JP5284896B2 - Electrode for lithium non-aqueous electrolyte battery, positive electrode current collector for lithium non-aqueous electrolyte battery, and method for producing the same - Google Patents
Electrode for lithium non-aqueous electrolyte battery, positive electrode current collector for lithium non-aqueous electrolyte battery, and method for producing the same Download PDFInfo
- Publication number
- JP5284896B2 JP5284896B2 JP2009164478A JP2009164478A JP5284896B2 JP 5284896 B2 JP5284896 B2 JP 5284896B2 JP 2009164478 A JP2009164478 A JP 2009164478A JP 2009164478 A JP2009164478 A JP 2009164478A JP 5284896 B2 JP5284896 B2 JP 5284896B2
- Authority
- JP
- Japan
- Prior art keywords
- electrode
- electrolyte battery
- current collector
- aqueous electrolyte
- binder
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000011255 nonaqueous electrolyte Substances 0.000 title claims description 40
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims description 27
- 229910052744 lithium Inorganic materials 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title description 6
- 239000011230 binding agent Substances 0.000 claims description 38
- 239000000203 mixture Substances 0.000 claims description 34
- 229920001661 Chitosan Polymers 0.000 claims description 30
- 239000011149 active material Substances 0.000 claims description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 16
- 229910052782 aluminium Inorganic materials 0.000 claims description 16
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000000126 substance Substances 0.000 claims description 11
- 239000006230 acetylene black Substances 0.000 claims description 8
- 239000002482 conductive additive Substances 0.000 claims description 8
- 230000006196 deacetylation Effects 0.000 claims description 4
- 238000003381 deacetylation reaction Methods 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 125000000524 functional group Chemical group 0.000 claims description 2
- 239000010409 thin film Substances 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims 1
- 239000010408 film Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 21
- 239000008151 electrolyte solution Substances 0.000 description 15
- 239000011888 foil Substances 0.000 description 15
- 229920006254 polymer film Polymers 0.000 description 14
- 239000003792 electrolyte Substances 0.000 description 12
- 239000010410 layer Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 11
- 239000002184 metal Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 9
- 230000001070 adhesive effect Effects 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 239000002033 PVDF binder Substances 0.000 description 8
- 239000003960 organic solvent Substances 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 6
- 210000004027 cell Anatomy 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000005486 organic electrolyte Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- -1 polypropylene Polymers 0.000 description 5
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005238 degreasing Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 150000002894 organic compounds Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000011109 contamination Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910013684 LiClO 4 Inorganic materials 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000010407 anodic oxide Substances 0.000 description 2
- 238000007743 anodising Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 2
- 210000005056 cell body Anatomy 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 238000003618 dip coating Methods 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000003349 gelling agent Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- ZUQUTHURQVDNKF-KEWYIRBNSA-N 1-[(3R,4R,5S,6R)-3-amino-2,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl]ethanone Chemical compound CC(=O)C1(O)O[C@H](CO)[C@@H](O)[C@H](O)[C@H]1N ZUQUTHURQVDNKF-KEWYIRBNSA-N 0.000 description 1
- FLDCSPABIQBYKP-UHFFFAOYSA-N 5-chloro-1,2-dimethylbenzimidazole Chemical compound ClC1=CC=C2N(C)C(C)=NC2=C1 FLDCSPABIQBYKP-UHFFFAOYSA-N 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- 239000001741 Ammonium adipate Substances 0.000 description 1
- 229920002101 Chitin Polymers 0.000 description 1
- 241000238557 Decapoda Species 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- FZHXIRIBWMQPQF-UHFFFAOYSA-N Glc-NH2 Natural products O=CC(N)C(O)C(O)C(O)CO FZHXIRIBWMQPQF-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010586 LiFeO 2 Inorganic materials 0.000 description 1
- 229910014689 LiMnO Inorganic materials 0.000 description 1
- 229910013290 LiNiO 2 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012790 adhesive layer Substances 0.000 description 1
- FZHXIRIBWMQPQF-SLPGGIOYSA-N aldehydo-D-glucosamine Chemical compound O=C[C@H](N)[C@@H](O)[C@H](O)[C@H](O)CO FZHXIRIBWMQPQF-SLPGGIOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 235000019293 ammonium adipate Nutrition 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- MSWZFWKMSRAUBD-UHFFFAOYSA-N beta-D-galactosamine Natural products NC1C(O)OC(CO)C(O)C1O MSWZFWKMSRAUBD-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000006182 cathode active material Substances 0.000 description 1
- 230000000850 deacetylating effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000002612 dispersion medium Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- KLKFAASOGCDTDT-UHFFFAOYSA-N ethoxymethoxyethane Chemical compound CCOCOCC KLKFAASOGCDTDT-UHFFFAOYSA-N 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012212 insulator Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000015110 jellies Nutrition 0.000 description 1
- 239000008274 jelly Substances 0.000 description 1
- 239000005001 laminate film Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000010721 machine oil Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 239000011356 non-aqueous organic solvent Substances 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920001690 polydopamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 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
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000009974 thixotropic effect Effects 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Cell Electrode Carriers And Collectors (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
本発明は、リチウム非水電解質電池に関し、特に改善された電極集電体との接触抵抗を有する電極合材を用いたリチウム非水電解質電池およびその製造方法に関する。 The present invention relates to a lithium nonaqueous electrolyte battery, and more particularly to a lithium nonaqueous electrolyte battery using an electrode mixture having improved contact resistance with an electrode current collector and a method for manufacturing the same.
近年、ディジタルカメラや、PDAのような小型携帯型電子機器が広く用いられるようになってきた。これらの電子機器は、容積を最小限にかつ重量を軽くすることが常に求められてきており、搭載される電池においても同様に小型、軽量かつ大容量の電池の実現が求められている。また、自動車搭載用などの大型二次 電池においても、従来の鉛蓄電池に代えて、大型の非水電解質二次電池の実現が望まれている。 In recent years, small portable electronic devices such as digital cameras and PDAs have come to be widely used. These electronic devices are always required to have a minimum volume and light weight, and it is also required to realize a small, light and large-capacity battery for the mounted battery. In addition, for large secondary batteries for use in automobiles, it is desired to realize a large nonaqueous electrolyte secondary battery instead of the conventional lead storage battery.
そのような要求に応え、リチウム非水電解質電池の開発が活発に行われている。水溶液系の電池では、水の分解電圧が1.23Vであることの制限を受けるため、水素あるいは酸素過電圧を考慮にいれても2Vの鉛電池が最高電圧である。しかし、リチウム非水電解質電池においては、高電圧で分解されない有機溶媒と電解質を改善することによって、高いエネルギー密度を実現することが可能となる。もっとも、有機電解液の導電率は、水溶液に比べると著しく、低く、比導電率は約10mS/cm程度であり、5%硫酸水溶液(鉛電池の水溶液)や6M KOH水溶液(アルカリマンガン電池の電解液)の1/10から数10分の1の導電率である。従って電流特性を改善するためには、電極面積を大きくする必要があり、従来の乾電池などの電池で用いられたボビン型でなく、アルミ電解コンデンサなどに採用されたジェリーロール型の電池構造が用いられている。 In response to such demands, lithium non-aqueous electrolyte batteries are being actively developed. In an aqueous battery, since the water decomposition voltage is limited to 1.23 V, a 2 V lead battery has the highest voltage even when hydrogen or oxygen overvoltage is taken into consideration. However, in a lithium non-aqueous electrolyte battery, it is possible to realize a high energy density by improving an organic solvent and an electrolyte that are not decomposed at a high voltage. However, the conductivity of the organic electrolyte is remarkably lower than that of the aqueous solution, and the specific conductivity is about 10 mS / cm. 5% sulfuric acid aqueous solution (lead battery aqueous solution) and 6M KOH aqueous solution (alkali manganese battery electrolysis). Conductivity) of 1/10 to 1/10 of (liquid). Therefore, in order to improve current characteristics, it is necessary to increase the electrode area, and instead of the bobbin type used in conventional batteries such as dry batteries, the jelly roll type battery structure adopted for aluminum electrolytic capacitors etc. is used. It has been.
ジェリーロール型のリチウム非水電解質電池の構造を、その一部欠截図である図1、および、リチウム非水電解質電池の発電要素であるセル本体の断面図である図2に示す。図1および図2に見られるように、この電池10は、負極集電体21、負極合材22、電解液とゲル化剤などからなる電解質層24、セパレータ25、電解質層26、正極合材27、および正極集電体層29からなるセル本体12を気密性の高い外装材11で被覆されている。そして、前記セル本体12に接続される電極は、前記集電体21、29からタブ状の端子13、14として外部に導出される。
The structure of the jelly-roll type lithium non-aqueous electrolyte battery is shown in FIG. 1 which is a partial cutaway view thereof, and FIG. 2 which is a cross-sectional view of a cell body which is a power generation element of the lithium non-aqueous electrolyte battery. As shown in FIGS. 1 and 2, the
図2に示すような、積層構造を有するリチウム非水電解質電池において、高い電流特性を確保するためには、電極面積を大きくすることに加えて、各層界面の接触抵抗の低減が不可欠である。 In a lithium nonaqueous electrolyte battery having a laminated structure as shown in FIG. 2, in order to ensure high current characteristics, in addition to increasing the electrode area, it is indispensable to reduce the contact resistance at the interface of each layer.
従来、正極電極集電体としては、有機電解液に優れた耐食性を有し、軽量で機械加工が容易なアルミニウムが主に用いられている。
また、電極合材としては、リチウム含有塩などの活物質やカーボン粉末などの導電助剤の粉末を、バインダー(結着材)と混合しスラリー状にしたものが用いられている。
バインダーとしては、一般には、PVDF(ポリふっ化ビニリデン)系の材料が用いられる。このバインダーは、電極集電体と電極合材を接着するために電極合材に含有される。
Conventionally, as the positive electrode current collector, aluminum that has excellent corrosion resistance with an organic electrolyte, is lightweight, and easy to machine is mainly used.
As the electrode mixture, an active material such as a lithium-containing salt or a conductive auxiliary powder such as carbon powder is mixed with a binder (binder) to form a slurry.
As the binder, PVDF (polyvinylidene fluoride) -based material is generally used. This binder is contained in the electrode mixture in order to bond the electrode current collector and the electrode mixture.
ここで、リチウム非水電解質電池の通常使用条件下においては、電極集電体であるアルミニウムの表面には絶縁物である酸化皮膜が形成される。そのため、電極集電体と電極合材の界面には、絶縁性の酸化被膜が介在することになり、接触抵抗の上昇が特に問題となる。 Here, under the normal use conditions of the lithium nonaqueous electrolyte battery, an oxide film that is an insulator is formed on the surface of aluminum that is the electrode current collector. For this reason, an insulating oxide film is interposed at the interface between the electrode current collector and the electrode mixture, and an increase in contact resistance is particularly problematic.
このように、積層構造を有するリチウム非水電解質電池においては、高い電流特性を確保するために各層界面接触抵抗低減、特にその性質上、抵抗上昇が生じやすい電極と電極合材界面の接触抵抗の低減が求められている。
しかし、これまでの電極合材材料では、高い電流特性を確保するために十分な電極集電体と電極合材界面の接触抵抗低減が実現できていなかったため、リチウム非水電解質電池の性能向上が困難であった。
As described above, in a lithium nonaqueous electrolyte battery having a laminated structure, in order to ensure high current characteristics, the contact resistance of each layer is reduced, and in particular, the contact resistance between the electrode and the electrode mixture interface where resistance is likely to increase. Reduction is required.
However, conventional electrode composite materials have not been able to reduce the contact resistance between the electrode current collector and the electrode composite interface enough to ensure high current characteristics, so the performance of lithium nonaqueous electrolyte batteries has been improved. It was difficult.
本発明は、従来のリチウム非水電解質電池等に用いられる電極合材における問題点を解決するためになされたもので、電極集電体と電極合材界面の接触抵抗を低減化することによって、電流特性が改善されたリチウム非水電解質電池を実現することを目的としている。 The present invention was made to solve the problems in the electrode mixture used in conventional lithium non-aqueous electrolyte batteries, etc., and by reducing the contact resistance between the electrode current collector and the electrode mixture, The object is to realize a lithium non-aqueous electrolyte battery with improved current characteristics.
第1の本発明は、アルミニウム薄膜からなる正極集電体表面に、活物質、導電助剤および化学式1で表わされる脱アセチル化度が80%以上のキトサン誘導体からなる組成物層を形成してなることを特徴とするリチウム非水電解質電池用電極である。 According to a first aspect of the present invention, a composition layer composed of an active material, a conductive additive, and a chitosan derivative having a degree of deacetylation represented by Chemical Formula 1 of 80% or more is formed on the surface of a positive electrode current collector composed of an aluminum thin film. This is an electrode for a lithium non-aqueous electrolyte battery.
第1の発明において、前記導電助剤が、アセチレンブラックであることが好ましい。 In the first invention, the conductive auxiliary agent is preferably acetylene black.
第1の発明において、前記組成物が、活物質100質量部、導電助剤1〜15質量部、およびキトサン誘導体を含むバインダー1〜6質量部からなるものであることが好ましい。 1st invention WHEREIN: It is preferable that the said composition consists of 1-6 mass parts of binders containing 100 mass parts of active materials, 1-15 mass parts of conductive support agents, and a chitosan derivative.
第2の本発明は、アルミニウム箔表面膜に、導電助剤および化学式1で表わされるキトサン誘導体からなる組成物層を形成してなることを特徴とするリチウム非水電解質電池用正極集電体である。 According to a second aspect of the present invention, there is provided a positive electrode current collector for a lithium non-aqueous electrolyte battery, wherein a composition layer comprising a conductive aid and a chitosan derivative represented by Chemical Formula 1 is formed on an aluminum foil surface film. is there.
第3の発明は、アルミニウム箔表面に、導電助剤および化学式1で表わされるキトサン誘導体を水もしくは有機溶剤に分散した分散液を塗布した後、乾燥させることを特徴とするリチウム非水電解質電池用正極集電体の製造方法である。 A third invention is a lithium non-aqueous electrolyte battery characterized in that a conductive auxiliary agent and a dispersion in which a chitosan derivative represented by Chemical Formula 1 is dispersed in water or an organic solvent are applied to the surface of the aluminum foil and then dried. It is a manufacturing method of a positive electrode electrical power collector.
第3の発明において、分散液が、さらに分子内にカルボキシル基を少なくとも1個有する有機化合物を含有することが好ましい。 In the third invention, the dispersion preferably further contains an organic compound having at least one carboxyl group in the molecule.
本発明によれば、絶縁性の酸化被膜が形成されたアルミニウムなどの集電体と電極合材との界面の接触抵抗を低減することができ、電流特性が改善されたリチウム非水電解質電池を得ることができる。また、集電体表面への活物質等の密着性に優れ、活物質等の集電体からの剥離も見られず、長寿命の電池を実現することができる。 According to the present invention, there is provided a lithium non-aqueous electrolyte battery having an improved current characteristic, which can reduce the contact resistance at the interface between a current collector such as aluminum on which an insulating oxide film is formed and an electrode mixture. Can be obtained. Moreover, it is excellent in the adhesiveness of the active material etc. to the surface of a collector, and the active material etc. are not peeled off from the collector, and a long-life battery can be realized.
本発明は前述したように、キトサン誘導体、アセチレンブラックおよび活物質を含有する電極合材を用いた点に特徴を有している。 As described above, the present invention is characterized in that an electrode mixture containing a chitosan derivative, acetylene black and an active material is used.
[非水電解質電池]
本発明を適用するのに適した非水電解質電池は、図1および図2に示すように、以下の構造を有するものである。すなわち、金属箔と、高分子フィルムとを接着剤で接合したシート体を用いて成形した外装材11の内部に、正極及び負極が、セパレータ25を介して重ね合わせられ、もしくは捲回後扁平化されてなる長方形状の電極体ユニット12が収納された構造であって、セパレータ25には電解質が含浸されている。この電極体ユニット12には、正極側表面に正極集電板29、負極側表面には負極集電板21が配設されており、正極集電板の表面には正極合剤層が形成されており、また負極集電体表面には負極合材層が形成されている。正極集電板のリード端子及び負極集電板のリード端子が外装体11の上縁部から外部に突出して外部へ導出するタブ端子13、14を形成している。これらのタブ端子13,14の表面には、オレフィン系フィルム15a,15bが貼着されており、前記外装材11を用いてヒートシールによって封止する際に、このタブ端子13,14表面に外装材11が気密に接着するようになっている。このオレフィン系フィルムとしては、マレイン化ポリプロピレンのような変成ポリオレフィンが適している。
[Nonaqueous electrolyte battery]
As shown in FIGS. 1 and 2, the nonaqueous electrolyte battery suitable for applying the present invention has the following structure. That is, a positive electrode and a negative electrode are overlapped with a
本発明のキトサン誘導体をバインダーとし、アセチレンブラックを導電助剤として用いた電極合剤は正極および負極のいずれにも用いることができるが、正極合剤に適用した場合、従来と比較して優れた効果を発揮する。 The electrode mixture using the chitosan derivative of the present invention as a binder and acetylene black as a conductive additive can be used for both the positive electrode and the negative electrode, but when applied to the positive electrode mixture, it is superior to the conventional one. Demonstrate the effect.
(電極合材)
電極合材としては、活物質、導電助剤、およびバインダーを含む組成物が用いられる。
この電極合材に用いられるバインダーの主成分である化学式1のキトサン誘導体は、カニ、エビ、昆虫などの甲殻あるいはキノコなどから得られる天然由来の高分子物質であるキチン、すなわちβ−ポリ−N−アセチル−D−グルコサミンを脱アセチル化して得られる2−アミノ−2−デオキシ−D−グルコースを構成単位とするアミノ基を含む多糖類であるキトサンの官能基の一部をグリセリル化することにより得られる。
(Electrode mixture)
As the electrode mixture, a composition containing an active material, a conductive additive, and a binder is used.
The chitosan derivative of Chemical Formula 1, which is the main component of the binder used in this electrode mixture, is chitin, a β-poly-N, which is a naturally-derived polymer substance obtained from crab, shrimp, shells of insects, mushrooms and the like. - to glycerin Li Le a part of the functional groups of chitosan is a polysaccharide containing amino groups for the 2-amino-2-deoxy -D- glucose obtained by deacetylating the acetyl -D- glucosamine and the structural unit Can be obtained.
このようなキトサン誘導体類は、工業的に生産されていて、種々のグレードのものが供給されており、市場で入手可能である。
本発明においては、キトサン誘導体としては、脱アセチル化度80%以上のものが適している。脱アセチル化度が、前記範囲を下回った場合、水に溶解して水溶液とする点で、水に溶解しにくくなり、本発明には不適切である。
また、重量平均分子量は、1000以上〜200万以下が好ましく、1万〜100万の範囲であることがより好ましい。分子量が、この範囲を下回った場合、接着層の皮膜形成の点で本発明で用いるには不適切であり、一方、分子量が、この範囲を上回った場合、水溶液とした溶液の粘度が高くなりすぎるため、作業性などの取り扱い上の点で本発明で用いるには不適切である。
Such chitosan derivatives are produced industrially, are supplied in various grades, and are commercially available.
In the present invention, a chitosan derivative having a degree of deacetylation of 80% or more is suitable. When the degree of deacetylation is lower than the above range, it becomes difficult to dissolve in water because it dissolves in water to form an aqueous solution, which is inappropriate for the present invention.
Moreover, 1000 or more and 2 million or less are preferable, and, as for a weight average molecular weight, it is more preferable that it is the range of 10,000-1 million. If the molecular weight is below this range, it is inappropriate for use in the present invention in terms of film formation of the adhesive layer. On the other hand, if the molecular weight exceeds this range, the viscosity of the aqueous solution increases. Therefore, it is inappropriate for use in the present invention in terms of handling such as workability.
また、バインダーの仕様としては、これらキトサン誘導体に、さらに分子内にカルボキシル基を少なくとも1個有する有機化合物を含有することが好ましい。 In addition, as a specification of the binder, it is preferable that these chitosan derivatives further contain an organic compound having at least one carboxyl group in the molecule.
本発明においては、キトサン誘導体を含有するバインダーを用いて非水電解質電池の電極集電体と電極合材の接合を行うが、このバインダーとしては、キトサン誘導体を水に溶解した水溶液として用いることができる。その濃度は、0.1〜20質量%の範囲が好ましい。キトサン誘導体の濃度が、0.1質量%を下回ると、接着強度が上がらず、実用的ではない。一方キトサン誘導体の濃度が上記範囲を上回った場合、粘度が上昇して取り扱いが困難になる。
また、このバインダーとして、キトサン誘導体以外に、分子内にカルボキシル基を少なくとも1個有する有機化合物、レオロジー特性改善剤(チキソトロピー性改善剤)、防腐剤、酸化防止剤等の添加剤を併用することができる。
In the present invention, the electrode collector of the non-aqueous electrolyte battery and the electrode mixture are joined using a binder containing a chitosan derivative. As the binder, an aqueous solution in which the chitosan derivative is dissolved in water can be used. it can. The concentration is preferably in the range of 0.1 to 20% by mass. When the concentration of the chitosan derivative is less than 0.1% by mass, the adhesive strength is not increased and it is not practical. On the other hand, when the concentration of the chitosan derivative exceeds the above range, the viscosity increases and handling becomes difficult.
In addition to the chitosan derivative, an additive such as an organic compound having at least one carboxyl group in the molecule, a rheological property improver (thixotropic improver), a preservative, an antioxidant may be used as the binder. it can.
本実施の形態の活物質材料としては、特に制限を受けることなく、非水電解質電池として一般に公知の材料を用いることができる。
具体的には例えば、正極活物質としてはリチウム含有塩(LiCoO2,LiNiO2,LiMnO2,LiFeO2等)など、負極活物質としては黒鉛粉末などを用いることができる。
As the active material of the present embodiment, a material generally known as a nonaqueous electrolyte battery can be used without any particular limitation.
Specifically, for example, lithium-containing salt as the cathode active material (LiCoO 2, LiNiO 2, LiMnO 2, LiFeO 2 and the like), or the like can be used graphite powder as a negative electrode active material.
また、電極合材内の電気抵抗低減と、電極集電体との界面接触抵抗低減のために、導電助剤が電極合材に含有される。導電助剤としては、粒状炭素であるカーボンブラックを用いることができるが、特に、粒径が小さく、界面接触抵抗の低減が著しいアセチレンブラックが好ましい。 Moreover, a conductive additive is contained in the electrode mixture in order to reduce the electrical resistance in the electrode mixture and to reduce the interface contact resistance with the electrode current collector. As the conductive additive, carbon black, which is granular carbon, can be used. In particular, acetylene black having a small particle size and a remarkable reduction in interfacial contact resistance is preferable.
電極合剤の組成物の配合比率は、活物質100質量部、導電助剤1〜15質量部、およびキトサン誘導体を含むバインダー1〜6質量部の範囲とすることができる。活物質量がこの範囲を下回ると電池容量が低減し好ましくない。一方バインダー量この範囲を下回ると集電体表面に製膜した際に剥離が生じやすく、取り扱いが困難となる。また、導電助剤量がこの範囲を下回ると、電極合剤と集電体との接触抵抗が増加し、電池の電気特性が低下する。 The mixing ratio of the composition of the electrode mixture can be in the range of 100 parts by mass of the active material, 1 to 15 parts by mass of the conductive additive, and 1 to 6 parts by mass of the binder containing the chitosan derivative. If the amount of the active material is less than this range, the battery capacity is undesirably reduced. On the other hand, if the amount of the binder is less than this range, peeling is likely to occur when the current collector is formed into a film, and handling becomes difficult. On the other hand, when the amount of the conductive assistant is below this range, the contact resistance between the electrode mixture and the current collector increases, and the electrical characteristics of the battery deteriorate.
前述のバインダー、活物質およびアセチレンブラックを混合し水もしくは有機溶剤を添加してスラリー状にし、後述の電極集電体表面に塗布、乾燥させることによって電極合材と集電体との積層構造を形成する。この有機溶剤としては、通常塗料、接着剤等において用いられている有機溶剤を採用することができる。 The above-mentioned binder, active material and acetylene black are mixed and water or an organic solvent is added to form a slurry, which is applied to the surface of the electrode current collector described later and dried to form a laminated structure of the electrode mixture and the current collector. Form. As the organic solvent, organic solvents that are usually used in paints, adhesives and the like can be employed.
(集電体)
電極集電体21、29によって電池外部へ電気が取り出される。
本実施の形態の電極集電体としては、特に制限を受けることなく、非水電解質電池として一般に公知の材料を用いることができる。
具体的には例えば、正極集電体には、アルミニウム、タンクル、ニオブ、チタン、ハフニウム、ジルコニウム、亜鉛、タングステン、ビスマス、アンチモンなど、負極集電体には銅などを用いることができる。
正極集電体としては、有機電解液に優れた耐食性を有し、軽量で機械加工が容易なアルミニウムが好ましい。
(Current collector)
Electricity is taken out of the battery by the electrode
As the electrode current collector of the present embodiment, a generally known material can be used as a nonaqueous electrolyte battery without any particular limitation.
Specifically, for example, aluminum, tantalum, niobium, titanium, hafnium, zirconium, zinc, tungsten, bismuth, antimony, or the like can be used for the positive electrode current collector, and copper or the like can be used for the negative electrode current collector.
As the positive electrode current collector, aluminum that has excellent corrosion resistance to an organic electrolyte, is lightweight, and is easy to machine is preferable.
(外装材)
非水有機溶媒を用いるリチウム非水電解質電池において、外装材としては金属箔と高分子フィルムとを接着した積層構造体を用いている。これは、電池内外の有機溶媒を含む気体の流通を阻止し、かつ、機械的強度を改善するためにこれらの材料を複合して用いているものである。
(Exterior material)
In a lithium nonaqueous electrolyte battery using a nonaqueous organic solvent, a laminated structure in which a metal foil and a polymer film are bonded is used as an exterior material. This is a combination of these materials in order to prevent the gas containing the organic solvent inside and outside the battery from flowing and to improve the mechanical strength.
本実施の形態の積層構造体は、図3に示すように、高分子フィルム31、キトサン誘導体を主要成分とする接着剤32、金属箔33、接着剤34、および高分子フィルム35からなっているものである。
As shown in FIG. 3, the laminated structure of the present embodiment includes a
本発明で用いる金属箔は、アルミニウム、銅、ニッケル、鉄、ステンレス等の金属あるいはこれらの合金の箔であり、その厚さは、特に制限されるものではないが、電池に用いる場合であれば、10〜100μmの範囲が好ましい。その表面は、圧延加工した加工面そのままであってもよいし、粗面化してもよい。 The metal foil used in the present invention is a foil of a metal such as aluminum, copper, nickel, iron, stainless steel, or an alloy thereof, and the thickness thereof is not particularly limited. The range of 10-100 micrometers is preferable. The surface may be a rolled processed surface as it is, or may be roughened.
本発明において用いる高分子フィルムとしては、機械的強度、気密性、電気絶縁性、耐熱性などを考慮して決めることが好ましい。これらの特性を備えた材料として、ポリプロピレン、ポリエチレン、ポリエステル、ポリアミド、ポリイミド、ポリフッ化ビニリデン、ポリウレタン等の材料が適している。前記外装材に適した積層構造体としては、ナイロンのようなポリアミドフィルム、金属箔、およびポリオレフィンフィルムからなる積層構造体が適している。
このフィルムの厚さは、何ら制限されるものではないが、この構造体を電池に採用するにあたっては、10〜100μmの範囲が好ましい。
The polymer film used in the present invention is preferably determined in consideration of mechanical strength, airtightness, electrical insulation, heat resistance, and the like. As materials having these characteristics, materials such as polypropylene, polyethylene, polyester, polyamide, polyimide, polyvinylidene fluoride, and polyurethane are suitable. As a laminated structure suitable for the exterior material, a laminated structure made of a polyamide film such as nylon, a metal foil, and a polyolefin film is suitable.
The thickness of the film is not limited at all, but when the structure is used in a battery, a range of 10 to 100 μm is preferable.
(セパレータ)
セパレータは、正極と負極が直接接触して電池内でショートすることを防止するものであって、非水電解質電池において公知の材料を用いることができる。具体的には、ポリオレフィンなどの多孔質高分子フィルムあるいは紙などからなっている。この多孔質高分子フィルムとしては、ポリエチレン、ポリプロピレンなどのフィルムが電解液によって影響を受けないため、好ましい。このセパレータは、正極や負極よりも若干大きいサイズに形成され、その端部は、正極や負極の端部よりも外に伸びており、両極が接触しないようになっている。
(Separator)
The separator prevents the positive electrode and the negative electrode from coming into direct contact and short-circuits in the battery, and a known material can be used in the nonaqueous electrolyte battery. Specifically, it is made of a porous polymer film such as polyolefin or paper. As this porous polymer film, a film made of polyethylene, polypropylene, or the like is preferable because it is not affected by the electrolyte. The separator is formed in a size slightly larger than that of the positive electrode or the negative electrode, and its end portion extends outward from the end portion of the positive electrode or the negative electrode so that the two electrodes do not come into contact with each other.
このセパレータには、正極と負極との間でイオン伝導が十分になされるように、多孔質膜における正極や負極に挟まれている箇所には電解質が充填されている。 In this separator, an electrolyte is filled in a portion of the porous membrane sandwiched between the positive electrode and the negative electrode so that ion conduction is sufficiently performed between the positive electrode and the negative electrode.
(電解質)
本実施の形態の非水電解質としては、非水溶媒と非水電解質物質とを含有しゲル状となっているものが用いられている。
非水電解液の溶媒としては、例えば、エチレンカーボネート、プロピレンカーボネートなどの有機溶媒、或はこれらとジメチルカーボネート、ジエチルカーボネート、1,2−ジメトキシエタン、1,2−ジエトキシエタン、エトキシメトキシエタンなどの低沸点溶媒との混合溶媒が挙げられ、非水電解液の溶質である電解質としては、LiPF6、LiClO4、LiCF3SO3が挙げられる。
(Electrolytes)
As the nonaqueous electrolyte of the present embodiment, a gel containing a nonaqueous solvent and a nonaqueous electrolyte substance is used.
Examples of the solvent for the nonaqueous electrolytic solution include organic solvents such as ethylene carbonate and propylene carbonate, or dimethyl carbonate, diethyl carbonate, 1,2-dimethoxyethane, 1,2-diethoxyethane, ethoxymethoxyethane, and the like. Examples of the electrolyte that is a solute of the nonaqueous electrolytic solution include LiPF 6 , LiClO 4 , and LiCF 3 SO 3 .
(タブ端子部)
前述の通り、タブ端子は、正負極集電体から導出される端子であり、外装材の封止接合界面から外部に導出される構造となっている。このタブ端子13,14は、アルミニウム、ニッケルなどの金属箔からなるものであって、これは、外装材をヒートシールしても、タブ端子と外装材との間で、気密性のある接着が生じないため、タブ端子13,14表面には、予め高分子フィルム15a,15bを接着しておくことが好ましい
(Tab terminal part)
As described above, the tab terminal is a terminal derived from the positive and negative electrode collectors, and has a structure derived from the sealing joint interface of the exterior material to the outside. The
本実施の形態のリチウム非水電解質電池は、上記した構造を有するものであり、この構造において、キトサン誘導体、アセチレンブラックおよび活物質を含有する電極合材を用いることが、電極集電体と電極合材との接触抵抗を低減し、高い電流特性を確保し、電池性能を向上させる上で好ましい。 The lithium non-aqueous electrolyte battery according to the present embodiment has the above-described structure, and in this structure, an electrode mixture containing a chitosan derivative, acetylene black and an active material is used. It is preferable for reducing contact resistance with the composite material, ensuring high current characteristics, and improving battery performance.
(非水電解質電池の製造方法)
この非水電解質電池は、以下のようにして製造することができる。
(1)電極体ユニットの作製
導電性金属箔を所定形状に切断することによって正極集電板及び負極集電板を作製する。正極および負極は、正負極活物質、導電助材、およびバインダーを、水もしくは有機溶剤に分散させて分散液とし、集電板の表面に塗布乾燥することによって作製する。この正負極においてバインダーとしてキトサン誘導体と分子内にカルボキシル基を少なくとも1個有する有機化合物を含有する接着剤を用いることが好ましい。セパレータは、ポリオレフィン系多孔質フィルムを所定形状に切断することによって作製する。これらの正極、セパレータ、負極をそれぞれ複数枚重ね合わせて電極体ユニットを作成する。
また、長尺の正極、セパレータ、負極、及び第2のセパレータをコイル状に捲回し、これを偏平に圧縮して電極体ユニットとすることもできる。
(Method for producing non-aqueous electrolyte battery)
This non-aqueous electrolyte battery can be manufactured as follows.
(1) Production of electrode body unit A positive electrode current collector plate and a negative electrode current collector plate are produced by cutting a conductive metal foil into a predetermined shape. The positive electrode and the negative electrode are prepared by dispersing a positive and negative electrode active material, a conductive additive, and a binder in water or an organic solvent to form a dispersion, and applying and drying on the surface of the current collector plate. In this positive and negative electrode, an adhesive containing a chitosan derivative and an organic compound having at least one carboxyl group in the molecule is preferably used as a binder. The separator is produced by cutting a polyolefin-based porous film into a predetermined shape. A plurality of these positive electrodes, separators, and negative electrodes are overlapped to form an electrode body unit.
Moreover, a long positive electrode, a separator, a negative electrode, and a 2nd separator can be wound in a coil shape, and this can be compressed flatly to make an electrode body unit.
(2)電解液の含浸
非水溶媒、非水電解質、及び場合によってゲル化剤を添加配合し、電解液を調整する。この電解液に前記電極体ユニットを浸漬することによって、電解液の含浸を行うことができる。尚、電解液の粘度が高い場合には、十分量の電解液が電極体ユニットに含浸されるのに長時間を要する。このような場合には、減圧できる容器中に電極体ユニットを配置し、減圧した後、容器中に電解液を注入することによって、効率的に含浸を行うことができる。
(2) Impregnation of electrolytic solution A nonaqueous solvent, a nonaqueous electrolyte, and optionally a gelling agent are added and blended to adjust the electrolytic solution. By immersing the electrode body unit in the electrolytic solution, the electrolytic solution can be impregnated. When the viscosity of the electrolytic solution is high, it takes a long time for the electrode body unit to be impregnated with a sufficient amount of the electrolytic solution. In such a case, the impregnation can be efficiently performed by disposing the electrode body unit in a container that can be depressurized, injecting the electrolytic solution into the container after depressurizing.
(3)外装材
その後、電解液を含浸した電極体ユニットを被包するように第1の高分子フィルム、金属箔、第2の高分子フィルムを有する積層体を配置し、表面に高分子フィルムで電極体ユニットから導出されるタブ状リード端子を挟持した状態で積層体フィルムをシールする。このシールは、積層体フィルムの相対する面が高分子フィルムであれば、加熱して接着させるヒートシールによって行うことができる。一方、相対する面が金属箔であれば、接着剤を用いてシールを行うことができる。
(3) Exterior material After that, a laminated body having a first polymer film, a metal foil, and a second polymer film is disposed so as to enclose the electrode body unit impregnated with the electrolytic solution, and the polymer film is disposed on the surface. The laminated film is sealed in a state where the tab-shaped lead terminal led out from the electrode body unit is sandwiched. This sealing can be performed by heat sealing when the opposite surfaces of the laminate film are polymer films, which are heated and bonded. On the other hand, if the opposing surface is a metal foil, sealing can be performed using an adhesive.
なお、上記(2)の含浸工程は、セパレータを正極,負極と重ね合わせる前に行ってもよいし、多孔質膜を正極板,負極板と重ね合わせて電極体ユニットを形成した後で行ってもよい。 The impregnation step (2) may be performed before the separator is overlaid with the positive electrode and the negative electrode, or after the porous film is overlaid with the positive electrode plate and the negative electrode plate to form the electrode body unit. Also good.
以上の製造方法によって、非水電解質電池を作製することができる。 A non-aqueous electrolyte battery can be produced by the above manufacturing method.
以下、本発明を実験例および比較例によって説明する。 Hereinafter, the present invention will be described with reference to experimental examples and comparative examples.
(電極の作成方法)
正極集電体には、アルミニウム箔(多結晶性99.99%、0.1mm厚み、電解コンデンサ用)を用いた。このアルミニウム箔を7mm×7mmの旗型電極とし、電極面積が両面で10−4m2(=1cm2)になるようにした。柄の部分はアノード分極による濡れ性変化に伴う浸漬面積の変化を抑制するため液面近傍を予めアジピン酸アンモニウム水溶液中でアノード酸化した)。この柄の部分をネジに直接挟み込んで固定し試料極とした。旗型電極は工業試験においてももっとも多く用いられる。電極面積を一定にするためには電極のリ一ドの部分をマスキングするのが効果的である。液面近傍はアノード酸化皮膜の濡れ性の変化によりノイズを生じやすい。そこで柄の部分を予め高い電圧でアノード酸化することにより、見かけの電極面積が一定となるようにした。アノード酸化皮膜によるマスキング方法は密着性が高く、樹脂やテープによるシーリングに比べて作成が簡便で確実である利点がある。反面、塩化物イオンを含む溶液中では使用できないなどの制限もある。
(Electrode creation method)
As the positive electrode current collector, an aluminum foil (polycrystalline 99.99%, 0.1 mm thickness, for electrolytic capacitor) was used. This aluminum foil was used as a 7 mm × 7 mm flag electrode, and the electrode area was 10 −4 m 2 (= 1 cm 2 ) on both sides. The handle portion was previously anodized in an aqueous solution of ammonium adipate in order to suppress the change in the immersion area accompanying the change in wettability due to anode polarization). This handle portion was directly sandwiched between screws and fixed to obtain a sample electrode. Flag electrodes are most often used in industrial tests. In order to make the electrode area constant, it is effective to mask the lead portion of the electrode. The vicinity of the liquid surface is likely to generate noise due to the change in wettability of the anodic oxide film. Therefore, the apparent electrode area was made constant by anodizing the pattern portion at a high voltage in advance. The masking method using an anodic oxide film has the advantage that the adhesion is high and the preparation is simpler and more reliable than sealing with resin or tape. On the other hand, there is a limitation that it cannot be used in a solution containing chloride ions.
溶液に露出する面は7×7mm2角とし、両面で1cm2とした。この試験片の形状は、EIAJの規格を参考にした。柄の部分は液面変動による電極面積の変化の影響を少なくするために、予め測定電位より高い電位までアノード酸化してマスキングとした。 The surface exposed to the solution was 7 × 7 mm square, and 1 cm 2 on both sides. The shape of this test piece was referred to the EIAJ standard. In order to reduce the influence of the change in the electrode area due to the liquid level fluctuation, the handle portion was masked by anodizing to a potential higher than the measurement potential in advance.
電極の前処理としてアルカリ脱脂を行った。アルミニウムの表面は自然酸化皮膜で覆われており、圧延時の機械油なども付着している。したがって再現性の高い結果を得るには測定前の処理が重要である。アルミニウムの前処理については電解研磨、アルカリ脱脂など種々の方法が検討されているが、ここでは簡便かつ迅速であり、比較的良好な再現性が得られるアルカリ脱脂を用いた。アルカリ脱脂は、1M NaOH中で60秒、蒸留水で10秒すすぎ、0.65M HNO3で30秒中和し、再度蒸留水で10秒すすいだ。水分の除去が必要なときにはMeOHに浸すことによって行った。 Alkaline degreasing was performed as a pretreatment of the electrode. The surface of aluminum is covered with a natural oxide film, and machine oil during rolling is also attached. Therefore, pre-measurement processing is important for obtaining highly reproducible results. Various methods such as electrolytic polishing and alkaline degreasing have been studied for pretreatment of aluminum. Here, alkaline degreasing which is simple and quick and relatively good reproducibility is obtained was used. Alkaline degreasing was rinsed in 1 M NaOH for 60 seconds, distilled water for 10 seconds, neutralized with 0.65 M HNO 3 for 30 seconds, and again rinsed with distilled water for 10 seconds. When it was necessary to remove moisture, it was performed by soaking in MeOH.
(バインダー試料)
バインダー試料はキトサン誘導体系バインダー(協立化学産業株式会社製)と、比較として一般的にリチウムイオン二次電池のバインダーとして用いられているPVDF系のバインダーとの2種類のバインダーを用いた。
(Binder sample)
As binder samples, two types of binders were used: a chitosan derivative binder (manufactured by Kyoritsu Chemical Industry Co., Ltd.) and a PVDF binder generally used as a binder for lithium ion secondary batteries as a comparison.
(バインダーと炭素(AB:アセチレンブラック)の混合)
バインダーとABの混合は、始めに分散媒体、バインダーとABをサンプル瓶に入れる。サンプル瓶ごと超音波処理しバインダー中にABの分散した炭素分散液を作製した。
(Mixture of binder and carbon (AB: acetylene black))
To mix the binder and AB, first put the dispersion medium, binder and AB into the sample bottle. The sample bottle was sonicated to prepare a carbon dispersion in which AB was dispersed in a binder.
(バインダーと炭素(AB)の集電体への塗布)
集電体へのバインダーの塗布は、ディップコーティングした後、乾燥することによって行った。ディップコーティング後の乾燥条件は、第1ステップが大気中、80℃、0.5時間の条件、第2ステップが真空中、160℃、4時間の条件で行った。そして、乾燥処理後、熱処理を260℃大気中にて行った。
(Application of binder and carbon (AB) to current collector)
The binder was applied to the current collector by dip coating and then drying. The drying conditions after the dip coating were performed under the conditions that the first step was in the atmosphere at 80 ° C. for 0.5 hours, and the second step was in vacuum at 160 ° C. for 4 hours. Then, after the drying treatment, heat treatment was performed in the atmosphere at 260 ° C.
(電解液)
本実施例の有機電解液としてはLiBF4、LiClO4を電解質とし、非プロトン製で誘電率の高いプロピレンカーボネート(PC)とジメトキシエタン(DME)の混合溶媒に溶解した電解液を使用した。
(Electrolyte)
As the organic electrolytic solution of this example, an electrolytic solution containing LiBF 4 and LiClO 4 as an electrolyte and dissolved in a mixed solvent of propylene carbonate (PC) and dimethoxyethane (DME) having high dielectric constant was used.
(電解セル)
リチウム電池を取り扱う有機電解液系のセルにおいては、特に水分による汚染に注意を払わなくてはならない。そこで比較的短い時間での環象を観察する電解セルは、アルゴン置換したグローブボックス内で組み立ておよび測定を行った。グローブボックスの外で有機電解液を用いて測定する場合には、気密セルをグローブボックス内で組み立ててから取り出した。有機電解液の電解セルの対極にPt、擬似参照極としてAgを用いた。リチウムイオン二次電池の電気化学測定ではLiを参照極に用いることが多いが、本実施例ではAgを擬似参照電極として用いている。Agを擬似参照電極として用いるのはボテンショスタットのアノード側の電位制御範囲を広げ、水溶液系との比較をしやすくするためである。Ag擬似参照電極の電位はLiに対して+3.0Vであることを実測により確認している。
水溶液系の電解セル対極にPt、参照極に銀/塩化銀電極を用いた。アノード酸化を行う際は塩化物イオンの混入を極力防がなければならない。そこで塩化物イオンの汚染を防ぐために、参照極は二重塩橋で接続した。対極には白金を用い、参照極には電解液と同じ溶液で満たした二重塩橋で接続した飽和KCl−銀/塩化銀電極を用い、3極式で測定を行った。
(Electrolytic cell)
In an organic electrolyte cell that handles a lithium battery, special attention must be paid to moisture contamination. Therefore, the electrolytic cell for observing the image in a relatively short time was assembled and measured in a glove box substituted with argon. When measuring using an organic electrolyte outside the glove box, the airtight cell was assembled in the glove box and taken out. Pt was used as the counter electrode of the electrolytic cell of the organic electrolyte, and Ag was used as the pseudo reference electrode. In electrochemical measurement of a lithium ion secondary battery, Li is often used as a reference electrode, but in this embodiment, Ag is used as a pseudo reference electrode. The reason why Ag is used as a pseudo reference electrode is to expand the potential control range on the anode side of the potentiostat and facilitate comparison with the aqueous solution system. It has been confirmed by actual measurement that the potential of the Ag pseudo reference electrode is +3.0 V with respect to Li.
Pt was used for the counter electrode of the aqueous electrolytic cell, and a silver / silver chloride electrode was used for the reference electrode. When anodic oxidation is performed, it is necessary to prevent contamination of chloride ions as much as possible. In order to prevent chloride ion contamination, the reference electrode was connected with a double salt bridge. The measurement was performed in a three-pole system using platinum as a counter electrode and a saturated KCl-silver / silver chloride electrode connected by a double salt bridge filled with the same solution as the electrolytic solution as a reference electrode.
以下に、評価を行う試験方法について説明する。
(サイクリックボルタンメトリー(電位−電流))
電気化学的測定法としてもっとも一般的手法であるサイクリックボルタンメトリー試験を行った。この方法は、電位掃引を折り返し行い、そのときの電流応答を観察する手法である。一般的に取り扱われる固/液界面では生成物の拡散状態や系の可逆系などさまざまな場合について検討されている例があるが、皮膜生成系や電池系での取り扱った例は見られない.皮膜の厚みをファラデーの法則を用いて堆定する場合に、電位の絶対値を対象とすると、初期皮膜厚がわからない、副反応の影響がわからないなどの欠点を有する。しかし、電位掃引速度をから求めることで初期皮膜厚がわからなくても内部電場強度を評価し電流平坦部の様子から副反応の有無を評価することができる。
また、電流電圧特性から、Alとバインダーの接触抵抗を求めることが可能となる。
Below, the test method which evaluates is demonstrated.
(Cyclic voltammetry (potential-current))
A cyclic voltammetry test, which is the most general method for electrochemical measurement, was performed. This method is a method of observing the current response at the time when the potential sweep is repeated. There are examples that have been studied in various cases such as the diffusion state of the product and the reversible system of the system at the solid / liquid interface that is generally handled, but there are no examples in the film generation system or battery system. When the thickness of the film is deposited using Faraday's law, if the absolute value of the potential is used, the initial film thickness is not known, and the influence of side reactions is not known. However, by obtaining the potential sweep rate, the internal electric field strength can be evaluated and the presence or absence of a side reaction can be evaluated from the state of the current flat portion even if the initial film thickness is not known.
Further, the contact resistance between Al and the binder can be obtained from the current-voltage characteristics.
(実験例1)
キトサン誘導体系バインダー3質量%と炭素(AB)3質量%を集電体に塗布し、サイクリックボルタンメトリー評価を行った。
(Experimental example 1)
3% by mass of a chitosan derivative-based binder and 3% by mass of carbon (AB) were applied to a current collector, and cyclic voltammetry evaluation was performed.
(比較例1)
PVDFバインダー3質量%と炭素(AB)3質量%を集電体に塗布し、サイクリックボルタンメトリー評価を行った。
(Comparative Example 1)
3% by mass of PVDF binder and 3% by mass of carbon (AB) were applied to a current collector and subjected to cyclic voltammetry evaluation.
(結果)
上記実験例及び比較例について、サイクリックボルタンメトリー試験を行った結果、本実施例のキトサン誘導体を用いた場合でも、従来のPVDFバインダーを用いた実験例と比較して遜色のない結果が得られた。
(result)
As a result of conducting a cyclic voltammetry test on the above experimental example and comparative example, even when the chitosan derivative of this example was used, a result comparable to the experimental example using the conventional PVDF binder was obtained. .
(バインダーの接着状態)
前記実験例及び比較例とも、乾燥条件では変色、剥離は起こらなかった。
(Binder adhesion state)
In both the experimental example and the comparative example, discoloration and peeling did not occur under dry conditions.
(Alとバインダーの接触抵抗)
サイクリックボルタンメトリー評価より得られた電流−電圧特性から、Alとバインダーの接触抵抗を求めた。その結果、PVDFバインダーに比べ、キトサン誘電体系バインダーを用いる方が、Alとバインダーの接触抵抗が低下することが明らかになった。
(Contact resistance between Al and binder)
The contact resistance between Al and the binder was determined from the current-voltage characteristics obtained from the cyclic voltammetry evaluation. As a result, it has been clarified that the contact resistance between Al and the binder is lowered when the chitosan dielectric binder is used as compared with the PVDF binder.
(活物質の剥離)
本発明のキトサン誘導体のバインダーを用いた場合には、長時間の使用においても集電体からの活物質の剥離は見られなかった。一方、PVDFバインダーを用いた場合には、剥離が見られた。
(Peeling of active material)
In the case of using the chitosan derivative binder of the present invention, no peeling of the active material from the current collector was observed even after long-term use. On the other hand, when the PVDF binder was used, peeling was observed.
(結果のまとめ)
以上の結果から、本発明のキトサン誘導体をバインダーとして用いた場合には、非水電解質中においても、活物質の剥離も見られず、長寿命の電池を実現できることが明らかとなった。また、従来のPVDFバインダーを用いた場合と比較して、電気化学的には遜色が無かった。
(Summary of results)
From the above results, it was revealed that when the chitosan derivative of the present invention was used as a binder, the active material was not peeled even in the nonaqueous electrolyte, and a long-life battery could be realized. Moreover, compared with the case where the conventional PVDF binder was used, there was no fading electrochemically.
10…非水電解質電池
11…外装材
12…発電要素(電極体ユニット)
13、14…タブ状端子
21…負極集電体
23…負極混合材
24…電解液を含む電解質層
25…セパレータ
26…電解質層
27…正極混合材
29…正極集電体層
31…第1の高分子フィルム
32…接着剤
33…金属箔
34…接着剤
35…高分子フィルム
DESCRIPTION OF
DESCRIPTION OF
Claims (4)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009164478A JP5284896B2 (en) | 2009-07-13 | 2009-07-13 | Electrode for lithium non-aqueous electrolyte battery, positive electrode current collector for lithium non-aqueous electrolyte battery, and method for producing the same |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2009164478A JP5284896B2 (en) | 2009-07-13 | 2009-07-13 | Electrode for lithium non-aqueous electrolyte battery, positive electrode current collector for lithium non-aqueous electrolyte battery, and method for producing the same |
Related Parent Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2005103382A Division JP2006286344A (en) | 2005-03-31 | 2005-03-31 | Lithium nonaqueous electrolyte battery and its manufacturing method |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2013078358A Division JP2013152950A (en) | 2013-04-04 | 2013-04-04 | Cathode collector for lithium nonaqueous electrolyte battery and method for producing the same |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2009277660A JP2009277660A (en) | 2009-11-26 |
JP5284896B2 true JP5284896B2 (en) | 2013-09-11 |
Family
ID=41442864
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2009164478A Active JP5284896B2 (en) | 2009-07-13 | 2009-07-13 | Electrode for lithium non-aqueous electrolyte battery, positive electrode current collector for lithium non-aqueous electrolyte battery, and method for producing the same |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP5284896B2 (en) |
Families Citing this family (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2012114835A1 (en) * | 2011-02-23 | 2012-08-30 | 大日精化工業株式会社 | Aqueous liquid composition, aqueous coating, functional coating film, and composite material |
US20140193709A1 (en) * | 2011-06-24 | 2014-07-10 | Mitsubishi Rayon Co., Ltd. | Binder for electrode of electrochemical element, composition for electrode of electrochemical element, electrode of electrochemical element and electrochemical element |
WO2013018688A1 (en) * | 2011-07-29 | 2013-02-07 | 古河スカイ株式会社 | Collector, electrode structure, non-aqueous electrolyte cell, and electricity storage component |
US20150093649A1 (en) * | 2012-04-09 | 2015-04-02 | Showa Denko K.K. | Method of producing current collector for electrochemical element, method of producing electrode for electrochemical element, current collector for electrochemical element, electrochemical element, and coating liquid for fabricating current collector for electrochemical element |
EP2843735A4 (en) | 2012-04-27 | 2015-12-02 | Showa Denko Kk | Method for producing anode active material for secondary battery, anode active material for secondary battery, method for producing anode for secondary battery, anode for secondary battery, and secondary battery |
WO2013161749A1 (en) | 2012-04-27 | 2013-10-31 | 昭和電工株式会社 | Anode for secondary battery, method for producing same, and secondary battery |
JP2015165452A (en) * | 2012-07-05 | 2015-09-17 | 昭和電工株式会社 | Method of using electrochemical element |
US20150255788A1 (en) * | 2012-09-26 | 2015-09-10 | Showa Denko K.K. | Negative electrode for secondary battery and secondary battery |
JP2013152950A (en) * | 2013-04-04 | 2013-08-08 | Kyoritsu Kagaku Sangyo Kk | Cathode collector for lithium nonaqueous electrolyte battery and method for producing the same |
JP6350150B2 (en) | 2013-09-30 | 2018-07-04 | 株式会社Gsユアサ | Electricity storage element |
KR101583142B1 (en) * | 2014-06-12 | 2016-01-06 | 경희대학교 산학협력단 | Method of producing the same and Electrode for a rechargeable battery employing the same |
JP6184552B2 (en) * | 2016-05-11 | 2017-08-23 | 株式会社Uacj | Current collector, electrode structure, non-aqueous electrolyte battery, and power storage component |
CN113937295B (en) * | 2021-10-15 | 2023-04-18 | 山东大学 | Self-assembled MXene/chitosan composite membrane and preparation method and application thereof |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3223423A1 (en) * | 1982-06-23 | 1983-12-29 | Wella Ag, 6100 Darmstadt | COSMETIC AGENTS BASED ON CHITOSAN DERIVATIVES, NEW CHITOSAN DERIVATIVES AND METHOD FOR PRODUCING THESE DERIVATIVES |
JP3066682B2 (en) * | 1992-09-10 | 2000-07-17 | 富士写真フイルム株式会社 | Chemical battery |
JP2840013B2 (en) * | 1993-09-30 | 1998-12-24 | 自動車機器株式会社 | Traction control device and method |
JP3958536B2 (en) * | 2000-07-12 | 2007-08-15 | 大日精化工業株式会社 | Aqueous solution composition and article surface modification method |
JP2002035141A (en) * | 2000-07-31 | 2002-02-05 | Yasutake Hichi | Bio-electrode, method for manufacturing the same, clothing with bio-electrode, electrocardiograph, low frequency therapeutic instrument and high frequency therapeutic instrument |
-
2009
- 2009-07-13 JP JP2009164478A patent/JP5284896B2/en active Active
Also Published As
Publication number | Publication date |
---|---|
JP2009277660A (en) | 2009-11-26 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP5284896B2 (en) | Electrode for lithium non-aqueous electrolyte battery, positive electrode current collector for lithium non-aqueous electrolyte battery, and method for producing the same | |
US11603321B2 (en) | Rechargeable aluminum ion battery | |
JP7150730B2 (en) | Energy storage devices and systems | |
US10559855B2 (en) | Rechargeable aluminum ion battery | |
JP3825593B2 (en) | Manufacturing method of package | |
JPH097896A (en) | Electric double-layer capacitor | |
US20110159361A1 (en) | Nonaqueous electrolyte secondary battery and method for producing the same | |
JP2002203562A (en) | Non-aqueous electrolyte secondary battery | |
EP3526878A1 (en) | Rechargeable aluminum ion battery | |
JP2006286344A (en) | Lithium nonaqueous electrolyte battery and its manufacturing method | |
CN108432025B (en) | Nonaqueous electrolyte battery and battery pack | |
JP2004146361A (en) | Lithium battery negative electrode, and lithium battery including same | |
JP4365791B2 (en) | Non-aqueous electrolyte battery adhesive and non-aqueous electrolyte battery using the same | |
EP4145567A1 (en) | Non-aqueous electrolyte secondary battery | |
CA2374706A1 (en) | Electrode body evaluation method and lithium secondary cell using the same | |
US6780545B2 (en) | Method for manufacturing galvanic elements having a liquid organic electrolyte | |
JP2008027771A (en) | Nonaqueous electrolyte battery tab lead material, method for fabrication thereof and nonaqueous electrolyte battery including the same | |
TWI359524B (en) | A method of identifying defective electrodes durin | |
WO2022000308A1 (en) | Bipolar current collector, electrochemical device, and electronic device | |
JPH07161389A (en) | Nonaqueous electrolyte battery | |
JP2012212621A (en) | Binder for electrochemical cell, and paste and electrode comprising the binder | |
JP3587982B2 (en) | Polymer solid electrolyte and lithium secondary battery and electric double layer capacitor using the same | |
JP4845245B2 (en) | Lithium battery | |
CN110100332B (en) | Electrochemical device | |
TW200835023A (en) | Forming polymer electrolyte coating on lithium-ion polymer battery electrode |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20120717 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20120918 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A821 Effective date: 20120918 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20121018 |
|
A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20130108 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20130404 |
|
A911 | Transfer to examiner for re-examination before appeal (zenchi) |
Free format text: JAPANESE INTERMEDIATE CODE: A911 Effective date: 20130513 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20130528 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20130530 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 5284896 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |