢で解砕し、粉末状の負極用バインダー10を得た。粉末状の負極用バインダー10の120℃揮発分は0.1%であった。
上記負極用粒子状重合体1の水分散体からロータリーエバポレーターにて40℃で水分を除去する際に、水分の除去を途中で停止し、粉末状の負極用バインダー11を得た。粉末状の負極用バインダー11の120℃揮発分は2%であった。
上記負極用粒子状重合体1の水分散体からロータリーエバポレーターにて60℃で水分を除去したのち、真空乾燥機にて60℃、0.6kPaの条件で乾燥させた。その後フィルム化した負極用粒子状重合体1を乳鉢で粉砕した後、さらにジェットミルで平均粒子径が5000nm程度となるまで粉砕を行い、粉末状の負極用バインダー12を得た。粉末状の負極用バインダー12の120℃揮発分は0.1%であった。
(正極用粒子状重合体1の製造)
メカニカルスターラー及びコンデンサを装着した反応器に、窒素雰囲気下、イオン交換水210部を仕込み、撹拌しながら70℃に加熱し、1.96%過硫酸カリウム水溶液25.5部を反応器に添加した。次いで、メカニカルスターラーを装着した上記とは別の容器に、窒素雰囲気下、アクリル酸ブチル(以下、「BA」と略記することがある。)20部、メタクリル酸エチル(以下、「EMA」と略記することがある。)77.5部、メタクリル酸(以下、「MAA」と略記することがある。)2.4部、メタクリル酸アリル(以下、「AMA」と略記することがある。)0.1部、乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で1.0部、及びイオン交換水22.7部を添加し、これを攪拌乳化させて単量体混合液を調製した。そして、この単量体混合液を攪拌乳化させた状態にて、2.5時間かけて一定の速度で、イオン交換水210部及び過硫酸カリウム水溶液を仕込んだ反応器に添加し、重合転化率が95%になるまで反応させて、正極用粒子状重合体1(アクリル系重合体;以下、「アクリル系」と略記することがある。)の水分散体を得た。また、正極用粒子状重合体1の最低製膜温度は45℃であり、ガラス転移温度(Tg)は40℃、一次粒子径は310nmであった。
上記正極用粒子状重合体1の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて30℃、0.6kPaの条件にて乾燥させ、粉末状の正極用バインダー1を得た。粉末状の正極用バインダー1の120℃揮発分は、0.1%であった。
正極活物質としてNMC(111)92.5部と、導電剤としてアセチレンブラックを6部および上記正極用バインダーを固形分換算量で1.5部を、ヘンシェルミキサー(三井三池社製)を用いて10分間混合し、正極活物質に正極用バインダーを付着させ、粒子複合体を得た。
上記で得られた粒子複合体を、定量フィーダ(ニッカ社製「ニッカスプレーK-V))を用いてロールプレス機(ヒラノ技研工業社製「押し切り粗面熱ロール」)のプレス用ロール(ロール温度100℃、プレス線圧500kN/m)に供給した。プレス用ロール間に、厚さ20μmのアルミニウム箔を挿入し、定量フィーダから供給された上記粒子複合体をアルミニウム箔上に付着させ、成形速度1.5m/分で加圧成形し、正極活物質を有する正極を得た。
負極活物質として人造黒鉛(平均粒子径:24.5μm、黒鉛層間距離(X線回折法による(002)面の面間隔(d値):0.354nm)96部、スチレン-ブタジエン共重合ラテックス(BM-400B)を固形分換算量で3.0部、カルボキシメチルセルロースの1.5%水溶液(DN-800H:ダイセル化学工業社製)を固形分換算量で1.0部混合し、さらにイオン交換水を固形分濃度が50%となるように加え、混合分散して負極用スラリーを得た。この負極用スラリーを厚さ18μmの銅箔に塗布し、120℃で30分間乾燥した後、ロールプレスして厚さ50μmの負極を得た。
単層のポリプロピレン製セパレーター(幅65mm、長さ500mm、厚さ25μm、乾式法により製造、気孔率55%)を、5×5cm2の正方形に切り抜いた。
電池の外装として、アルミ包材外装を用意した。上記で得られた正極を、4×4cm2の正方形に切り出し、集電体側の表面がアルミ包材外装に接するように配置した。また、上記で得られた正極の正極活物質層の面上に、上記で得られた正方形のセパレーターを配置した。さらに、上記で得られた負極を、4.2×4.2cm2の正方形に切り出し、負極活物質層側の表面がセパレーターに向かい合うように、セパレーター上に配置した。更に、ビニレンカーボネートを2.0%含有する、濃度1.0モル/LのLiPF6溶液を充填した。このLiPF6溶液の溶媒はエチレンカーボネート(EC)とエチルメチルカーボネート(EMC)との混合溶媒(EC/EMC=3/7(体積比))である。さらに、アルミニウム包材の開口を密封するために、150℃でヒートシールをしてアルミニウム外装を閉口し、ラミネート型のリチウムイオン二次電池(ラミネート型セル)を製造した。
(正極用粒子状重合体2の製造)
メカニカルスターラー及びコンデンサを装着した反応器に、窒素雰囲気下、イオン交換水210部を仕込み、撹拌しながら70℃に加熱し、1.96%過硫酸カリウム水溶液25.5部を反応器に添加した。次いで、メカニカルスターラーを装着した上記とは別の容器に、窒素雰囲気下、アクリル酸ブチル12部、メタクリル酸エチル85.5部、メタクリル酸2.4部、メタクリル酸アリル0.1部、乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で1.0部、及びイオン交換水22.7部を添加し、これを攪拌乳化させて単量体混合液を調製した。そして、この単量体混合液を攪拌乳化させた状態にて、2.5時間かけて一定の速度で、イオン交換水210部及び過硫酸カリウム水溶液を仕込んだ反応器に添加し、重合転化率が95%になるまで反応させて、正極用粒子状重合体2の水分散体を得た。また、正極用粒子状重合体2の最低製膜温度は52℃であり、ガラス転移温度(Tg)は50℃、一次粒子径は319nmであった。
上記正極用粒子状重合体2の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて40℃、0.6kPaの条件にて乾燥させ、粉末状の正極用バインダー2を得た。粉末状の正極用バインダー2の120℃揮発分は、0.1%であった。
(正極用粒子状重合体3の製造)
メカニカルスターラー及びコンデンサを装着した反応器に、窒素雰囲気下、イオン交換水210部を仕込み、撹拌しながら70℃に加熱し、1.96%過硫酸カリウム水溶液25.5部を反応器に添加した。次いで、メカニカルスターラーを装着した上記とは別の容器に、窒素雰囲気下、アクリル酸ブチル6部、メタクリル酸エチル91.5部、メタクリル酸2.4部、メタクリル酸アリル0.1部、乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で1.0部、及びイオン交換水22.7部を添加し、これを攪拌乳化させて単量体混合液を調製した。そして、この単量体混合液を攪拌乳化させた状態にて、2.5時間かけて一定の速度で、イオン交換水210部及び過硫酸カリウム水溶液を仕込んだ反応器に添加し、重合転化率が95%になるまで反応させて、正極用粒子状重合体3の水分散体を得た。また、正極用粒子状重合体3の最低製膜温度は65℃であり、ガラス転移温度(Tg)は60℃、一次粒子径は331nmであった。
上記正極用粒子状重合体3の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて40℃、0.6kPaの条件にて乾燥させ、粉末状の正極用バインダー3を得た。粉末状の正極用バインダー3の120℃揮発分は、0.1%であった。
(正極用粒子状重合体4の製造)
メカニカルスターラー及びコンデンサを装着した反応器に、窒素雰囲気下、イオン交換水210部、乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.5部、を仕込み、撹拌しながら70℃に加熱し、1.96%過硫酸カリウム水溶液25.5部を反応器に添加した。次いで、メカニカルスターラーを装着した上記とは別の容器に、窒素雰囲気下、アクリル酸ブチル20部、メタクリル酸エチル77.5部、メタクリル酸2.4部、メタクリル酸アリル0.1部、乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.5部、及びイオン交換水22.7部を添加し、これを攪拌乳化させて単量体混合液を調製した。そして、この単量体混合液を攪拌乳化させた状態にて、2.5時間かけて一定の速度で、イオン交換水210部及び過硫酸カリウム水溶液を仕込んだ反応器に添加し、重合転化率が95%になるまで反応させて、正極用粒子状重合体4の水分散体を得た。また、正極用粒子状重合体4の最低製膜温度は43℃であり、ガラス転移温度(Tg)は40℃、一次粒子径は139nmであった。
上記正極用粒子状重合体4の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて30℃、0.6kPaの条件にて乾燥させ、粉末状の正極用バインダー4を得た。粉末状の正極用バインダー4の120℃揮発分は、0.1%であった。
(正極用粒子状重合体5の製造)
メカニカルスターラー及びコンデンサを装着した反応器に、窒素雰囲気下、イオン交換水210部、乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.8部仕込み、撹拌しながら70℃に加熱し、1.96%過硫酸カリウム水溶液25.5部を反応器に添加した。次いで、メカニカルスターラーを装着した上記とは別の容器に、窒素雰囲気下、アクリル酸ブチル20部、メタクリル酸エチル77.5部、メタクリル酸2.4部、メタクリル酸アリル0.1部、乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.8部、及びイオン交換水22.7部を添加し、これを攪拌乳化させて単量体混合液を調製した。そして、この単量体混合液を攪拌乳化させた状態にて、2.5時間かけて一定の速度で、イオン交換水210部及び過硫酸カリウム水溶液を仕込んだ反応器に添加し、重合転化率が95%になるまで反応させて、正極用粒子状重合体5の水分散体を得た。また、正極用粒子状重合体5の最低製膜温度は43℃であり、ガラス転移温度(Tg)は40℃、一次粒子径は100nmであった。
上記正極用粒子状重合体5の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて30℃、0.6kPaの条件にて乾燥させ、粉末状の正極用バインダー5を得た。粉末状の正極用バインダー5の120℃揮発分は、0.1%であった。
(正極用粒子状重合体6の製造)
メカニカルスターラー及びコンデンサを装着した反応器に、窒素雰囲気下、イオン交換水210部を仕込み、撹拌しながら70℃に加熱し、1.96%過硫酸カリウム水溶液25.5部を反応器に添加した。次いで、メカニカルスターラーを装着した上記とは別の容器に、窒素雰囲気下、アクリル酸ブチル20部、メタクリル酸エチル77.5部、メタクリル酸2.4部、メタクリル酸アリル0.1部、乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で0.4部、及びイオン交換水22.7部を添加し、これを攪拌乳化させて単量体混合液を調製した。そして、この単量体混合液を攪拌乳化させた状態にて、2.5時間かけて一定の速度で、イオン交換水210部及び過硫酸カリウム水溶液を仕込んだ反応器に添加し、重合転化率が95%になるまで反応させて、正極用粒子状重合体6の水分散体を得た。また、正極用粒子状重合体6の最低製膜温度は48℃であり、ガラス転移温度(Tg)は40℃、一次粒子径は625nmであった。
上記正極用粒子状重合体6の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて30℃、0.6kPaの条件にて乾燥させ、粉末状の正極用バインダー6を得た。粉末状の正極用バインダー6の120℃揮発分は、0.1%であった。
上記正極用粒子状重合体1の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、粒子を得た。その後、得られた粒子を真空乾燥機にて30℃、0.6kPaの条件にて乾燥を行わなかった以外は、実施例8と同様に粒子状重合体の乾燥を行い、粉末状の正極用バインダー7を得た。粉末状の正極用バインダー7の120℃揮発分は0.8%であった。
(正極用粒子状重合体7の製造)
メカニカルスターラー及びコンデンサを装着した反応器に、窒素雰囲気下、イオン交換水210部を仕込み、撹拌しながら70℃に加熱し、1.96%過硫酸カリウム水溶液25.5部を反応器に添加した。次いで、メカニカルスターラーを装着した上記とは別の容器に、窒素雰囲気下、アクリル酸ブチル27.6部、メタクリル酸エチル70.0部、メタクリル酸2.4部、メタクリル酸アリル0.1部、乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で1.0部、及びイオン交換水22.7部を添加し、これを攪拌乳化させて単量体混合液を調製した。そして、この単量体混合液を攪拌乳化させた状態にて、2.5時間かけて一定の速度で、イオン交換水210部及び過硫酸カリウム水溶液を仕込んだ反応器に添加し、重合転化率が95%になるまで反応させて、正極用粒子状重合体7の水分散体を得た。また、正極用粒子状重合体7の最低製膜温度は27℃であり、ガラス転移温度(Tg)は30℃、一次粒子径は307nmであった。
上記正極用粒子状重合体7の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて25℃、0.6kPaの条件にて乾燥させ、粉末状の正極用バインダー8を得た。粉末状の正極用バインダー8の120℃揮発分は、0.1%であった。
(正極用粒子状重合体8の製造)
メカニカルスターラー及びコンデンサを装着した反応器に、窒素雰囲気下、イオン交換水210部を仕込み、撹拌しながら70℃に加熱し、1.96%過硫酸カリウム水溶液25.5部を反応器に添加した。次いで、メカニカルスターラーを装着した上記とは別の容器に、窒素雰囲気下、メタクリル酸エチル22.5部、メタクリル酸メチル(以下、「MMA」と略記することがある。)75.0部、メタクリル酸2.4部、メタクリル酸アリル0.1部、乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で1.0部、及びイオン交換水22.7部を添加し、これを攪拌乳化させて単量体混合液を調製した。そして、この単量体混合液を攪拌乳化させた状態にて、2.5時間かけて一定の速度で、イオン交換水210部及び過硫酸カリウム水溶液を仕込んだ反応器に添加し、重合転化率が95%になるまで反応させて、正極用粒子状重合体8の水分散体を得た。また、正極用粒子状重合体8の最低製膜温度は115℃であり、ガラス転移温度(Tg)は100℃、一次粒子径は280nmであった。
上記正極用粒子状重合体8の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて80℃、0.6kPaの条件にて乾燥させ、粉末状の正極用バインダー9を得た。粉末状の正極用バインダー9の120℃揮発分は、0.1%であった。
(正極用粒子状重合体9の製造)
メカニカルスターラー及びコンデンサを装着した反応器に、窒素雰囲気下、イオン交換水831部と乳化剤として濃度30%のアルキルジフェニルオキシドジスルホネート(ダウファックス(登録商標)2A1、ダウ・ケミカル社製)を固形分相当量で10部添加し、アクリル酸ブチル6部、メタクリル酸エチル91.5部、メタクリル酸2.4部、メタクリル酸アリル0.1部を添加し、この単量体混合液を攪拌乳化させた。これを撹拌しながら60℃に加熱し、1.96%過硫酸カリウム水溶液51部を反応器に添加した。重合転化率が98%になるまで反応させて、正極用粒子状重合体9の水分散体を得た。また、正極用粒子状重合体9の最低製膜温度は42℃であり、ガラス転移温度(Tg)は60℃、一次粒子径は50nmであった。
上記正極用粒子状重合体9の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて40℃、0.6kPaの条件にて乾燥させ、粉末状の正極用バインダー10を得た。粉末状の正極用バインダー10の120℃揮発分は、0.1%であった。
(正極用粒子状重合体10の製造)
正極用粒子状重合体1の水分散体に対して重合体重量10部に対してトルエンを100部の重量比で添加し、乳化分散装置(マイルダーMDN303V;太平洋機工社製)にて15000rpmで乳化した。その後、その乳化液をロータリーエバポレーターを用いて溶剤を除去し、正極用粒子状重合体10の水分散体を得た。正極用粒子状重合体10の最低製膜温度は53℃であり、ガラス転移温度(Tg)は40℃、一次粒子径は3050nmであった。
上記正極用粒子状重合体10の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて40℃、0.6kPaの条件にて乾燥させ、粉末状の正極用バインダー11を得た。粉末状の正極用バインダー11の120℃揮発分は、0.1%であった。
上記正極用粒子状重合体1の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度30℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥させずに、粉末状の正極用バインダー12を得た。粉末状の正極用バインダー12の120℃揮発分は2%であった。
上記正極用粒子状重合体1の水分散体をスプレー乾燥機(大川原化工機社製)において、回転円盤方式のアトマイザ(直径65mm)を用い、回転数25,000rpm、熱風温度40℃として、噴霧乾燥造粒を行い、得られた粒子を真空乾燥機にて70℃、0.6kPaの条件で乾燥させた。その後フィルム化した正極用粒子状重合体1を乳鉢で粉砕した後、さらにジェットミルで平均粒子径が5000nm程度となるまで粉砕を行い、粉末状の正極用バインダー13を得た。粉末状の正極用バインダー13の120℃揮発分は0.1%であった。
Claims (9)
- ガラス転移温度が35~80℃、一次粒子の体積基準のD50平均粒子径が80~1000nmである重合体からなり、120℃における揮発分が1重量%未満であり、粉末状複合化粒子であることを特徴とする電気化学素子電極用バインダー。
- 前記重合体が分散された粒子状重合体の水分散体を前記粒子状重合体の最低製膜温度未満で乾燥することにより得られることを特徴とする請求項1記載の電気化学素子電極用バインダー。
- 共役ジエン単量体単位、アクリル酸エステル単量体単位、メタクリル酸エステル単量体単位、芳香族ビニル化合物単量体単位、エチレン性不飽和ニトリル単量体単位、エチレン性不飽和カルボン酸単量体単位、エチレン性不飽和アミド単量体単位、多官能エチレン単量体単位のうちから選ばれる少なくとも一種の単量体単位を含むことを特徴とする請求項1または2記載の電気化学素子電極用バインダー。
- 請求項1~3の何れか一項に記載の電気化学素子電極用バインダーと、電極活物質とを乾式混合することにより得られることを特徴とする電気化学素子電極用粒子複合体。
- 請求項4記載の電気化学素子電極用粒子複合体の体積基準のD50平均粒子径(Da)と前記電極活物質の体積基準のD50平均粒子径(Db)との比(Da/Db)が0.5~2であることを特徴とする電気化学素子電極用粒子複合体。
- 請求項5に記載の電気化学素子電極用粒子複合体を含む電極活物質層を集電体上に積層してなることを特徴とする電気化学素子電極。
- 前記電極活物質層は、前記電気化学素子電極用粒子複合体を含む電極材料を前記集電体上に加圧成形することにより得られることを特徴とする請求項6記載の電気化学素子電極。
- 請求項6または7に記載の電気化学素子電極を備えることを特徴とする電気化学素子。
- ガラス転移温度が35~80℃、一次粒子の体積基準の平均粒子径D50が80~1000nmの球形である粒子状重合体が分散された水分散体を前記粒子状重合体の最低製膜温度未満で乾燥することにより粉末状複合化粒子を得る乾燥工程と、
前記粉末状複合化粒子と、電極活物質とを乾式混合して粒子複合体を得る混合工程と
前記粒子複合体を用いて電極を製造する電極製造工程と
を含むことを特徴とする電気化学素子電極の製造方法。
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US11183693B2 (en) | 2016-07-29 | 2021-11-23 | Kao Corporation | Resin composition for power storage device electrode |
JP2018125127A (ja) * | 2017-01-31 | 2018-08-09 | 株式会社Gsユアサ | 非水電解質蓄電素子及びその製造方法 |
WO2019146720A1 (ja) * | 2018-01-26 | 2019-08-01 | 花王株式会社 | リチウムイオン二次電池用正極 |
JP2019133908A (ja) * | 2018-01-26 | 2019-08-08 | 花王株式会社 | リチウムイオン二次電池用正極 |
WO2023182248A1 (ja) * | 2022-03-24 | 2023-09-28 | 東亞合成株式会社 | 二次電池正極用粉末状バインダー及びその利用 |
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CN105190968A (zh) | 2015-12-23 |
KR20160013867A (ko) | 2016-02-05 |
JPWO2014192652A1 (ja) | 2017-02-23 |
JP6327249B2 (ja) | 2018-05-23 |
CN105190968B (zh) | 2018-07-24 |
KR102232551B1 (ko) | 2021-03-25 |
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