JP2022081421A - Negative electrode body for zinc battery and zinc battery - Google Patents
Negative electrode body for zinc battery and zinc battery Download PDFInfo
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- JP2022081421A JP2022081421A JP2021178565A JP2021178565A JP2022081421A JP 2022081421 A JP2022081421 A JP 2022081421A JP 2021178565 A JP2021178565 A JP 2021178565A JP 2021178565 A JP2021178565 A JP 2021178565A JP 2022081421 A JP2022081421 A JP 2022081421A
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- negative electrode
- electrode material
- porous member
- zinc battery
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- 239000011701 zinc Substances 0.000 title claims abstract description 80
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 76
- 239000007773 negative electrode material Substances 0.000 claims abstract description 114
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 238000004080 punching Methods 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 description 26
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 25
- 238000000034 method Methods 0.000 description 20
- 239000010410 layer Substances 0.000 description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 18
- 239000000126 substance Substances 0.000 description 18
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 16
- 239000007772 electrode material Substances 0.000 description 16
- -1 polytetrafluoroethylene Polymers 0.000 description 16
- 239000003054 catalyst Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- 239000012528 membrane Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- 239000004020 conductor Substances 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 11
- 208000028659 discharge Diseases 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052759 nickel Inorganic materials 0.000 description 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 8
- 239000011787 zinc oxide Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 7
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 7
- 229940007718 zinc hydroxide Drugs 0.000 description 7
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 6
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 6
- 239000004698 Polyethylene Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
- 229920000573 polyethylene Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 210000001787 dendrite Anatomy 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- BSWGGJHLVUUXTL-UHFFFAOYSA-N silver zinc Chemical compound [Zn].[Ag] BSWGGJHLVUUXTL-UHFFFAOYSA-N 0.000 description 5
- 238000011282 treatment Methods 0.000 description 5
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- 229910001923 silver oxide Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 230000004308 accommodation Effects 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 3
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 3
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 3
- 230000002093 peripheral effect Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 125000006850 spacer group Chemical group 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004952 Polyamide Substances 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229920004890 Triton X-100 Polymers 0.000 description 2
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Chemical compound [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 2
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 2
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 2
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000007514 bases Chemical class 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000019241 carbon black Nutrition 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 150000001869 cobalt compounds Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- PMHQVHHXPFUNSP-UHFFFAOYSA-M copper(1+);methylsulfanylmethane;bromide Chemical compound Br[Cu].CSC PMHQVHHXPFUNSP-UHFFFAOYSA-M 0.000 description 1
- 238000003851 corona treatment Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010559 graft polymerization reaction Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 229920001600 hydrophobic polymer Polymers 0.000 description 1
- 150000002472 indium compounds Chemical class 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004660 morphological change Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 239000011698 potassium fluoride Substances 0.000 description 1
- 235000003270 potassium fluoride Nutrition 0.000 description 1
- 229910000160 potassium phosphate Inorganic materials 0.000 description 1
- 235000011009 potassium phosphates Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 150000002909 rare earth metal compounds Chemical class 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000011775 sodium fluoride Substances 0.000 description 1
- 235000013024 sodium fluoride Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 235000011008 sodium phosphates Nutrition 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000010959 steel Substances 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
- 238000004381 surface treatment Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
本開示は、亜鉛電池用負極体、亜鉛電池等に関する。 The present disclosure relates to a negative electrode body for a zinc battery, a zinc battery, and the like.
ニッケル亜鉛電池は、水酸化カリウム水溶液等の水系電解液を用いる水系電池であることから、高い安全性を有すると共に、亜鉛電極とニッケル電極との組み合わせにより、水系電池としては高い起電力を有することが知られている。さらに、ニッケル亜鉛電池は、優れた入出力性能に加えて、低コストであることから、産業用途（例えば、バックアップ電源等の用途）及び自動車用途（例えば、ハイブリッド自動車等の用途）への適用可能性が検討されている。 Since the nickel-zinc battery is an aqueous battery that uses an aqueous electrolyte solution such as an aqueous potassium hydroxide solution, it has high safety and has a high electromotive force as an aqueous battery due to the combination of the zinc electrode and the nickel electrode. It has been known. Further, since the nickel-zinc battery has excellent input / output performance and low cost, it can be applied to industrial applications (for example, applications such as backup power supply) and automobile applications (for example, applications such as hybrid automobiles). Gender is being considered.
ニッケル亜鉛電池の充放電反応は、例えば、下記式に従って進行する（放電反応：右向き、充電反応：左向き）。
（正極）２ＮｉＯＯＨ＋２Ｈ２Ｏ＋２ｅ－ → ２Ｎｉ（ＯＨ）２＋２ＯＨ－
（負極）Ｚｎ＋２ＯＨ－ → Ｚｎ（ＯＨ）２＋２ｅ－
The charge / discharge reaction of the nickel-zinc battery proceeds according to, for example, the following formula (discharge reaction: facing right, charging reaction: facing left).
(Positive electrode) 2NiOOH + 2H 2O + 2e － → 2Ni (OH) 2 + 2OH －
(Negative electrode) Zn + 2OH- → Zn (OH) 2 + 2e-
上記式に示されるように、ニッケル亜鉛電池では、放電反応により水酸化亜鉛（Ｚｎ（ＯＨ）２）が生成する。水酸化亜鉛は電解液に可溶であり、水酸化亜鉛が電解液に溶解すると、テトラヒドロキシド亜鉛酸イオン（［Ｚｎ（ＯＨ）４］２－）が電解液中に拡散する。その結果、負極の形態変化（変形）が進行すると共に充電電流の分布が不均一となること等により、負極上の局所で亜鉛の析出が起こり、デンドライト（樹枝状結晶）が発生する。ニッケル亜鉛電池では、充放電の繰り返しによりデンドライトが成長した場合、デンドライトがセパレータを貫通して短絡が発生するため、上記デンドライトの発生は寿命性能の低下につながる。これに対し、例えば、特許文献１では、ニッケルめっきを施した不織布を正負極板間に介在させて亜鉛デンドライトによる正負極間の内部ショートを防止する技術が開示されている。 As shown in the above formula, in a nickel-zinc battery, zinc hydroxide (Zn (OH) 2 ) is produced by a discharge reaction. Zinc hydroxide is soluble in the electrolytic solution, and when zinc hydroxide is dissolved in the electrolytic solution, tetrahydroxydozincate ions ([Zn (OH) 4 ] 2- ) diffuse into the electrolytic solution. As a result, as the morphological change (deformation) of the negative electrode progresses and the distribution of the charging current becomes non-uniform, zinc precipitates locally on the negative electrode and dendrites (dendritic crystals) are generated. In a nickel-zinc battery, when dendrite grows due to repeated charging and discharging, the dendrite penetrates the separator and a short circuit occurs. Therefore, the generation of the dendrite leads to a decrease in life performance. On the other hand, for example, Patent Document 1 discloses a technique in which a nickel-plated nonwoven fabric is interposed between positive and negative electrode plates to prevent an internal short circuit between positive and negative electrodes due to zinc dendrite.
ニッケル亜鉛電池等の亜鉛電池に対しては、寿命性能の更なる向上が求められており、寿命性能を向上させるための新たな技術の開発が求められている。 For zinc batteries such as nickel-zinc batteries, further improvement in life performance is required, and development of new techniques for improving life performance is required.
本開示の一側面は、亜鉛電池において優れた寿命性能を得ることが可能な亜鉛電池用負極体を提供することを目的とする。本開示の他の一側面は、当該亜鉛電池用負極を備える亜鉛電池を提供することを目的とする。 One aspect of the present disclosure is to provide a negative electrode body for a zinc battery capable of obtaining excellent life performance in a zinc battery. Another aspect of the present disclosure is to provide a zinc battery comprising the negative electrode for the zinc battery.
本開示の一側面は、負極と、多孔部材と、を備え、前記負極が、集電体と、当該集電体に支持された負極材と、を有し、前記多孔部材が前記負極材の主面に対向し、前記多孔部材における前記主面に対向する部分の厚さが前記負極材における最大厚さと最小厚さとの差より大きい、亜鉛電池用負極体を提供する。 One aspect of the present disclosure comprises a negative electrode and a porous member, wherein the negative electrode has a current collector and a negative electrode material supported by the current collector, and the porous member is the negative electrode material. Provided is a negative electrode body for a zinc battery, wherein the thickness of the portion of the porous member facing the main surface facing the main surface is larger than the difference between the maximum thickness and the minimum thickness of the negative electrode material.
本開示の他の一側面は、上述の亜鉛電池用負極体と、正極と、を備える、亜鉛電池を提供する。 Another aspect of the present disclosure provides a zinc battery comprising the above-mentioned negative electrode body for a zinc battery and a positive electrode.
上述の亜鉛電池用負極体及び亜鉛電池によれば、充放電を繰り返した際に優れた寿命性能を得ることができる。 According to the above-mentioned negative electrode body for zinc battery and zinc battery, excellent life performance can be obtained when charging and discharging are repeated.
本開示の一側面によれば、亜鉛電池において優れた寿命性能を得ることが可能な亜鉛電池用負極体を提供することができる。本開示の他の一側面によれば、当該亜鉛電池用負極を備える亜鉛電池を提供することができる。 According to one aspect of the present disclosure, it is possible to provide a negative electrode body for a zinc battery capable of obtaining excellent life performance in a zinc battery. According to another aspect of the present disclosure, it is possible to provide a zinc battery including the negative electrode for the zinc battery.
本明細書において、「～」を用いて示された数値範囲は、「～」の前後に記載される数値をそれぞれ最小値及び最大値として含む範囲を示す。数値範囲の「Ａ以上」とは、Ａ、及び、Ａを超える範囲を意味する。数値範囲の「Ａ以下」とは、Ａ、及び、Ａ未満の範囲を意味する。本明細書に段階的に記載されている数値範囲において、ある段階の数値範囲の上限値又は下限値は、他の段階の数値範囲の上限値又は下限値と任意に組み合わせることができる。本明細書に記載されている数値範囲において、その数値範囲の上限値又は下限値は、実施例に示されている値に置き換えてよい。「Ａ又はＢ」とは、Ａ及びＢのどちらか一方を含んでいればよく、両方とも含んでいてもよい。本明細書に例示する材料は、特に断らない限り、１種を単独で又は２種以上を組み合わせて用いることができる。本明細書において、組成物中の各成分の量は、組成物中に各成分に該当する物質が複数存在する場合、特に断らない限り、組成物中に存在する当該複数の物質の合計量を意味する。本明細書において「膜」又は「層」との語は、平面図として観察したときに、全面に形成されている形状の構造に加え、一部に形成されている形状の構造も包含される。本明細書において「工程」との語は、独立した工程だけではなく、他の工程と明確に区別できない場合であってもその工程の所期の作用が達成されれば、本用語に含まれる。 In the present specification, the numerical range indicated by using "-" indicates a range including the numerical values before and after "-" as the minimum value and the maximum value, respectively. "A or more" in the numerical range means A and a range exceeding A. "A or less" in the numerical range means A and a range less than A. Within the numerical range described stepwise herein, the upper or lower limit of the numerical range at one stage may be optionally combined with the upper or lower limit of the numerical range at another stage. In the numerical range described herein, the upper or lower limit of the numerical range may be replaced with the values shown in the examples. "A or B" may include either A or B, and may include both. Unless otherwise specified, the materials exemplified in the present specification may be used alone or in combination of two or more. In the present specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. means. In the present specification, the term "membrane" or "layer" includes not only a structure having a shape formed on the entire surface but also a structure having a shape partially formed when observed as a plan view. .. In the present specification, the term "process" is included in this term not only as an independent process but also as long as the intended action of the process is achieved even if it cannot be clearly distinguished from other processes. ..
以下、本開示の実施形態について詳細に説明する。但し、本開示は、以下の実施形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, embodiments of the present disclosure will be described in detail. However, the present disclosure is not limited to the following embodiments, and can be variously modified and implemented within the scope of the gist thereof.
本実施形態に係る亜鉛電池用負極体は、負極と、多孔部材と、を備え、負極が、集電体と、当該集電体に支持された負極材と、を有し、多孔部材が負極材の主面に対向（負極材の主面を被覆）し、多孔部材における負極材の主面に対向する部分（負極材の主面を被覆する部分）の厚さＴが負極材における最大厚さＴｍａｘと最小厚さＴｍｉｎとの差Ｄより大きい（Ｔｍａｘ－Ｔｍｉｎ＝Ｄ＜Ｔ）。本実施形態に係る亜鉛電池用負極体によれば、亜鉛電池において充放電を繰り返した際に優れた寿命性能（サイクル寿命性能）を得ることができる。 The negative electrode body for a zinc battery according to the present embodiment includes a negative electrode and a porous member, the negative electrode has a current collector and a negative electrode material supported by the current collector, and the porous member is a negative electrode. The thickness T of the portion of the porous member facing the main surface of the negative electrode material (the portion covering the main surface of the negative electrode material) facing the main surface of the material (covering the main surface of the negative electrode material) is the maximum thickness of the negative electrode material. The difference D between T max and the minimum thickness T min is larger than D (T max −T min = D <T). According to the negative electrode body for a zinc battery according to the present embodiment, excellent life performance (cycle life performance) can be obtained when charging and discharging are repeated in the zinc battery.
本発明者は、亜鉛電池において負極の負極材の厚さにムラが生じる傾向があること（後述の実施例における負極材の厚さの測定結果を参照）に着目した上で、負極材における最大厚さＴｍａｘと最小厚さＴｍｉｎとの差Ｄと、多孔部材における負極材の主面に対向する部分（負極材の主面を被覆する部分）の厚さＴとの関係を調整することが寿命性能の向上に寄与することを見出し、多孔部材における負極材の主面に対向する部分の厚さＴが負極材における最大厚さＴｍａｘと最小厚さＴｍｉｎとの差Ｄより大きいことにより優れた寿命性能を得ることができることを見出した。 The present inventor pays attention to the fact that the thickness of the negative electrode material of the negative electrode tends to be uneven in the zinc battery (see the measurement result of the thickness of the negative electrode material in the examples described later), and the maximum in the negative electrode material. Adjusting the relationship between the difference D between the thickness T max and the minimum thickness T min and the thickness T of the portion of the porous member facing the main surface of the negative electrode material (the portion covering the main surface of the negative electrode material). Is found to contribute to the improvement of life performance, and the thickness T of the portion of the porous member facing the main surface of the negative electrode material is larger than the difference D between the maximum thickness T max and the minimum thickness T min in the negative electrode material. It has been found that more excellent life performance can be obtained.
図１を用いて、優れた寿命性能が得られる要因の一例について説明する。図１（ａ）は、厚い多孔部材を備える負極体を示し、図１（ｂ）は、薄い多孔部材を備える負極体を示す。図１（ａ）に示す負極体１００は、負極１０、及び、厚さＴを有する多孔部材２０を備え、負極１０は、集電体１２及び負極材１４を有する。図１（ｂ）に示す負極体１００ａは、負極体１００と同一の負極１０、及び、厚さＴａを有する多孔部材２０ａを備える。負極材１４は、最小厚さＴｍｉｎを有する部分Ａ、及び、最大厚さＴｍａｘを有する部分Ｂを有し、最大厚さＴｍａｘと最小厚さＴｍｉｎとの差Ｄが生じている。多孔部材２０，２０ａは、負極材１４の主面１４ａに対向している（負極材１４の主面１４ａを被覆している）。
An example of a factor for obtaining excellent life performance will be described with reference to FIG. 1. FIG. 1A shows a negative electrode body having a thick porous member, and FIG. 1B shows a negative electrode body having a thin porous member. The
負極の負極材の厚さにムラが生じていると、負極材における最大厚さを有する部分Ｂは多孔部材に接触しやすいのに対し、負極材における最小厚さを有する部分Ａは部分Ｂと比較して多孔部材に接触しにくい。しかしながら、負極、正極、多孔部材等の各部材を電池の収容空間に収容する場合、各部材に圧力（群厚）が負荷され、当該圧力の大きさに応じて部分Ａも多孔部材に接触し得る。電池の収容空間が同一体積である態様同士を比較すると、多孔部材が厚い場合には、充分な圧力が生じやすいことから、図１（ａ）に示すように、負極材１４の部分Ａが多孔部材２０に接触しやすく、部分Ａと多孔部材２０との間に隙間が生じにくいため、充放電に伴い亜鉛が溶出すること等が抑制されることから充分な寿命性能が得られる。一方、多孔部材が薄い場合には、充分な圧力が生じにくいことから、図１（ｂ）に示すように、負極材１４の部分Ａが多孔部材２０ａに接触しにくく、部分Ａと多孔部材２０との間に隙間が生じ、充放電に伴い亜鉛が溶出する等して充分な寿命性能が得られない。なお、電池の収容空間において、多孔部材が負極及び正極の間に配置された状態における多孔部材と正極との間等に弾性部材（例えば不織布）が配置されている場合であっても、多孔部材が、多孔部材に対する負極材１４の部分Ａの接触しやすさに支配的に作用し得ると推察され、例えば、電池の収容空間において、負極を収容する多孔部材と正極との間等に弾性部材（例えば不織布）が配置されている場合であっても、負極を収容し負極に近接する多孔部材が、多孔部材に対する負極材１４の部分Ａの接触しやすさに支配的に作用し得ると推察される。但し、優れた寿命性能が得られる要因はこれらの内容に限られない。
When the thickness of the negative electrode material of the negative electrode is uneven, the portion B having the maximum thickness in the negative electrode material tends to come into contact with the porous member, whereas the portion A having the minimum thickness in the negative electrode material is the portion B. In comparison, it is hard to come into contact with the porous member. However, when each member such as the negative electrode, the positive electrode, and the porous member is accommodated in the battery accommodation space, a pressure (group thickness) is applied to each member, and the portion A also comes into contact with the porous member according to the magnitude of the pressure. obtain. Comparing the modes in which the batteries have the same volume, when the porous member is thick, sufficient pressure is likely to be generated. Therefore, as shown in FIG. 1A, the portion A of the
本実施形態に係る亜鉛電池（例えば亜鉛二次電池）としては、ニッケル亜鉛電池（例えばニッケル亜鉛二次電池）、空気亜鉛電池、銀亜鉛電池等が挙げられる。本実施形態に係る亜鉛電池の基本構成としては、従来の亜鉛電池と同様の構成を用いることができる。本実施形態に係る亜鉛電池は、化成前及び化成後のいずれであってもよい。 Examples of the zinc battery (for example, a zinc secondary battery) according to the present embodiment include a nickel-zinc battery (for example, a nickel-zinc secondary battery), a zinc-air battery, and a silver-zinc battery. As the basic configuration of the zinc battery according to the present embodiment, the same configuration as that of the conventional zinc battery can be used. The zinc battery according to this embodiment may be either pre-chemical or post-chemical.
本実施形態に係る亜鉛電池は、負極体（亜鉛電池用負極体）と、正極（亜鉛電池用正極。例えば正極板）と、を備える。本実施形態に係る負極体（亜鉛電池用負極体）は、負極（亜鉛電池用負極。例えば負極板）と、多孔部材と、を備える。亜鉛電池において多孔部材は負極材に接触しており、負極材の少なくとも一部が多孔部材の内部に延在していてもよい。正極は、多孔部材を介して負極と対向してよい。本実施形態に係る亜鉛電池は、負極体、正極等を収容する電槽を備えてよい。 The zinc battery according to the present embodiment includes a negative electrode body (negative electrode body for zinc battery) and a positive electrode (positive electrode for zinc battery, for example, a positive electrode plate). The negative electrode body (negative electrode body for a zinc battery) according to the present embodiment includes a negative electrode (negative electrode for a zinc battery, for example, a negative electrode plate) and a porous member. In the zinc battery, the porous member is in contact with the negative electrode material, and at least a part of the negative electrode material may extend inside the porous member. The positive electrode may face the negative electrode via the porous member. The zinc battery according to the present embodiment may include an electric tank for accommodating a negative electrode body, a positive electrode, and the like.
本実施形態に係る亜鉛電池は、負極と、正極と、負極及び正極の間に配置されたセパレータと、を有してよく、セパレータが上述の多孔部材を有する。負極及び正極は、例えば、負極の主面と正極の主面とが対向した状態で、セパレータを介して交互に積層されている。本実施形態に係る亜鉛電池は、複数の負極及び複数の正極から構成される電極群を有してよい。複数の負極同士及び複数の正極同士は、例えば、ストラップで連結されていてよい。 The zinc battery according to the present embodiment may have a negative electrode, a positive electrode, and a separator arranged between the negative electrode and the positive electrode, and the separator has the above-mentioned porous member. The negative electrode and the positive electrode are alternately laminated via a separator, for example, with the main surface of the negative electrode and the main surface of the positive electrode facing each other. The zinc battery according to the present embodiment may have a plurality of negative electrodes and a group of electrodes composed of a plurality of positive electrodes. The plurality of negative electrodes and the plurality of positive electrodes may be connected to each other by, for example, a strap.
負極は、負極集電体（集電体）と、当該負極集電体に支持された負極材と、を有している。負極材は、負極集電体の少なくとも一方の主面に配置されてよく、負極集電体の両方の主面に配置されてよい。正極は、正極集電体と、当該正極集電体に支持された正極材と、を有している。負極及び正極のそれぞれは、化成前及び化成後のいずれであってもよい。 The negative electrode has a negative electrode current collector (current collector) and a negative electrode material supported by the negative electrode current collector. The negative electrode material may be arranged on at least one main surface of the negative electrode current collector, or may be arranged on both main surfaces of the negative electrode current collector. The positive electrode has a positive electrode current collector and a positive electrode material supported by the positive electrode current collector. Each of the negative electrode and the positive electrode may be either before or after chemical conversion.
集電体（負極集電体又は正極集電体）は、電極材（負極材又は正極材）からの電流の導電路を構成する。集電体は、例えば、平板状、シート状等の形状を有している。集電体は、発泡金属、エキスパンドメタル、パンチングメタル、金属繊維のフェルト状物等によって構成された３次元網目構造の集電体などであってよい。負極集電体は、開口（例えば貫通孔）を有する集電体であってよく、例えばパンチングメタルであってよい。開口を有する集電体を用いる場合、負極材の厚さにムラが生じやすいものの、本実施形態によれば、このような集電体を用いる場合であっても充分な寿命性能を得ることができる。 The current collector (negative electrode current collector or positive electrode current collector) constitutes a conductive path for current from the electrode material (negative electrode material or positive electrode material). The current collector has a shape such as a flat plate shape or a sheet shape. The current collector may be a current collector having a three-dimensional network structure composed of foamed metal, expanded metal, punching metal, felt-like material of metal fibers, or the like. The negative electrode current collector may be a current collector having an opening (for example, a through hole), and may be, for example, a punching metal. When a current collector having an opening is used, the thickness of the negative electrode material tends to be uneven, but according to the present embodiment, sufficient life performance can be obtained even when such a current collector is used. can.
集電体を構成する材料の具体例としては、白金；ニッケル（発泡ニッケル等）；錫、ニッケル等の金属めっきを施した金属材料（銅、真鍮、鋼等）などが挙げられる。 Specific examples of the material constituting the current collector include platinum; nickel (foamed nickel, etc.); a metal material plated with metal such as tin, nickel, etc. (copper, brass, steel, etc.).
電極材（負極材又は正極材）は、層状の電極材層（負極材層又は正極材層）であってよい。例えば、集電体上に電極材層が形成されていてよく、集電体が３次元網目構造を有する場合には、集電体の網目の間に電極材が充填されて電極材層が形成されていてもよい。 The electrode material (negative electrode material or positive electrode material) may be a layered electrode material layer (negative electrode material layer or positive electrode material layer). For example, an electrode material layer may be formed on the current collector, and when the current collector has a three-dimensional network structure, the electrode material is filled between the meshes of the current collector to form the electrode material layer. It may have been done.
集電体の厚さは、０．０１ｍｍ以上、０．０５ｍｍ以上、０．０８ｍｍ以上、又は、０．１０ｍｍ以上であってよい。集電体の厚さは、１．０ｍｍ以下、０．８０ｍｍ以下、０．５０ｍｍ以下、０．３０ｍｍ以下、０．２０ｍｍ以下、又は、０．１０ｍｍ以下であってよい。これらの観点から、集電体の厚さは、０．０１～１．０ｍｍであってよい。 The thickness of the current collector may be 0.01 mm or more, 0.05 mm or more, 0.08 mm or more, or 0.10 mm or more. The thickness of the current collector may be 1.0 mm or less, 0.80 mm or less, 0.50 mm or less, 0.30 mm or less, 0.20 mm or less, or 0.10 mm or less. From these viewpoints, the thickness of the current collector may be 0.01 to 1.0 mm.
負極材の平均厚さは、優れた寿命性能を得やすい観点から、０．０１ｍｍ以上、０．０５ｍｍ以上、０．１０ｍｍ以上、又は、０．１５ｍｍ以上であってよい。負極材の平均厚さは、優れた高率放電性能を得やすい観点から、１．０ｍｍ以下、０．８０ｍｍ以下、０．５０ｍｍ以下、０．３０ｍｍ以下、又は、０．２０ｍｍ以下であってよい。これらの観点から、負極材の平均厚さは、０．０１～１．０ｍｍであってよい。 The average thickness of the negative electrode material may be 0.01 mm or more, 0.05 mm or more, 0.10 mm or more, or 0.15 mm or more from the viewpoint of easily obtaining excellent life performance. The average thickness of the negative electrode material may be 1.0 mm or less, 0.80 mm or less, 0.50 mm or less, 0.30 mm or less, or 0.20 mm or less from the viewpoint of easily obtaining excellent high-rate discharge performance. .. From these viewpoints, the average thickness of the negative electrode material may be 0.01 to 1.0 mm.
負極材における最大厚さＴｍａｘと最小厚さＴｍｉｎとの差Ｄは、下記の範囲であってよい。差Ｄは、１０μｍ以上、３０μｍ以上、５０μｍ以上、８０μｍ以上、又は、８０μｍ超であってよい。差Ｄは、５００μｍ以下、３００μｍ以下、２００μｍ以下、又は、１００μｍ以下であってよい。これらの観点から、差Ｄは、１０～５００μｍであってよい。負極材における最大厚さＴｍａｘと最小厚さＴｍｉｎは、負極材を支持する負極集電体の主面からの負極材の厚さである。 The difference D between the maximum thickness T max and the minimum thickness T min in the negative electrode material may be in the following range. The difference D may be 10 μm or more, 30 μm or more, 50 μm or more, 80 μm or more, or more than 80 μm. The difference D may be 500 μm or less, 300 μm or less, 200 μm or less, or 100 μm or less. From these viewpoints, the difference D may be 10 to 500 μm. The maximum thickness T max and the minimum thickness T min in the negative electrode material are the thicknesses of the negative electrode material from the main surface of the negative electrode current collector that supports the negative electrode material.
負極材の平均厚さ及び差Ｄは、負極材の主面に直交する方向から負極材を見て、負極材の中央部と、負極材の外周部における略等間隔に離間した８箇所との合計９箇所の平均値であってよい。 The average thickness and difference D of the negative electrode material are the central portion of the negative electrode material and the outer peripheral portion of the negative electrode material at eight locations separated at approximately equal intervals when the negative electrode material is viewed from the direction orthogonal to the main surface of the negative electrode material. It may be an average value of a total of 9 locations.
負極材は、亜鉛を含む負極活物質を含有する。負極活物質としては、金属亜鉛、酸化亜鉛、水酸化亜鉛等が挙げられる。負極材は、例えば、満充電状態では金属亜鉛を含有し、放電末状態では酸化亜鉛及び水酸化亜鉛を含有する。負極活物質は、例えば粒子状であってよく、金属亜鉛粒子、酸化亜鉛粒子、水酸化亜鉛粒子等を含んでよい。 The negative electrode material contains a negative electrode active material containing zinc. Examples of the negative electrode active material include metallic zinc, zinc oxide, zinc hydroxide and the like. The negative electrode material contains, for example, metallic zinc in a fully charged state, and zinc oxide and zinc hydroxide in a discharge end state. The negative electrode active material may be, for example, in the form of particles, and may contain metallic zinc particles, zinc oxide particles, zinc hydroxide particles, and the like.
負極活物質の含有量は、負極材の全質量を基準として下記の範囲であってよい。負極活物質の含有量は、優れた寿命性能を得やすい観点から、５０質量％以上、７０質量％以上、７５質量％以上、８０質量％以上、８５質量％以上、９０質量％以上、又は、９５質量％以上であってよい。負極活物質の含有量は、優れた寿命性能を得やすい観点から、９９質量％以下、９８質量％以下、又は、９６質量％以下であってよい。これらの観点から、負極活物質の含有量は、５０～９９質量％であってよい。 The content of the negative electrode active material may be in the following range based on the total mass of the negative electrode material. The content of the negative electrode active material is 50% by mass or more, 70% by mass or more, 75% by mass or more, 80% by mass or more, 85% by mass or more, 90% by mass or more, or from the viewpoint of easily obtaining excellent life performance. It may be 95% by mass or more. The content of the negative electrode active material may be 99% by mass or less, 98% by mass or less, or 96% by mass or less from the viewpoint of easily obtaining excellent life performance. From these viewpoints, the content of the negative electrode active material may be 50 to 99% by mass.
負極材は、負極活物質以外の添加剤を含有することができる。添加剤としては、結着剤（バインダー）、界面活性剤、導電剤等が挙げられる。結着剤としては、ポリテトラフルオロエチレン、ヒドロキシエチルセルロース（ＨＥＣ）、カルボキシメチルセルロース、ポリエチレンオキシド、ポリエチレン、ポリプロピレン等が挙げられる。結着剤の含有量は、例えば、負極活物質１００質量部に対して０．５～１０質量部であってよい。界面活性剤としては、ＢＡＳＦ社製、商品名：Ｄｉｓｐｅｘ ＡＡ ４１４０等が挙げられる。導電剤としては、インジウム化合物（酸化インジウム等）などが挙げられる。導電剤の含有量は、例えば、負極活物質１００質量部に対して１～２０質量部であってよい。 The negative electrode material can contain additives other than the negative electrode active material. Examples of the additive include a binder, a surfactant, a conductive agent and the like. Examples of the binder include polytetrafluoroethylene, hydroxyethyl cellulose (HEC), carboxymethyl cellulose, polyethylene oxide, polyethylene, polypropylene and the like. The content of the binder may be, for example, 0.5 to 10 parts by mass with respect to 100 parts by mass of the negative electrode active material. Examples of the surfactant include BASF, trade name: Dispex AA 4140 and the like. Examples of the conductive agent include indium compounds (indium oxide and the like). The content of the conductive agent may be, for example, 1 to 20 parts by mass with respect to 100 parts by mass of the negative electrode active material.
正極材は、正極活物質を含有する。亜鉛電池がニッケル亜鉛電池である場合、正極活物質は、ニッケルを含むことができる。正極活物質としては、オキシ水酸化ニッケル（ＮｉＯＯＨ）、水酸化ニッケル等が挙げられる。正極材は、例えば、満充電状態ではオキシ水酸化ニッケルを含有し、放電末状態では水酸化ニッケルを含有する。正極活物質の含有量は、例えば、正極材の全質量を基準として５０～９９質量％であってよい。 The positive electrode material contains a positive electrode active material. When the zinc battery is a nickel-zinc battery, the positive electrode active material can contain nickel. Examples of the positive electrode active material include nickel oxyhydroxide (NiOOH) and nickel hydroxide. The positive electrode material contains, for example, nickel oxyhydroxide in a fully charged state and nickel hydroxide in a discharge end state. The content of the positive electrode active material may be, for example, 50 to 99% by mass based on the total mass of the positive electrode material.
正極材は、正極活物質以外の添加剤を含有することができる。添加剤としては、結着剤（バインダー）、導電剤、膨張抑制剤、希土類金属化合物（例えば酸化イットリウム）等が挙げられる。結着剤としては、親水性又は疎水性のポリマー等が挙げられ、ヒドロキシエチルセルロース（ＨＥＣ）、ヒドロキシプロピルメチルセルロース（ＨＰＭＣ）、カルボキシメチルセルロース（ＣＭＣ）、ポリアクリル酸ナトリウム（ＳＰＡ）、フッ素系ポリマー（ポリテトラフルオロエチレン（ＰＴＦＥ）等）などが挙げられる。結着剤の含有量は、例えば、正極活物質１００質量部に対して０．０１～５質量部であってよい。導電剤としては、コバルト化合物（金属コバルト、酸化コバルト、水酸化コバルト等）などが挙げられる。導電剤の含有量は、例えば、正極活物質１００質量部に対して１～２０質量部であってよい。膨張抑制剤としては、酸化亜鉛等が挙げられる。膨張抑制剤の含有量は、例えば、正極活物質１００質量部に対して０．０１～５質量部であってよい。 The positive electrode material can contain additives other than the positive electrode active material. Examples of the additive include a binder, a conductive agent, an expansion inhibitor, a rare earth metal compound (for example, yttrium oxide), and the like. Examples of the binder include hydrophilic or hydrophobic polymers, and examples thereof include hydroxyethyl cellulose (HEC), hydroxypropylmethyl cellulose (HPMC), carboxymethyl cellulose (CMC), sodium polyacrylate (SPA), and fluoropolymers (poly). (Tetrafluoroethylene (PTFE), etc.) and the like. The content of the binder may be, for example, 0.01 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material. Examples of the conductive agent include cobalt compounds (metal cobalt, cobalt oxide, cobalt hydroxide, etc.) and the like. The content of the conductive agent may be, for example, 1 to 20 parts by mass with respect to 100 parts by mass of the positive electrode active material. Examples of the swelling inhibitor include zinc oxide and the like. The content of the expansion inhibitor may be, for example, 0.01 to 5 parts by mass with respect to 100 parts by mass of the positive electrode active material.
多孔部材は、負極材の主面に対向している（負極材の主面を被覆している）。この場合、多孔部材が負極材の主面の少なくとも一部に対向していればよく、多孔部材が負極材の主面の全体に対向していてもよい。多孔部材は、負極を収容してよく、例えば、負極の一方面側の負極材の主面と、負極の他方面側（負極の他方面側の負極材；負極集電体等）の一部又は全部と、負極の外周部（負極材の主面の面方向に位置する側部）の少なくとも一部と、を被覆することにより負極を収容してよい。多孔部材が負極の外周部の少なくとも一部を被覆する被覆部を有する場合、亜鉛電池において当該被覆部を鉛直方向の下側（底部側）に位置させることにより、負極材から脱落した負極活物質が電解液に広く拡散することに起因する不具合を抑制しやすい。 The porous member faces the main surface of the negative electrode material (covers the main surface of the negative electrode material). In this case, the porous member may face at least a part of the main surface of the negative electrode material, and the porous member may face the entire main surface of the negative electrode material. The porous member may accommodate the negative electrode, for example, a part of the main surface of the negative electrode material on one side of the negative electrode and the other side of the negative electrode (negative electrode material on the other side of the negative electrode; negative electrode current collector, etc.). Alternatively, the negative electrode may be accommodated by covering the entire surface and at least a part of the outer peripheral portion (side portion of the negative electrode material located in the surface direction of the main surface) of the negative electrode. When the porous member has a coating portion that covers at least a part of the outer peripheral portion of the negative electrode, the negative electrode active material that has fallen off from the negative electrode material by locating the coating portion on the lower side (bottom side) in the vertical direction in the zinc battery. Is easy to suppress the trouble caused by the wide diffusion of zinc in the electrolytic solution.
多孔部材は、負極を挿入するための開口部等として、開口部を有する袋状であってよい。亜鉛電池において、例えば、当該開口部は鉛直方向上方に開口する。袋状の多孔部材において当該開口部の開口方向に直交する方向の側部（例えば、負極体が亜鉛電池に収容された場合に水平方向に位置する側部）は、遮蔽されていてよく、開口していてよい。熱溶着等により多孔部材に遮蔽部を形成できる。多孔部材は、単層の多孔膜であってよく、複数の多孔膜の積層体であってよい。 The porous member may have a bag shape having an opening as an opening or the like for inserting the negative electrode. In a zinc battery, for example, the opening opens upward in the vertical direction. In the bag-shaped porous member, the side portion in the direction orthogonal to the opening direction of the opening (for example, the side portion located horizontally when the negative electrode body is housed in the zinc battery) may be shielded and may be open. You can do it. A shielding portion can be formed on the porous member by heat welding or the like. The porous member may be a single-layer porous membrane or a laminate of a plurality of porous membranes.
多孔部材における負極材の主面に対向する部分（負極材の主面を被覆する部分）の厚さＴ（総厚）は、負極材における最大厚さＴｍａｘと最小厚さＴｍｉｎとの差Ｄより大きい。厚さＴ及び差Ｄは、電池の作製前後で大きく相違しない傾向がある。 The thickness T (total thickness) of the portion of the porous member facing the main surface of the negative electrode material (the portion covering the main surface of the negative electrode material) is the difference between the maximum thickness T max and the minimum thickness T min of the negative electrode material. Greater than D. The thickness T and the difference D tend not to differ significantly before and after the battery is manufactured.
厚さＴは、多孔部材における負極材の主面に対向する部分の厚さの平均値であってよく、上述の負極材の厚さと同様の方法により測定してよい。厚さＴは、負極材と多孔部材との間に隙間が生じることを抑制しやすいことから優れた寿命性能を得やすい観点から、１０μｍ以上、３０μｍ以上、５０μｍ以上、７０μｍ以上、９０μｍ以上、１００μｍ以上、１１０μｍ以上、１１５μｍ以上、１２０μｍ以上、又は、１２５μｍ以上であってよい。厚さＴは、優れたエネルギー密度を得やすい観点から、５００μｍ以下、４００μｍ以下、３００μｍ以下、２００μｍ以下、１８０μｍ以下、１５０μｍ以下、１４０μｍ以下、１３０μｍ以下、１２５μｍ以下、又は、１２０μｍ以下であってよい。これらの観点から、厚さＴは、１０～５００μｍであってよい。多孔部材の全体における平均厚さは、多孔部材における負極材の主面に対向する部分（負極材の主面を被覆する部分）の厚さと同等であってよい。 The thickness T may be an average value of the thicknesses of the portions of the porous member facing the main surface of the negative electrode material, and may be measured by the same method as the thickness of the negative electrode material described above. The thickness T is 10 μm or more, 30 μm or more, 50 μm or more, 70 μm or more, 90 μm or more, 100 μm from the viewpoint of easily obtaining excellent life performance because it is easy to suppress the formation of a gap between the negative electrode material and the porous member. As mentioned above, it may be 110 μm or more, 115 μm or more, 120 μm or more, or 125 μm or more. The thickness T may be 500 μm or less, 400 μm or less, 300 μm or less, 200 μm or less, 180 μm or less, 150 μm or less, 140 μm or less, 130 μm or less, 125 μm or less, or 120 μm or less from the viewpoint of easily obtaining an excellent energy density. .. From these viewpoints, the thickness T may be 10 to 500 μm. The average thickness of the entire porous member may be equal to the thickness of the portion of the porous member facing the main surface of the negative electrode material (the portion covering the main surface of the negative electrode material).
多孔部材の材料としては、有機材料（樹脂材料等）、無機材料などが挙げられる。樹脂材料としては、ポリアミド系ポリマー（例えばポリアミド）、オレフィン系ポリマー（例えば、ポリエチレン、ポリプロピレン等のポリオレフィン）、ナイロン系ポリマー（例えばナイロン）等が挙げられる。無機材料としては、アルミナ、チタニア、二酸化珪素等の酸化物；窒化アルミニウム、窒化珪素等の窒化物；硫酸バリウム、硫酸カルシウム等の硫酸塩などが挙げられる。多孔部材は、イオン交換樹脂膜、セロハン系再生樹脂膜、無機－有機セパレータ、ポリオレフィン系不織布等であってよい。多孔部材の製造方法としては、湿式法（相分離法）、乾式法（延伸開孔法）、メルトブロー、エレクトロスピニング等が挙げられる。多孔部材は、優れた寿命性能を得やすい観点から、ポリオレフィンを含んでよく、ポリエチレン及びポリプロピレンからなる群より選ばれる少なくとも一種を含んでよく、ポリエチレンを含んでよい。 Examples of the material of the porous member include an organic material (resin material and the like), an inorganic material and the like. Examples of the resin material include a polyamide polymer (for example, polyamide), an olefin polymer (for example, a polyolefin such as polyethylene and polypropylene), a nylon polymer (for example, nylon) and the like. Examples of the inorganic material include oxides such as alumina, titania and silicon dioxide; nitrides such as aluminum nitride and silicon nitride; and sulfates such as barium sulfate and calcium sulfate. The porous member may be an ion exchange resin film, a cellophane-based recycled resin film, an inorganic-organic separator, a polyolefin-based non-woven fabric, or the like. Examples of the method for manufacturing the porous member include a wet method (phase separation method), a dry method (stretched pore opening method), melt blowing, and electrospinning. The porous member may contain polyolefin from the viewpoint of easily obtaining excellent life performance, may contain at least one selected from the group consisting of polyethylene and polypropylene, and may contain polyethylene.
多孔部材は、親水化する観点から、アニオン性界面活性剤、カチオン性界面活性剤、両性界面活性剤、非イオン性界面活性剤等を含有してよく、界面活性剤処理、スルホン化処理、フッ素ガス処理、アクリル酸グラフト重合処理、コロナ放電処理、プラズマ処理等により表面処理が施されていてよい。親水化することにより、電解液と馴染みやすく、充分な電流密度を得やすい。 From the viewpoint of making the porous member hydrophilic, the porous member may contain an anionic surfactant, a cationic surfactant, an amphoteric surfactant, a nonionic surfactant, etc., and may contain a surfactant treatment, a sulfonate treatment, and fluorine. Surface treatment may be performed by gas treatment, acrylic acid graft polymerization treatment, corona discharge treatment, plasma treatment, or the like. By making it hydrophilic, it is easy to be compatible with the electrolytic solution and it is easy to obtain a sufficient current density.
本実施形態に係る亜鉛電池は、多孔部材が負極及び正極の間に配置された状態において多孔部材と正極との間に弾性部材を備えてよく、負極を収容する多孔部材と正極との間に弾性部材を備えてよい。弾性部材としては、負極を収容しない多孔部材等が挙げられ、不織布等が挙げられる。 The zinc battery according to the present embodiment may be provided with an elastic member between the porous member and the positive electrode in a state where the porous member is arranged between the negative electrode and the positive electrode, and is between the porous member accommodating the negative electrode and the positive electrode. An elastic member may be provided. Examples of the elastic member include a porous member that does not accommodate a negative electrode, and a non-woven fabric and the like.
本実施形態に係る亜鉛電池は、電解液を備えてよい。電解液は、例えば、溶媒及び電解質を含有している。溶媒としては、水（例えばイオン交換水）等が挙げられる。電解質としては、塩基性化合物等が挙げられ、水酸化カリウム（ＫＯＨ）、水酸化ナトリウム（ＮａＯＨ）、水酸化リチウム（ＬｉＯＨ）等のアルカリ金属水酸化物などが挙げられる。本実施形態に係る亜鉛電池は、アルカリ電解液を用いたアルカリ亜鉛電池として用いることができる。電解液は、溶媒及び電解質以外の成分を含有してよく、例えば、リン酸カリウム、フッ化カリウム、炭酸カリウム、リン酸ナトリウム、フッ化ナトリウム、水酸化ナトリウム、水酸化リチウム、酸化亜鉛、酸化アンチモン、二酸化チタン、非イオン性界面活性剤、アニオン性界面活性剤等を含有してよい。 The zinc battery according to this embodiment may include an electrolytic solution. The electrolytic solution contains, for example, a solvent and an electrolyte. Examples of the solvent include water (for example, ion-exchanged water) and the like. Examples of the electrolyte include basic compounds and the like, and examples thereof include alkali metal hydroxides such as potassium hydroxide (KOH), sodium hydroxide (NaOH) and lithium hydroxide (LiOH). The zinc battery according to this embodiment can be used as an alkaline zinc battery using an alkaline electrolytic solution. The electrolyte may contain components other than the solvent and electrolyte, such as potassium phosphate, potassium fluoride, potassium carbonate, sodium phosphate, sodium fluoride, sodium hydroxide, lithium hydroxide, zinc oxide, antimony oxide. , Titanium dioxide, nonionic surfactant, anionic surfactant and the like may be contained.
本実施形態に係る亜鉛電池（例えばニッケル亜鉛電池）の製造方法は、例えば、電極（負極及び正極）を得る電極製造工程と、負極体を含む構成部材を組み立てて亜鉛電池を得る組立工程と、を備える。 The method for manufacturing a zinc battery (for example, nickel-zinc battery) according to the present embodiment includes, for example, an electrode manufacturing step for obtaining electrodes (negative electrode and positive electrode), and an assembly step for assembling components including a negative electrode body to obtain a zinc battery. To prepare for.
電極製造工程では、電極（負極及び正極）を製造する。例えば、電極材（負極材及び正極材）の原料に対して溶媒（例えば水）を加えて混練することにより電極材ペースト（ペースト状の電極材）を得た後、電極材ペーストを用いて電極材層を形成する。 In the electrode manufacturing process, electrodes (negative electrode and positive electrode) are manufactured. For example, a solvent (for example, water) is added to the raw materials of the electrode material (negative electrode material and positive electrode material) and kneaded to obtain an electrode material paste (paste-like electrode material), and then the electrode material paste is used for the electrode. Form a material layer.
負極材の原料としては、負極活物質の原料（例えば金属亜鉛、酸化亜鉛及び水酸化亜鉛）、添加剤（例えば結着剤）等が挙げられる。正極材の原料としては、正極活物質の原料（例えば水酸化ニッケル）、添加剤（例えば結着剤）等が挙げられる。 Examples of the raw material of the negative electrode material include raw materials of the negative electrode active material (for example, metallic zinc, zinc oxide and zinc hydroxide), additives (for example, a binder) and the like. Examples of the raw material of the positive electrode material include a raw material of a positive electrode active material (for example, nickel hydroxide), an additive (for example, a binder) and the like.
電極材層を形成する方法としては、例えば、電極材ペーストを集電体に塗布又は充填した後に乾燥することで電極材層を得る方法が挙げられる。電極材層は、必要に応じて、プレス等によって密度を高めてよい。 Examples of the method for forming the electrode material layer include a method for obtaining the electrode material layer by applying or filling the current collector with the electrode material paste and then drying the electrode material layer. The density of the electrode material layer may be increased by pressing or the like, if necessary.
組立工程では、まず、電極と多孔部材とを備える電極体（例えば負極体）を得た後、セパレータを介して負極体及び正極体を交互に積層し、正極同士及び負極同士をストラップで連結させて電極群を作製してよく、例えば、電極製造工程で得られた電極を多孔部材に収容することにより、電極と、電極を収容する多孔部材と、を備える電極体（例えば負極体）を得た後、セパレータを介して負極体及び正極体を交互に積層し、正極同士及び負極同士をストラップで連結させて電極群を作製してよい。負極体及び正極体の間に不織布等の弾性部材を配置してもよい。次いで、この電極群を電槽内に配置した後、電槽の上面に蓋体を接着して未化成の亜鉛電池を得る。 In the assembly process, first, an electrode body (for example, a negative electrode body) including an electrode and a porous member is obtained, then the negative electrode body and the positive electrode body are alternately laminated via a separator, and the positive electrodes and the negative electrodes are connected by a strap. For example, by accommodating the electrode obtained in the electrode manufacturing process in the porous member, an electrode body (for example, a negative electrode body) including the electrode and the porous member accommodating the electrode can be obtained. After that, the negative electrode body and the positive electrode body may be alternately laminated via the separator, and the positive electrodes and the negative electrodes may be connected by a strap to prepare an electrode group. An elastic member such as a non-woven fabric may be arranged between the negative electrode body and the positive electrode body. Next, after arranging this electrode group in the electric tank, a lid is adhered to the upper surface of the electric tank to obtain a non-chemical zinc battery.
次いで、電解液を未化成の亜鉛電池の電槽内に注入した後、一定時間放置する。次いで、所定の条件にて充電を行うことで化成することにより亜鉛電池を得る。化成条件は、電極活物質（負極活物質及び正極活物質）の性状に応じて調整することができる。 Then, after injecting the electrolytic solution into the electric tank of the unchemical zinc battery, it is left for a certain period of time. Next, a zinc battery is obtained by chemical conversion by charging under predetermined conditions. The chemical formation conditions can be adjusted according to the properties of the electrode active material (negative electrode active material and positive electrode active material).
以上、本開示の実施形態について説明したが、本開示は、上述の実施形態に限定されるものではない。例えば、上述の実施形態では、正極がニッケル電極であるニッケル亜鉛電池の例を説明したが、亜鉛電池は、正極が空気極である空気亜鉛電池（例えば空気亜鉛二次電池）であってもよく、正極が酸化銀極である銀亜鉛電池（例えば銀亜鉛二次電池）であってもよい。 Although the embodiments of the present disclosure have been described above, the present disclosure is not limited to the above-described embodiments. For example, in the above-described embodiment, an example of a zinc-air battery having a positive electrode as a nickel electrode has been described, but the zinc battery may be an air zinc battery having an air electrode as a positive electrode (for example, an air zinc secondary battery). , A silver-zinc battery (for example, a silver-zinc secondary battery) in which the positive electrode is a silver oxide electrode may be used.
空気亜鉛電池の空気極としては、空気亜鉛電池に使用される公知の空気極を用いることができる。空気極は、例えば、空気極触媒、電子伝導性材料等を含む。空気極触媒としては、電子伝導性材料としても機能する空気極触媒を用いることができる。 As the air electrode of the zinc-air battery, a known air electrode used in the zinc-air battery can be used. The air electrode includes, for example, an air electrode catalyst, an electron conductive material, and the like. As the air electrode catalyst, an air electrode catalyst that also functions as an electron conductive material can be used.
空気極触媒としては、空気亜鉛電池における正極として機能するものを用いることが可能であり、酸素を正極活物質として利用可能な種々の空気極触媒が使用できる。空気極触媒としては、酸化還元触媒機能を有するカーボン系材料（黒鉛等）、酸化還元触媒機能を有する金属材料（白金、ニッケル等）、酸化還元触媒機能を有する無機酸化物材料（ペロブスカイト型酸化物、二酸化マンガン、酸化ニッケル、酸化コバルト、スピネル酸化物等）などが挙げられる。空気極触媒の形状は、特に限定されないが、例えば粒子状であってよい。空気極における空気極触媒の含有量は、空気極の合計量に対して５～７０体積％であってよい。 As the air electrode catalyst, one that functions as a positive electrode in an air zinc battery can be used, and various air electrode catalysts that can use oxygen as a positive electrode active material can be used. As the air electrode catalyst, a carbon-based material having a redox catalyst function (graphite, etc.), a metal material having a redox catalyst function (platinum, nickel, etc.), and an inorganic oxide material having a redox catalyst function (perovskite type oxide) , Manganese dioxide, nickel oxide, cobalt oxide, spinel oxide, etc.). The shape of the air electrode catalyst is not particularly limited, but may be, for example, in the form of particles. The content of the air electrode catalyst in the air electrode may be 5 to 70% by volume with respect to the total amount of the air electrode.
電子伝導性材料としては、導電性を有し、かつ、空気極触媒とセパレータとの間の電子伝導を可能とするものを用いることができる。電子伝導性材料としては、ケッチェンブラック、アセチレンブラック、チャンネルブラック、ファーネスブラック、ランプブラック、サーマルブラック等のカーボンブラック類；鱗片状黒鉛のような天然黒鉛、人造黒鉛、膨張黒鉛等のグラファイト類；炭素繊維、金属繊維等の導電性繊維類；銅、銀、ニッケル、アルミニウム等の金属粉末類；ポリフェニレン誘導体等の有機電子伝導性材料；これらの任意の混合物などが挙げられる。電子伝導性材料の形状は、粒子状であってよく、その他の形状であってもよい。電子伝導性材料は、空気極において厚さ方向に連続した相をもたらす形態で用いられてよい。例えば、電子伝導性材料は、多孔質材料であってよい。また、電子伝導性材料は、空気極触媒との混合物又は複合体の形態であってよく、前述したように、電子伝導性材料としても機能する空気極触媒であってもよい。空気極における電子伝導性材料の含有量は、空気極の合計量に対して１０～８０体積％であってよい。 As the electron conductive material, a material having conductivity and enabling electron conduction between the air electrode catalyst and the separator can be used. Examples of the electronically conductive material include carbon blacks such as Ketjen black, acetylene black, channel black, furnace black, lamp black, and thermal black; natural graphite such as scaly graphite, artificial graphite, and graphite such as expanded graphite; Conductive fibers such as carbon fibers and metal fibers; metal powders such as copper, silver, nickel and aluminum; organic electron conductive materials such as polyphenylene derivatives; any mixture thereof and the like can be mentioned. The shape of the electronically conductive material may be particulate or may be any other shape. The electronically conductive material may be used in a form that results in a continuous phase in the thickness direction at the air electrode. For example, the electron conductive material may be a porous material. Further, the electron conductive material may be in the form of a mixture or a composite with an air electrode catalyst, and as described above, it may be an air electrode catalyst that also functions as an electron conductive material. The content of the electron conductive material in the air electrode may be 10 to 80% by volume with respect to the total amount of the air electrode.
銀亜鉛電池の酸化銀極としては、銀亜鉛電池に使用される公知の酸化銀極を用いることができる。酸化銀極は、例えば酸化銀（Ｉ）を含む。 As the silver oxide pole of the silver-zinc battery, a known silver oxide pole used in the silver-zinc battery can be used. The silver oxide electrode contains, for example, silver (I) oxide.
以下、実施例により本開示を具体的に説明する。但し、本開示は下記の実施例に限定されるものではない。 Hereinafter, the present disclosure will be specifically described with reference to Examples. However, the present disclosure is not limited to the following examples.
＜負極の作製＞
負極集電体として、錫メッキを施した銅パンチングメタル（開孔率：５０％、厚さ：０．１０ｍｍ）を用意した。次いで、酸化亜鉛、金属亜鉛、ＨＥＣ、界面活性剤（ＢＡＳＦ社製、商品名：Ｄｉｓｐｅｘ ＡＡ ４１４０）及びイオン交換水を所定量秤量した後に混合することによって得られた混合液を攪拌することにより負極材ペーストを作製した。この際、固形分の質量比を「酸化亜鉛：金属亜鉛：ＨＥＣ：界面活性剤＝８４．５：１１．５：３．５：０．５」に調整した。負極材ペーストの水分量は、負極材ペーストの全質量基準で３２．５質量％に調整した。次いで、負極材ペーストを負極集電体の両面に塗布した後、８０℃で３０分乾燥した。その後、ロールプレスにて加圧成形し、負極材（負極材層）を両面に有する未化成の負極（平均厚さ（総厚）：０．４１ｍｍ）を得た。
<Manufacturing of negative electrode>
As a negative electrode current collector, a tin-plated copper punching metal (opening rate: 50%, thickness: 0.10 mm) was prepared. Next, a predetermined amount of zinc oxide, metallic zinc, HEC, a surfactant (manufactured by BASF, trade name: Discex AA 4140) and ion-exchanged water are weighed and then mixed to obtain a mixed solution. A material paste was prepared. At this time, the mass ratio of the solid content was adjusted to "zinc oxide: metallic zinc: HEC: surfactant = 84.5: 11.5: 3.5: 0.5". The water content of the negative electrode material paste was adjusted to 32.5% by mass based on the total mass of the negative electrode material paste. Next, the negative electrode material paste was applied to both sides of the negative electrode current collector, and then dried at 80 ° C. for 30 minutes. Then, it was pressure-molded by a roll press to obtain an unchemical negative electrode (average thickness (total thickness): 0.41 mm) having a negative electrode material (negative electrode material layer) on both sides.
上述の未化成の負極を１０枚準備した後、一方面側の負極材の厚さを測定することにより最大厚さＴｍａｘと最小厚さＴｍｉｎとの差Ｄを算出した。負極材の主面に直交する方向から負極材を見て、左上隅部、***部、右上隅部、左中央部、中央部、右中央部、左下隅部、下中央部、及び、右下中央部の９箇所について、マイクロメーター（ＰＭＵ１５０－２５ＭＸ、株式会社ミツトヨ製）を用いて厚さを測定した。１０枚の負極の負極材層における最大厚さＴｍａｘと最小厚さＴｍｉｎとの差Ｄは、９３μｍ、８６μｍ、９２μｍ、８７μｍ、９１μｍ、９６μｍ、１００μｍ、９８μｍ、９５μｍ、及び、９１μｍであり、１０枚の全ての負極において差Ｄは８０μｍを超えていた（Ｔｍａｘ－Ｔｍｉｎ＝Ｄ＞８０μｍ」であった）。 After preparing 10 of the above-mentioned unchemical negative electrodes, the difference D between the maximum thickness T max and the minimum thickness T min was calculated by measuring the thickness of the negative electrode material on one side. Looking at the negative electrode material from the direction orthogonal to the main surface of the negative electrode material, the upper left corner, the upper center, the upper right corner, the left center, the center, the right center, the lower left corner, the lower center, and the right. The thickness of 9 points in the lower center was measured using a micrometer (PMU150-25MX, manufactured by Mitutoyo Co., Ltd.). The difference D between the maximum thickness T max and the minimum thickness T min in the negative electrode material layer of 10 negative electrodes is 93 μm, 86 μm, 92 μm, 87 μm, 91 μm, 96 μm, 100 μm, 98 μm, 95 μm, and 91 μm. The difference D was more than 80 μm in all 10 negative electrodes (T max −T min = D> 80 μm ”).
＜正極の作製＞
空隙率９５％の発泡ニッケルからなる格子体を用意し、格子体を加圧成形することで正極集電体を得た。次いで、コバルトコート水酸化ニッケル粉末、金属コバルト、水酸化コバルト、酸化イットリウム、カルボキシメチルセルロース、ポリテトラフルオロエチレン及びイオン交換水を所定量秤量した後に混合することによって得られた混合液を攪拌することにより正極材ペーストを作製した。この際、固形分の質量比を、「水酸化ニッケル：金属コバルト：酸化イットリウム：水酸化コバルト：カルボキシメチルセルロース：ポリテトラフルオロエチレン＝８８：１０．３：１：０．３：０．３：０．１」に調整した。正極材ペーストの水分量は、正極材ペーストの全質量基準で２７．５質量％に調整した。次いで、正極材ペーストを正極集電体の両面に塗布した後、８０℃で３０分乾燥した。その後、ロールプレスにて加圧成形し、正極材（正極材層）を両面に有する未化成の正極を得た。
<Manufacturing of positive electrode>
A lattice body made of foamed nickel having a porosity of 95% was prepared, and the lattice body was pressure-molded to obtain a positive electrode current collector. Then, the mixed solution obtained by weighing a predetermined amount of cobalt-coated nickel hydroxide powder, metallic cobalt, cobalt hydroxide, yttrium oxide, carboxymethyl cellulose, polytetrafluoroethylene and ion-exchanged water and then mixing them is stirred. A positive material paste was prepared. At this time, the mass ratio of the solid content was set to "nickel hydroxide: metallic cobalt: yttrium oxide: cobalt hydroxide: carboxymethyl cellulose: polytetrafluoroethylene = 88: 10.3: 1: 0.3: 0.3: 0. It was adjusted to "1.1". The water content of the positive electrode material paste was adjusted to 27.5% by mass based on the total mass of the positive electrode material paste. Then, the positive electrode material paste was applied to both sides of the positive electrode current collector, and then dried at 80 ° C. for 30 minutes. Then, it was pressure-molded by a roll press to obtain an unchemical positive electrode having a positive electrode material (positive electrode material layer) on both sides.
＜ニッケル亜鉛電池の作製＞
（実施例１）
Ｘｉｎｘｉａｎｇ Ｚｈｏｎｇｋｅ Ｓｃｉｅｎｃｅ ＆ Ｔｅｃｈｎｏｌｏｇｙ Ｃｏ．， Ｌｔｄ．製の多孔膜（材料：ポリプロピレン、厚さ：４０μｍ、商品名：４０ｍｉｃｒｏｎ）を準備した。電池組立て前に、界面活性剤（ダウケミカル株式会社製、商品名：Ｔｒｉｔｏｎ（登録商標）－Ｘ１００）で多孔膜を親水化処理した。親水化処理は、Ｔｒｉｔｏｎ－Ｘ１００が１質量％含まれる水溶液に多孔膜を２４時間浸漬した後、室温で１時間乾燥することにより行った。多孔膜を３．０ｃｍ×１０．０ｃｍに裁断した後に半分に折ることにより多孔膜Ａ（３．０ｃｍ×５．０ｃｍ）を得た。この多孔膜Ａの一対の両側面（長辺）を熱溶着することで袋状の多孔部材を得た後、未化成の正極１枚をこの袋状の多孔部材に収容することにより正極体を得た。また、３枚の多孔膜Ａを３重に重ねることにより積層体を得た後、積層体の一対の両側面（長辺）を熱溶着することで袋状の多孔部材を得た。そして、未化成の負極１枚をこの袋状の多孔部材に収容することにより負極体を得た。
<Making nickel-zinc batteries>
(Example 1)
Xinxiang Zhongke Science & Technology Co., Ltd. , Ltd. A porous membrane (material: polypropylene, thickness: 40 μm, trade name: 40 micron) was prepared. Prior to battery assembly, the porous membrane was hydrophilized with a surfactant (manufactured by Dow Chemical Co., Ltd., trade name: Triton®-X100). The hydrophilization treatment was carried out by immersing the porous membrane in an aqueous solution containing 1% by mass of Triton-X100 for 24 hours and then drying at room temperature for 1 hour. The porous membrane was cut into 3.0 cm × 10.0 cm and then folded in half to obtain a porous membrane A (3.0 cm × 5.0 cm). A bag-shaped porous member is obtained by heat-welding a pair of both side surfaces (long sides) of the porous film A, and then one unchemical positive electrode is housed in the bag-shaped porous member to form a positive electrode body. Obtained. Further, a laminated body was obtained by stacking three porous films A in a triple layer, and then a pair of both side surfaces (long sides) of the laminated body were heat-welded to obtain a bag-shaped porous member. Then, a negative electrode body was obtained by accommodating one unchemical negative electrode in this bag-shaped porous member.
ニッポン高度紙工業製のＶＬ１００（材料：セルロース、厚さ：１００μｍ）を３．０ｃｍ×１０．０ｃｍに裁断した後に半分に折ることにより得られた不織布（３．０ｃｍ×５．０ｃｍ）を正極体と負極体との間に挟みつつ２枚の正極体と３枚の負極体とを交互に積層した後に同極性の極板同士をストラップで連結させることにより電極群（極板群）を作製した。この電極群を電槽内に配置した後、電槽の上面に蓋体を接着することにより未化成のニッケル亜鉛電池を得た。スペーサーを用いて、電槽厚みに対する電極群の厚みを９５．０％に調整した。次いで、電解液を未化成のニッケル亜鉛電池の電槽内に注入した後、２４時間放置した。その後、２４ｍＡ、１５時間の条件で充電を行うことにより、化成後のニッケル亜鉛電池（公称容量：３２０ｍＡｈ）を作製した。化成後のニッケル亜鉛電池において、負極体の多孔部材における負極材の主面に対向する部分（負極材の主面を被覆する部分）の厚さは１２０μｍであった。 A non-woven fabric (3.0 cm x 5.0 cm) obtained by cutting VL100 (material: cellulose, thickness: 100 μm) manufactured by Nippon Advanced Paper Industry into 3.0 cm × 10.0 cm and then folding it in half is used as a positive electrode body. An electrode group (electrode plate group) was produced by alternately laminating two positive electrode bodies and three negative electrode bodies while sandwiching them between the electrode body and the negative electrode body, and then connecting the electrode plates of the same polarity with a strap. .. After arranging this electrode group in the electric tank, a lid was adhered to the upper surface of the electric tank to obtain an unchemical nickel-zinc battery. Using a spacer, the thickness of the electrode group with respect to the thickness of the battery case was adjusted to 95.0%. Then, after injecting the electrolytic solution into the electric tank of the unchemical nickel-zinc battery, it was left for 24 hours. Then, by charging under the conditions of 24 mA and 15 hours, a nickel-zinc battery (nominal capacity: 320 mAh) after chemical conversion was produced. In the nickel-zinc battery after chemical conversion, the thickness of the portion of the porous member of the negative electrode body facing the main surface of the negative electrode material (the portion covering the main surface of the negative electrode material) was 120 μm.
（実施例２）
親水化処理される多孔膜として、宇部興産株式会社製の多孔膜（二枚のポリプロピレンフィルムに挟まれたポリエチレンフィルムを有する三層構造、総厚：２０μｍ、商品名：ＵＰ３３６４）を用いたこと、及び、袋状の多孔部材を得るための積層体として、６枚の多孔膜Ａを６重に重ねることにより得られた積層体を用いたことを除き実施例１と同様に行うことにより化成後のニッケル亜鉛電池（公称容量：３２０ｍＡｈ）を作製した。化成後のニッケル亜鉛電池において、負極体の多孔部材における負極材の主面に対向する部分（負極材の主面を被覆する部分）の厚さは１２０μｍであった。
(Example 2)
As the porous membrane to be hydrophilized, a porous membrane manufactured by Ube Kosan Co., Ltd. (three-layer structure having a polyethylene film sandwiched between two polypropylene films, total thickness: 20 μm, trade name: UP3364) was used. After the chemical formation, the process was carried out in the same manner as in Example 1 except that the laminate obtained by stacking six porous films A in six layers was used as the laminate for obtaining the bag-shaped porous member. Nickel-zinc battery (nominal capacity: 320 mAh) was manufactured. In the nickel-zinc battery after chemical conversion, the thickness of the portion of the porous member of the negative electrode body facing the main surface of the negative electrode material (the portion covering the main surface of the negative electrode material) was 120 μm.
（実施例３）
親水化処理される多孔膜として、宇部興産株式会社製の多孔膜（二枚のポリプロピレンフィルムに挟まれたポリエチレンフィルムを有する三層構造、総厚：２５μｍ、商品名：ＵＰ３３５５）を用いたこと、及び、袋状の多孔部材を得るための積層体として、５枚の多孔膜Ａを５重に重ねることにより得られた積層体を用いたことを除き実施例１と同様に行うことにより化成後のニッケル亜鉛電池（公称容量：３２０ｍＡｈ）を作製した。化成後のニッケル亜鉛電池において、負極体の多孔部材における負極材の主面に対向する部分（負極材の主面を被覆する部分）の厚さは１２５μｍであった。
(Example 3)
As the porous membrane to be hydrophilized, a porous membrane manufactured by Ube Kosan Co., Ltd. (three-layer structure having a polyethylene film sandwiched between two polypropylene films, total thickness: 25 μm, trade name: UP3355) was used. After the chemical formation, the process was carried out in the same manner as in Example 1 except that the laminate obtained by stacking five porous films A in five layers was used as the laminate for obtaining the bag-shaped porous member. Nickel-zinc battery (nominal capacity: 320 mAh) was manufactured. In the nickel-zinc battery after chemical conversion, the thickness of the portion of the porous member of the negative electrode body facing the main surface of the negative electrode material (the portion covering the main surface of the negative electrode material) was 125 μm.
（比較例１）
２枚の多孔膜Ａを２重に重ねることにより積層体を得た後、積層体の一対の両側面を熱溶着することで袋状の多孔部材を得たこと、及び、スペーサーの厚さを調整することにより電槽厚みに対する電極群の厚みを９５．０％に調整したことを除き実施例１と同様に行うことにより化成後のニッケル亜鉛電池（公称容量：３２０ｍＡｈ）を作製した。化成後のニッケル亜鉛電池において、負極体の多孔部材における負極材の主面に対向する部分（負極材の主面を被覆する部分）の厚さは８０μｍであった。
(Comparative Example 1)
After obtaining a laminated body by double stacking two porous films A, a bag-shaped porous member was obtained by heat welding a pair of both side surfaces of the laminated body, and the thickness of the spacer was determined. A nickel-zinc battery (nominal capacity: 320 mAh) after chemical welding was produced by performing the same procedure as in Example 1 except that the thickness of the electrode group with respect to the thickness of the battery case was adjusted to 95.0%. In the nickel-zinc battery after chemical conversion, the thickness of the portion of the porous member of the negative electrode body facing the main surface of the negative electrode material (the portion covering the main surface of the negative electrode material) was 80 μm.
（比較例２）
１枚の多孔膜Ａの一対の両側面を熱溶着することで袋状の多孔部材を得たこと、及び、スペーサーの厚さを調整することにより電槽厚みに対する電極群の厚みを９５．０％に調整したことを除き実施例１と同様に行うことにより化成後のニッケル亜鉛電池（公称容量：３２０ｍＡｈ）を作製した。化成後のニッケル亜鉛電池において、負極体の多孔部材における負極材の主面に対向する部分（負極材の主面を被覆する部分）の厚さは４０μｍであった。
(Comparative Example 2)
A bag-shaped porous member was obtained by heat-welding a pair of both side surfaces of one porous membrane A, and the thickness of the electrode group with respect to the battery thickness was 95.0 by adjusting the thickness of the spacer. A nickel-zinc battery after chemical welding (nominal capacity: 320 mAh) was produced by carrying out the same procedure as in Example 1 except that the temperature was adjusted to%. In the nickel-zinc battery after chemical conversion, the thickness of the portion of the porous member of the negative electrode body facing the main surface of the negative electrode material (the portion covering the main surface of the negative electrode material) was 40 μm.
＜寿命性能の評価＞
４０℃において、電流値が１６ｍＡ（０．０５Ｃ）に減衰するまで１０５．７ｍＡ（０．３３Ｃ）、１．８８Ｖの定電圧でニッケル亜鉛電池の充電を行った後、電池電圧が１．１Ｖに到達するまで１０５．７ｍＡ（０．３３Ｃ）の定電流でニッケル亜鉛電池の放電を行うことを１サイクルとする試験を行った。１サイクル目の放電容量に対して放電容量が６０％を下回った場合に試験を終了し、試験終了までに行ったサイクル数によって寿命性能（サイクル寿命性能）を評価した。実施例１は１４３サイクルであり、実施例２は１４６サイクルであり、実施例３は１４７サイクルであり、比較例１は４３サイクルであり、比較例２は４１サイクルであった。
<Evaluation of life performance>
At 40 ° C., the nickel-zinc battery is charged at a constant voltage of 105.7 mA (0.33C) and 1.88 V until the current value decays to 16 mA (0.05 C), and then the battery voltage becomes 1.1 V. A test was conducted in which one cycle was to discharge the nickel-zinc battery at a constant current of 105.7 mA (0.33 C) until it reached the point. The test was terminated when the discharge capacity was less than 60% of the discharge capacity of the first cycle, and the life performance (cycle life performance) was evaluated by the number of cycles performed until the end of the test. Example 1 had 143 cycles, Example 2 had 146 cycles, Example 3 had 147 cycles, Comparative Example 1 had 43 cycles, and Comparative Example 2 had 41 cycles.
１０…負極、１２…集電体、１４…負極材、１４ａ…主面、２０，２０ａ…多孔部材、１００，１００ａ…負極体、Ａ…負極材における最小厚さを有する部分、Ｂ…負極材における最大厚さを有する部分、Ｄ…負極材における最大厚さと最小厚さとの差、Ｔ，Ｔａ…多孔部材の厚さ、Ｔｍａｘ…負極材における最大厚さ、Ｔｍｉｎ…負極材における最小厚さ。
10 ... Negative electrode, 12 ... Current collector, 14 ... Negative electrode material, 14a ... Main surface, 20, 20a ... Porous member, 100, 100a ... Negative electrode body, A ... Negative electrode material with minimum thickness, B ... Negative electrode material , D ... the difference between the maximum thickness and the minimum thickness in the negative electrode material, T, Ta ... the thickness of the porous member, T max ... the maximum thickness in the negative electrode material, T min ... the minimum in the negative electrode material. thickness.
Claims (5)
前記負極が、集電体と、当該集電体に支持された負極材と、を有し、
前記多孔部材が前記負極材の主面に対向し、
前記多孔部材における前記主面に対向する部分の厚さが前記負極材における最大厚さと最小厚さとの差より大きい、亜鉛電池用負極体。 With a negative electrode and a porous member,
The negative electrode has a current collector and a negative electrode material supported by the current collector.
The porous member faces the main surface of the negative electrode material, and the porous member faces the main surface of the negative electrode material.
A negative electrode body for a zinc battery, wherein the thickness of the portion of the porous member facing the main surface is larger than the difference between the maximum thickness and the minimum thickness of the negative electrode material.
A zinc battery comprising the negative electrode body for a zinc battery according to any one of claims 1 to 4 and a positive electrode.
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