JP2023133607A - Electrolyte solution for zinc battery and zinc battery - Google Patents
Electrolyte solution for zinc battery and zinc battery Download PDFInfo
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- 239000008151 electrolyte solution Substances 0.000 title claims abstract description 58
- 239000011701 zinc Substances 0.000 title claims abstract description 51
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 47
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 63
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 51
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 50
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 230000035699 permeability Effects 0.000 claims description 35
- 239000003792 electrolyte Substances 0.000 claims description 30
- 238000007086 side reaction Methods 0.000 abstract description 25
- 239000000243 solution Substances 0.000 abstract 1
- 239000007774 positive electrode material Substances 0.000 description 33
- 239000007773 negative electrode material Substances 0.000 description 31
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 29
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 20
- 239000000463 material Substances 0.000 description 20
- 229910052751 metal Inorganic materials 0.000 description 19
- 239000002184 metal Substances 0.000 description 19
- 239000004745 nonwoven fabric Substances 0.000 description 18
- 235000011121 sodium hydroxide Nutrition 0.000 description 15
- 229910052759 nickel Inorganic materials 0.000 description 14
- 239000007772 electrode material Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000003054 catalyst Substances 0.000 description 11
- 239000004020 conductor Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- 238000007599 discharging Methods 0.000 description 10
- 239000012982 microporous membrane Substances 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 10
- 235000014692 zinc oxide Nutrition 0.000 description 10
- 239000011230 binding agent Substances 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 239000012528 membrane Substances 0.000 description 8
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 8
- 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
- -1 zincate ions Chemical class 0.000 description 7
- 239000004354 Hydroxyethyl cellulose Substances 0.000 description 6
- 229920000663 Hydroxyethyl cellulose Polymers 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 239000000654 additive Substances 0.000 description 6
- 239000006258 conductive agent Substances 0.000 description 6
- 210000001787 dendrite Anatomy 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 235000019447 hydroxyethyl cellulose Nutrition 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 238000002360 preparation method Methods 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
- 239000010941 cobalt Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000000835 fiber Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910001923 silver oxide Inorganic materials 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000003945 anionic surfactant Substances 0.000 description 3
- 229910000410 antimony oxide Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000003197 catalytic effect Effects 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
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000003112 inhibitor Substances 0.000 description 3
- 239000007769 metal material Substances 0.000 description 3
- 239000002736 nonionic surfactant Substances 0.000 description 3
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 description 3
- 235000011181 potassium carbonates Nutrition 0.000 description 3
- 239000011698 potassium fluoride Substances 0.000 description 3
- 235000003270 potassium fluoride Nutrition 0.000 description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 description 3
- 235000011009 potassium phosphates Nutrition 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 239000001488 sodium phosphate Substances 0.000 description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 description 3
- 235000011008 sodium phosphates Nutrition 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 3
- 229910001369 Brass Inorganic materials 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-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
- 239000003513 alkali Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 2
- 239000008112 carboxymethyl-cellulose Substances 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
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000001681 protective effect Effects 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
- 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
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-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
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920000265 Polyparaphenylene Polymers 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 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
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 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
- 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
- 239000013078 crystal Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000006232 furnace black Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 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
- 239000003273 ketjen black Substances 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000006233 lamp black Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 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
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 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
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 description 1
- 239000006234 thermal black Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
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
Abstract
Description
本発明は、亜鉛電池用電解液及び亜鉛電池に関する。 TECHNICAL FIELD The present invention relates to an electrolyte for a zinc battery and a zinc battery.
亜鉛電池としては、ニッケル亜鉛電池、空気亜鉛電池、銀亜鉛電池等が知られている。例えば、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ともに、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。 Known examples of zinc batteries include nickel-zinc batteries, zinc-air batteries, and silver-zinc batteries. For example, a nickel-zinc battery is a water-based battery that uses an aqueous electrolyte such as an aqueous potassium hydroxide solution, so it is highly safe, and the combination of a zinc electrode and a nickel electrode produces a high electromotive force for a water-based battery. It is known to have. Furthermore, in addition to excellent input/output performance, nickel-zinc batteries are low-cost and can be applied to industrial applications (e.g., backup power sources, etc.) and automotive applications (e.g., hybrid vehicles, etc.). 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 charging and discharging reaction of a nickel-zinc battery proceeds, for example, according to the following formula (discharging reaction: rightward, charging reaction: leftward).
(Positive electrode) 2NiOOH+2H 2 O+2e - → 2Ni(OH) 2 +2OH -
(Negative electrode) Zn+2OH - → Zn(OH) 2 +2e -
上記式に示されるように、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）が進行するととも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。従来の亜鉛電池では、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短絡が発生する場合がある。そのため、このようなデンドライトによる短絡を防止し、寿命性能を向上させる種々の試みがなされている。例えば、下記特許文献１には、ニッケルメッキを施した不織布を電極間に介在させることで、デンドライトによる短絡を防止する技術が開示されている。 As shown in the above formula, in a zinc battery, zinc hydroxide (Zn(OH) 2 ) is produced by a discharge reaction. Zinc hydroxide is soluble in the electrolyte, and when zinc hydroxide is dissolved in the electrolyte, tetrahydroxide zincate ions ([Zn(OH) 4 ] 2- ) diffuse into the electrolyte. As a result, as the shape change (deformation) of the negative electrode progresses, the distribution of charging current becomes non-uniform, etc., and as a result, zinc is locally precipitated on the negative electrode, and dendrites (dendritic crystals) are generated. In conventional zinc batteries, when dendrites grow due to repeated charging and discharging, the dendrites may penetrate the separator and cause a short circuit. Therefore, various attempts have been made to prevent short circuits caused by such dendrites and improve life performance. For example, Patent Document 1 listed below discloses a technique for preventing short circuits caused by dendrites by interposing a nickel-plated nonwoven fabric between electrodes.
ニッケル亜鉛電池の充放電時には、電解液の分解反応等の副反応が生じる場合がある。副反応の発生は、寿命性能の低下につながるため、副反応の発生を抑制することが求められる。また、亜鉛電池には、寿命性能を向上させることに加えて、高率放電性能を向上させることが求められている。 During charging and discharging of nickel-zinc batteries, side reactions such as decomposition reactions of the electrolyte may occur. Since the occurrence of side reactions leads to a decrease in life performance, it is required to suppress the occurrence of side reactions. Furthermore, zinc batteries are required to have improved high rate discharge performance in addition to improved life performance.
そこで、本発明は、優れた高率放電性能を有し、且つ、充放電時の副反応が抑制された亜鉛電池を提供することを目的とする。 Therefore, an object of the present invention is to provide a zinc battery that has excellent high-rate discharge performance and suppresses side reactions during charging and discharging.
本発明の一側面の亜鉛電池用電解液は、水酸化カリウムと、水酸化ナトリウム及び水酸化リチウムからなる群より選択される少なくとも一種と、を含む水溶液である。この電解液によれば、亜鉛電池の高率放電性能を向上させることができるとともに、充放電時の副反応の発生を抑制することができる。 The electrolytic solution for a zinc battery according to one aspect of the present invention is an aqueous solution containing potassium hydroxide and at least one selected from the group consisting of sodium hydroxide and lithium hydroxide. According to this electrolytic solution, the high rate discharge performance of the zinc battery can be improved, and the occurrence of side reactions during charging and discharging can be suppressed.
本発明の他の一側面の亜鉛電池は、上記電解液を備える。この亜鉛電池によれば、優れた高率放電性能が得られるとともに、充放電時の副反応が起こり難い。 A zinc battery according to another aspect of the present invention includes the electrolyte described above. According to this zinc battery, excellent high rate discharge performance can be obtained, and side reactions are unlikely to occur during charging and discharging.
亜鉛電池は、透気度の合計が５００～２５００ｓｅｃ／１００ｍＬである、一又は複数のセパレータと、当該一又は複数のセパレータを介して隣り合う正極及び負極と、を更に備えることが好ましい。隣り合う正極及び負極間に配置されるセパレータの透気度の合計が上記範囲である場合、デンドライトによる短絡の発生が抑制されやすくなり、より優れた寿命性能（例えばサイクル寿命性能）が得られやすい。また、本発明では、副反応（電解液の分解反応）の結果生じる酸素量が低減されているため、セパレータの透気度の合計が上記範囲であったとしても、負極に吸収されずに系外に排出される酸素の量が少ない。すなわち、電解液の減少が生じ難い。 Preferably, the zinc battery further includes one or more separators having a total air permeability of 500 to 2500 sec/100 mL, and a positive electrode and a negative electrode adjacent to each other with the one or more separators interposed therebetween. When the total air permeability of the separators placed between adjacent positive and negative electrodes is within the above range, the occurrence of short circuits due to dendrites is more likely to be suppressed, and better life performance (for example, cycle life performance) is more likely to be obtained. . In addition, in the present invention, since the amount of oxygen generated as a result of side reactions (decomposition reaction of electrolyte solution) is reduced, even if the total air permeability of the separator is within the above range, it will not be absorbed by the negative electrode and the oxygen will not be absorbed by the negative electrode. The amount of oxygen exhausted to the outside is small. That is, the electrolyte solution is less likely to decrease.
上記一又は複数のセパレータのうちの少なくとも一つは、０．１～１５０ｓｅｃ／１００ｍＬの透気度を有することが好ましい。この場合、より優れた高率放電性能及び寿命性能が得られやすい。 Preferably, at least one of the one or more separators has an air permeability of 0.1 to 150 sec/100 mL. In this case, better high rate discharge performance and life performance are likely to be obtained.
本発明によれば、優れた高率放電性能を有し、且つ、充放電時の副反応が抑制された亜鉛電池を提供することができる。 According to the present invention, it is possible to provide a zinc battery that has excellent high rate discharge performance and suppresses side reactions during charging and discharging.
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。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、実験例に示されている値に置き換えてもよい。「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使用量は、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。また、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。また、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 this specification, a numerical range indicated using "~" indicates a range that includes the numerical values written before and after "~" as the minimum and maximum values, respectively. In the numerical ranges described stepwise in this specification, the upper limit or lower limit of the numerical range of one step can be arbitrarily combined with the upper limit or lower limit of the numerical range of another step. In the numerical ranges described in this specification, the upper limit or lower limit of the numerical range may be replaced with the values shown in the experimental examples. "A or B" may include either A or B, or may include both. The materials exemplified herein can be used alone or in combination of two or more, unless otherwise specified. In the present specification, if there are multiple substances corresponding to each component in the composition, unless otherwise specified, the usage amount of each component in the composition refers to the total amount of the multiple substances present in the composition. means. Furthermore, in this specification, the term "film" or "layer" includes not only a structure formed on the entire surface but also a structure formed in a part when observed as a plan view. be done. In addition, in this specification, the term "process" does not only refer to an independent process, but also refers to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved. included.
以下、本発明の好適な実施形態について説明する。ただし、本発明は下記実施形態に何ら限定されるものではない。 Hereinafter, preferred embodiments of the present invention will be described. However, the present invention is not limited to the following embodiments.
＜亜鉛電池用電解液＞
［第一実施形態］
第一実施形態の電解液は、電解質として、水酸化カリウム及び水酸化ナトリウムを含む水溶液である。水酸化カリウム及び水酸化ナトリウムは、水溶液中で電離していてよく、塩として存在していてもよい。電解液の溶媒としては、例えば、イオン交換水を用いることができる。
<Electrolyte solution for zinc batteries>
[First embodiment]
The electrolytic solution of the first embodiment is an aqueous solution containing potassium hydroxide and sodium hydroxide as electrolytes. Potassium hydroxide and sodium hydroxide may be ionized in an aqueous solution or may exist as salts. For example, ion-exchanged water can be used as the solvent for the electrolytic solution.
電解液中の水酸化カリウムの濃度（含有量）は、高率放電性能に更に優れる観点から、電解液の全質量を基準として、３質量％以上、１０質量％以上又は１５質量％以上であってよい。電解液中の水酸化カリウムの濃度は、副反応を更に抑制できる観点から、電解液の全質量を基準として、３５質量％以下、３０質量％以下又は２５質量％以下であってよい。 The concentration (content) of potassium hydroxide in the electrolytic solution should be 3% by mass or more, 10% by mass or more, or 15% by mass or more based on the total mass of the electrolytic solution, from the viewpoint of further improving high-rate discharge performance. It's fine. The concentration of potassium hydroxide in the electrolytic solution may be 35% by mass or less, 30% by mass or less, or 25% by mass or less based on the total mass of the electrolytic solution, from the viewpoint of further suppressing side reactions.
電解液中の水酸化ナトリウムの濃度（含有量）は、副反応を更に抑制できる観点から、電解液の全質量を基準として、１質量％以上、３質量％以上又は５質量％以上であってよい。電解液中の水酸化ナトリウムの濃度は、高率放電性能に更に優れる観点から、電解液の全質量を基準として、２５質量％以下、１５質量％以下又は１０質量％以下であってよい。 The concentration (content) of sodium hydroxide in the electrolytic solution is 1% by mass or more, 3% by mass or more, or 5% by mass or more based on the total mass of the electrolytic solution, from the viewpoint of further suppressing side reactions. good. The concentration of sodium hydroxide in the electrolytic solution may be 25% by mass or less, 15% by mass or less, or 10% by mass or less based on the total mass of the electrolytic solution, from the viewpoint of further improving high-rate discharge performance.
電解液中の水酸化カリウム及び水酸化ナトリウムの含有量の合計は、高率放電性能に更に優れる観点及び副反応を更に抑制できる観点から、電解液の全質量を基準として、１２質量％以上、１５質量％以上又は１８質量％以上であってよく、３５質量％以下、３０質量％以下又は２８質量％以下であってよい。 The total content of potassium hydroxide and sodium hydroxide in the electrolytic solution is 12% by mass or more, based on the total mass of the electrolytic solution, from the viewpoint of further improving high-rate discharge performance and further suppressing side reactions. It may be 15% by weight or more or 18% by weight or more, and may be 35% by weight or less, 30% by weight or less, or 28% by weight or less.
電解液中の電解質の濃度（含有量）は、高率放電性能に更に優れる観点及び副反応を更に抑制できる観点から、電解液の全質量を基準として、１２質量％以上、１５質量％以上又は１８質量％以上であってよく、３５質量％以下、３０質量％以下又は２８質量％以下であってよい。 The concentration (content) of the electrolyte in the electrolytic solution is 12% by mass or more, 15% by mass or more, or It may be 18% by weight or more, and may be 35% by weight or less, 30% by weight or less, or 28% by weight or less.
電解液は、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更に含有してもよい。 The electrolyte contains potassium phosphate, potassium fluoride, potassium carbonate, sodium phosphate, sodium fluoride, lithium hydroxide, zinc oxide, antimony oxide, titanium dioxide, nonionic surfactant, anionic surfactant, etc. It may further contain.
［第二実施形態］
第二実施形態の電解液は、電解質として、水酸化カリウム及び水酸化リチウムを含む水溶液である。水酸化カリウム及び水酸化リチウムは、水溶液中で電離していてよく、塩として存在していてもよい。電解液の溶媒としては、例えば、イオン交換水を用いることができる。
[Second embodiment]
The electrolytic solution of the second embodiment is an aqueous solution containing potassium hydroxide and lithium hydroxide as electrolytes. Potassium hydroxide and lithium hydroxide may be ionized in an aqueous solution or may exist as a salt. For example, ion-exchanged water can be used as the solvent for the electrolytic solution.
電解液中の水酸化カリウムの濃度（含有量）は、高率放電性能に更に優れる観点から、電解液の全質量を基準として、１５質量％以上、１８質量％以上又は２０質量％以上であってよい。電解液中の水酸化カリウムの濃度は、副反応を更に抑制できる観点から、電解液の全質量を基準として、３５質量％以下、３０質量％以下又は２５質量％以下であってよい。 The concentration (content) of potassium hydroxide in the electrolytic solution is 15% by mass or more, 18% by mass or more, or 20% by mass or more based on the total mass of the electrolytic solution, from the viewpoint of further improving high rate discharge performance. It's fine. The concentration of potassium hydroxide in the electrolytic solution may be 35% by mass or less, 30% by mass or less, or 25% by mass or less based on the total mass of the electrolytic solution, from the viewpoint of further suppressing side reactions.
電解液中の水酸化リチウムの濃度（含有量）は、副反応を更に抑制できる観点から、電解液の全質量を基準として、０．０１質量％以上、０．１質量％以上又は０．２質量％以上であってよい。電解液中の水酸化リチウムの濃度は、高率放電性能に更に優れる観点から、電解液の全質量を基準として、１０質量％以下、５質量％以下又は３質量％以下であってよい。 The concentration (content) of lithium hydroxide in the electrolyte is 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass, based on the total mass of the electrolyte, from the viewpoint of further suppressing side reactions. It may be % by mass or more. The concentration of lithium hydroxide in the electrolytic solution may be 10% by mass or less, 5% by mass or less, or 3% by mass or less based on the total mass of the electrolytic solution, from the viewpoint of further improving high-rate discharge performance.
電解液中の水酸化カリウム及び水酸化リチウムの含有量の合計は、高率放電性能に更に優れる観点及び副反応を更に抑制できる観点から、電解液の全質量を基準として、１２質量％以上、１５質量％以上又は１８質量％以上であってよく、３５質量％以下、３０質量％以下又は２８質量％以下であってよい。 The total content of potassium hydroxide and lithium hydroxide in the electrolytic solution is 12% by mass or more, based on the total mass of the electrolytic solution, from the viewpoint of further improving high-rate discharge performance and further suppressing side reactions. It may be 15% by weight or more or 18% by weight or more, and may be 35% by weight or less, 30% by weight or less, or 28% by weight or less.
電解液中の電解質の濃度（含有量）は、高率放電性能に更に優れる観点及び副反応を更に抑制できる観点から、電解液の全質量を基準として、１２質量％以上、１５質量％以上又は１８質量％以上であってよく、３５質量％以下、３０質量％以下又は２８質量％以下であってよい。 The concentration (content) of the electrolyte in the electrolytic solution is 12% by mass or more, 15% by mass or more, or It may be 18% by weight or more, and may be 35% by weight or less, 30% by weight or less, or 28% by weight or less.
電解液は、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、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更に含有してもよい。 The electrolyte contains potassium phosphate, potassium fluoride, potassium carbonate, sodium phosphate, sodium fluoride, sodium hydroxide, zinc oxide, antimony oxide, titanium dioxide, nonionic surfactants, anionic surfactants, etc. It may further contain.
［第三実施形態］
第三実施形態の電解液は、電解質として、水酸化カリウム、水酸化ナトリウム及び水酸化リチウムを含む水溶液である。水酸化カリウム、水酸化ナトリウム及び水酸化リチウムは、水溶液中で電離していてよく、塩として存在していてもよい。電解液の溶媒としては、例えば、イオン交換水を用いることができる。
[Third embodiment]
The electrolytic solution of the third embodiment is an aqueous solution containing potassium hydroxide, sodium hydroxide, and lithium hydroxide as electrolytes. Potassium hydroxide, sodium hydroxide, and lithium hydroxide may be ionized in an aqueous solution or may exist as a salt. For example, ion-exchanged water can be used as the solvent for the electrolytic solution.
電解液中の水酸化カリウムの濃度（含有量）は、高率放電性能に更に優れる観点から、電解液の全質量を基準として、３質量％以上、１０質量％以上又は１５質量％以上であってよい。電解液中の水酸化カリウムの濃度は、副反応を更に抑制できる観点から、電解液の全質量を基準として、３５質量％以下、３０質量％以下又は２５質量％以下であってよい。 The concentration (content) of potassium hydroxide in the electrolytic solution should be 3% by mass or more, 10% by mass or more, or 15% by mass or more based on the total mass of the electrolytic solution, from the viewpoint of further improving high-rate discharge performance. It's fine. The concentration of potassium hydroxide in the electrolytic solution may be 35% by mass or less, 30% by mass or less, or 25% by mass or less based on the total mass of the electrolytic solution, from the viewpoint of further suppressing side reactions.
電解液中の水酸化ナトリウムの濃度（含有量）は、副反応を更に抑制できる観点から、電解液の全質量を基準として、１質量％以上、３質量％以上又は５質量％以上であってよい。電解液中の水酸化ナトリウムの濃度は、高率放電性能に更に優れる観点から、電解液の全質量を基準として、２５質量％以下、１５質量％以下又は１０質量％以下であってよい。 The concentration (content) of sodium hydroxide in the electrolytic solution is 1% by mass or more, 3% by mass or more, or 5% by mass or more based on the total mass of the electrolytic solution, from the viewpoint of further suppressing side reactions. good. The concentration of sodium hydroxide in the electrolytic solution may be 25% by mass or less, 15% by mass or less, or 10% by mass or less based on the total mass of the electrolytic solution, from the viewpoint of further improving high-rate discharge performance.
電解液中の水酸化リチウムの濃度（含有量）は、副反応を更に抑制できる観点から、電解液の全質量を基準として、０．０１質量％以上、０．１質量％以上又は０．２質量％以上であってよい。電解液中の水酸化リチウムの濃度は、高率放電性能に更に優れる観点から、電解液の全質量を基準として、１０質量％以下、５質量％以下又は３質量％以下であってよい。 The concentration (content) of lithium hydroxide in the electrolyte is 0.01% by mass or more, 0.1% by mass or more, or 0.2% by mass, based on the total mass of the electrolyte, from the viewpoint of further suppressing side reactions. It may be % by mass or more. The concentration of lithium hydroxide in the electrolytic solution may be 10% by mass or less, 5% by mass or less, or 3% by mass or less based on the total mass of the electrolytic solution, from the viewpoint of further improving high-rate discharge performance.
電解液中の水酸化カリウム、水酸化ナトリウム及び水酸化リチウムの含有量の合計は、高率放電性能に更に優れる観点及び副反応を更に抑制できる観点から、電解液の全質量を基準として、１２質量％以上、１５質量％以上又は１８質量％以上であってよく、３５質量％以下、３０質量％以下又は２５質量％以下であってよい。 The total content of potassium hydroxide, sodium hydroxide, and lithium hydroxide in the electrolytic solution is 12% based on the total mass of the electrolytic solution, from the viewpoint of further improving high-rate discharge performance and further suppressing side reactions. It may be at least 15% by mass, or at least 18% by mass, and up to 35% by mass, at most 30% by mass, or at most 25% by mass.
電解液中の電解質の濃度（含有量）は、高率放電性能に更に優れる観点及び副反応を更に抑制できる観点から電解液の全質量を基準として、１２質量％以上、１５質量％以上又は１８質量％以上であってよく、３５質量％以下、３０質量％以下又は２５質量％以下であってよい。 The concentration (content) of the electrolyte in the electrolytic solution is 12% by mass or more, 15% by mass or more, or 18% by mass, based on the total mass of the electrolytic solution, from the viewpoint of further improving high rate discharge performance and further suppressing side reactions. It may be 35% by mass or less, 30% by mass or less, or 25% by mass or less.
電解液は、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、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更に含有してもよい。 The electrolytic solution further contains potassium phosphate, potassium fluoride, potassium carbonate, sodium phosphate, sodium fluoride, zinc oxide, antimony oxide, titanium dioxide, nonionic surfactant, anionic surfactant, etc. Good too.
上記第一～第三実施形態の電解液は、亜鉛電池（例えば亜鉛二次電池）に組み込まれる亜鉛電池用電解液である。亜鉛電池としては、ニッケル亜鉛電池、空気亜鉛電池等が挙げられる。亜鉛電池では、亜鉛負極を用いることができる。以下、上記実施形態の電解液が用いられる亜鉛電池の一例として、ニッケル亜鉛電池について説明する。 The electrolytic solutions of the first to third embodiments described above are electrolytic solutions for zinc batteries that are incorporated into zinc batteries (for example, zinc secondary batteries). Examples of zinc batteries include nickel-zinc batteries and zinc-air batteries. In zinc batteries, a zinc negative electrode can be used. Hereinafter, a nickel-zinc battery will be described as an example of a zinc battery in which the electrolytic solution of the above embodiment is used.
＜ニッケル亜鉛電池＞
本実施形態のニッケル亜鉛電池（例えばニッケル亜鉛二次電池）は、例えば、電槽と、電槽に収容された電極群（例えば極板群）及び電解液と、を備える。本実施形態の亜鉛電池は化成後又は未化成のいずれであってもよい。
<Nickel zinc battery>
The nickel-zinc battery (for example, a nickel-zinc secondary battery) of this embodiment includes, for example, a battery case, an electrode group (for example, an electrode plate group), and an electrolytic solution housed in the battery case. The zinc battery of this embodiment may be either chemically formed or unformed.
電極群は、例えば、正極（例えば正極板）と、負極（例えば負極板）と、セパレータと、を備える。正極と負極とは、一又は複数のセパレータを介して隣り合っている。すなわち、隣り合う正極と負極との間には、一又は複数のセパレータが設けられてる。電極群は、複数の正極、負極及びセパレータを備えていてよい。電極群が複数の正極及び／又は複数の負極を備える場合、正極と負極は、セパレータを介して交互に積層されてよい。複数の正極同士及び複数の負極同士は、例えば、ストラップで連結されていてよい。本実施形態の正極はニッケル（Ｎｉ）電極であり、負極は亜鉛（Ｚｎ）電極である。すなわち、以下の説明における「正極」は「ニッケル電極」と置き換えてよく、「負極」は「亜鉛電極」と置き換えてよい。「正極材」、「負極材」等の記載についても同様である。 The electrode group includes, for example, a positive electrode (for example, a positive electrode plate), a negative electrode (for example, a negative electrode plate), and a separator. The positive electrode and the negative electrode are adjacent to each other with one or more separators in between. That is, one or more separators are provided between adjacent positive and negative electrodes. The electrode group may include a plurality of positive electrodes, negative electrodes, and separators. When the electrode group includes a plurality of positive electrodes and/or a plurality of negative electrodes, the positive electrodes and the negative electrodes may be alternately stacked with separators in between. The plurality of positive electrodes and the plurality of negative electrodes may be connected, for example, with a strap. The positive electrode of this embodiment is a nickel (Ni) electrode, and the negative electrode is a zinc (Zn) electrode. That is, in the following description, "positive electrode" may be replaced with "nickel electrode", and "negative electrode" may be replaced with "zinc electrode". The same applies to the descriptions of "positive electrode material", "negative electrode material", etc.
正極は、例えば、正極集電体と、当該正極集電体に支持された正極材と、を備えている。正極は、化成前及び化成後のいずれであってもよい。 The positive electrode includes, for example, a positive electrode current collector and a positive electrode material supported by the positive electrode current collector. The positive electrode may be either before or after chemical formation.
正極集電体は、正極材からの電流の導電路を構成する。正極集電体は、例えば、平板状、シート状等の形状を有している。正極集電体は、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もよい。正極集電体は、導電性及び耐アルカリ性を有する材料で構成されている。このような材料としては、例えば、正極の反応電位でも安定である材料（正極の反応電位よりも貴な酸化還元電位を有する材料、アルカリ水溶液中で基材表面に酸化被膜等の保護被膜を形成して安定化する材料など）を用いることができる。また、正極においては、副反応として電解液の分解反応が進行し酸素ガスが発生するが、酸素過電圧の高い材料はこのような副反応の進行を抑制できる点で好ましい。正極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）；ニッケル等の金属メッキを施した金属材料（銅、真鍮、鋼等）などが挙げられる。これらの中でも、発泡ニッケルで構成される正極集電体が好ましく用いられる。高率放電性能を更に向上させることができる観点から、少なくとも正極集電体における正極材を支持する部分（正極材支持部）が発泡ニッケルで構成されていることが好ましい。 The positive electrode current collector constitutes a current conduction path from the positive electrode material. The positive electrode current collector has a shape such as a flat plate or a sheet. The positive electrode current collector may be a three-dimensional network structure current collector made of foamed metal, expanded metal, punched metal, metal fiber felt, or the like. The positive electrode current collector is made of a material having conductivity and alkali resistance. Such materials include, for example, materials that are stable even at the reaction potential of the positive electrode (materials that have a redox potential that is more noble than the reaction potential of the positive electrode, and materials that form a protective film such as an oxide film on the surface of the substrate in an alkaline aqueous solution). (e.g., materials that are stabilized by Further, in the positive electrode, a decomposition reaction of the electrolytic solution proceeds as a side reaction and oxygen gas is generated, but a material with a high oxygen overvoltage is preferable in that it can suppress the progress of such side reactions. Specific examples of materials constituting the positive electrode current collector include platinum; nickel (foamed nickel, etc.); and metal materials plated with metal such as nickel (copper, brass, steel, etc.). Among these, a positive electrode current collector made of foamed nickel is preferably used. From the viewpoint of further improving the high rate discharge performance, it is preferable that at least a portion of the positive electrode current collector that supports the positive electrode material (positive electrode material support portion) is made of foamed nickel.
正極材は、例えば、層状を呈している。すなわち、正極は、正極材層を有していてよい。正極材層は、正極集電体上に形成されていてよい。正極集電体の正極材支持部が３次元網目構造を有する場合、当該集電体の網目の間に正極材が充填されて正極材層が形成されていてもよい。 For example, the positive electrode material has a layered shape. That is, the positive electrode may have a positive electrode material layer. The positive electrode material layer may be formed on the positive electrode current collector. When the positive electrode material supporting portion of the positive electrode current collector has a three-dimensional network structure, the positive electrode material may be filled between the meshes of the current collector to form a positive electrode material layer.
正極材は、ニッケルを含む正極活物質（電極活物質）を含有する。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５０～９５質量％であってもよい。 The positive electrode material contains a positive electrode active material (electrode active material) containing 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 fully discharged state. The content of the positive electrode active material may be, for example, 50 to 95% by mass based on the total mass of the positive electrode material.
正極材は、添加剤として、正極活物質以外の他の成分を更に含有してよい。添加剤としては、バインダー（結着剤）、導電剤、膨張抑制剤等が挙げられる。 The positive electrode material may further contain components other than the positive electrode active material as additives. Examples of additives include binders, conductive agents, and expansion inhibitors.
バインダーとしては、親水性又は疎水性のポリマー等が挙げられる。具体的には、例えば、カルボキシメチルセルロース（ＣＭＣ）、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）、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）などをバインダーとして用いることができる。バインダーの含有量は、例えば、正極活物質１００質量部に対して０．０１～５質量部である。 Examples of the binder include hydrophilic or hydrophobic polymers. Specifically, for example, carboxymethylcellulose (CMC), hydroxyethylcellulose (HEC), hydroxypropylmethylcellulose (HPMC), sodium polyacrylate (SPA), fluorine-based polymers (polytetrafluoroethylene (PTFE), etc.) are used as binders. It can be used as The content of the binder is, for example, 0.01 to 5 parts by weight based on 100 parts by weight of the positive electrode active material.
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質量部である。 Examples of the conductive agent include cobalt compounds (cobalt metal, cobalt oxide, cobalt hydroxide, etc.). The content of the conductive agent is, for example, 1 to 20 parts by weight based on 100 parts by weight of the positive electrode active material.
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質量部である。 Examples of the expansion inhibitor include zinc oxide and the like. The content of the expansion inhibitor is, for example, 0.01 to 5 parts by mass based on 100 parts by mass of the positive electrode active material.
負極は、負極集電体（集電体）と、該負極集電体に支持された負極材（電極材）と、を備える。負極は、化成前及び化成後のいずれであってもよい。 The negative electrode includes a negative electrode current collector (current collector) and a negative electrode material (electrode material) supported by the negative electrode current collector. The negative electrode may be either before or after chemical formation.
負極集電体は、負極材からの電流の導電路を構成する。負極集電体は、例えば、平板状、シート状等の形状を有している。負極集電体は、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もよい。負極集電体は、導電性及び耐アルカリ性を有する材料で構成されている。このような材料としては、例えば、負極の反応電位でも安定である材料（負極の反応電位よりも貴な酸化還元電位を有する材料、アルカリ水溶液中で基材表面に酸化被膜等の保護被膜を形成して安定化する材料など）を用いることができる。また、負極においては、副反応として電解液の分解反応が進行し水素ガスが発生するが、水素過電圧の高い材料はこのような副反応の進行を抑制できる点で好ましい。負極集電体を構成する材料の具体例としては、亜鉛；鉛；スズ；スズ等の金属メッキを施した金属材料（銅、真鍮、鋼、ニッケル等）などが挙げられる。 The negative electrode current collector constitutes a current conduction path from the negative electrode material. The negative electrode current collector has a shape such as a flat plate or a sheet. The negative electrode current collector may be a three-dimensional network structure current collector made of foamed metal, expanded metal, punched metal, metal fiber felt, or the like. The negative electrode current collector is made of a material having conductivity and alkali resistance. Examples of such materials include, for example, materials that are stable even at the reaction potential of the negative electrode (materials that have an oxidation-reduction potential that is more noble than the reaction potential of the negative electrode, and materials that form a protective film such as an oxide film on the surface of the base material in an alkaline aqueous solution). (e.g., materials that are stabilized by Further, in the negative electrode, a decomposition reaction of the electrolyte proceeds as a side reaction and hydrogen gas is generated, but a material with a high hydrogen overvoltage is preferable in that it can suppress the progress of such a side reaction. Specific examples of the material constituting the negative electrode current collector include metal materials (copper, brass, steel, nickel, etc.) plated with metals such as zinc; lead; tin; and tin.
負極材は、例えば、層状を呈している。すなわち、負極は、負極材層を有していてよい。負極材層は、負極集電体上に形成されていてよい。負極集電体の負極材を支持する部分が３次元網目構造を有する場合、当該集電体の網目の間に負極材が充填されて負極材層が形成されていてもよい。 For example, the negative electrode material has a layered shape. That is, the negative electrode may have a negative electrode material layer. The negative electrode material layer may be formed on the negative electrode current collector. When the portion of the negative electrode current collector that supports the negative electrode material has a three-dimensional network structure, the negative electrode material may be filled between the meshes of the current collector to form a negative electrode material layer.
負極材は、亜鉛を含む負極活物質（電極活物質）を含有する。負極活物質としては、例えば、金属亜鉛、酸化亜鉛及び水酸化亜鉛が挙げられる。負極活物質は、これらの成分のうちの一種を単独で含んでいてよく、複数種を含んでいてもよい。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る。すなわち、負極材は、金属亜鉛粒子、酸化亜鉛粒子及び水酸化亜鉛粒子からなる群より選択される少なくとも一種を含んでいてよい。負極活物質の含有量は、例えば、負極材の全質量を基準として５０～９５質量％である。 The negative electrode material contains a negative electrode active material (electrode active material) containing zinc. Examples of negative electrode active materials include metal zinc, zinc oxide, and zinc hydroxide. The negative electrode active material may contain one type of these components alone, or may contain multiple types of these components. For example, the negative electrode material contains metallic zinc in a fully charged state, and contains zinc oxide and zinc hydroxide in a fully discharged state. The negative electrode active material is, for example, in the form of particles. That is, the negative electrode material may contain at least one selected from the group consisting of metal zinc particles, zinc oxide particles, and zinc hydroxide particles. The content of the negative electrode active material is, for example, 50 to 95% by mass based on the total mass of the negative electrode material.
負極材は、添加剤を含有してよい。添加剤としては、例えば、結着剤、導電剤等が挙げられる。 The negative electrode material may contain additives. Examples of additives include binders, conductive agents, and the like.
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、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質量部であってもよい。 Examples of the binder include polytetrafluoroethylene, hydroxyethylcellulose, polyethylene oxide, polyethylene, and polypropylene. The content of the binder may be, for example, 0.5 to 10 parts by mass based on 100 parts by mass of the negative electrode active material.
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質量部である。 Examples of the conductive agent include indium compounds (indium oxide, etc.). The content of the conductive agent is, for example, 1 to 20 parts by weight based on 100 parts by weight of the negative electrode active material.
セパレータは、例えば、平板状、シート状等の形状を有するセパレータであってもよい。セパレータとしては、ポリオレフィン系微多孔膜、ナイロン系微多孔膜、耐酸化性のイオン交換樹脂膜、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が挙げられる。 The separator may have a shape such as a flat plate or a sheet. Examples of the separator include microporous polyolefin membranes, microporous nylon membranes, oxidation-resistant ion exchange resin membranes, recycled cellophane resin membranes, inorganic-organic separators, and polyolefin nonwoven fabrics.
セパレータの透気度の合計は、高率放電性能に更に優れる観点、及び、寿命性能（例えばサイクル寿命性能）に優れる観点から、５００～２５００ｓｅｃ／１００ｍＬであることが好ましい。セパレータの透気度の合計は、サイクル寿命性能に更に優れる観点から、より好ましくは１０００ｓｅｃ／１００ｍＬ以上であり、更に好ましくは１２００ｓｅｃ／１００ｍＬ以上であり、特に好ましくは１３００ｓｅｃ／１００ｍＬ以上であり、極めて好ましくは１３５０ｓｅｃ／１００ｍＬ以上である。セパレータの透気度の合計は、高率放電性能に更に優れる観点及びサイクル寿命性能に更に優れる観点から、より好ましくは２０００ｓｅｃ／１００ｍＬ以下であり、更に好ましくは１５００ｓｅｃ／１００ｍＬ以下であり、特に好ましくは１４００ｓｅｃ／１００ｍＬ以下である。ここで、上記透気度の合計とは、セパレータが１つである場合には、１つのセパレータの透気度を意味し、セパレータが複数である場合には、各セパレータの透気度の合計を意味する。また、上記透気度の合計は、隣り合う正極と負極との間に設けられるセパレータの透気度の合計である。すなわち、電極群が複数のセパレータを備える場合であっても、隣り合う正極と負極の間に配置されたセパレータが１つである場合には、透気度の合計は１つのセパレータの透気度を意味する。電極群が複数の正極及び／又は複数の負極を備える場合、隣り合う正極と負極との間に形成される空間のうちの少なくとも一つの空間において、当該空間に配置されたセパレータの透気度の合計が上記範囲となることが好ましく、全ての空間において、当該空間に配置されたセパレータの透気度の合計が上記範囲となることがより好ましい。 The total air permeability of the separator is preferably 500 to 2500 sec/100 mL from the viewpoint of further excellent high rate discharge performance and excellent life performance (eg, cycle life performance). The total air permeability of the separator is more preferably 1000 sec/100 mL or more, still more preferably 1200 sec/100 mL or more, particularly preferably 1300 sec/100 mL or more, and extremely preferably from the viewpoint of further excellent cycle life performance. is 1350sec/100mL or more. The total air permeability of the separator is more preferably 2000 sec/100 mL or less, still more preferably 1500 sec/100 mL or less, and particularly preferably It is 1400sec/100mL or less. Here, the above-mentioned total air permeability means the air permeability of one separator when there is one separator, and the total air permeability of each separator when there are multiple separators. means. Further, the above-mentioned total air permeability is the total air permeability of separators provided between adjacent positive electrodes and negative electrodes. In other words, even if the electrode group includes multiple separators, if there is only one separator placed between the adjacent positive and negative electrodes, the total air permeability is equal to the air permeability of one separator. means. When the electrode group includes a plurality of positive electrodes and/or a plurality of negative electrodes, in at least one of the spaces formed between adjacent positive electrodes and negative electrodes, the air permeability of the separator disposed in the space is It is preferable that the total is within the above range, and it is more preferable that the total air permeability of the separators disposed in all spaces is within the above range.
透気度は、膜に対する空気の透過性の尺度であり、ガーレー試験機法を用いて一定圧力差のもとで一定体積の空気が一定面積の膜を通過する秒数で示すことができる。セパレータの透気度は、ガーレー式デンソメータ（例えば、株式会社安田精機製作所製、商品名：Ｎｏ．３２３ ＧＵＲＬＥＹ ＴＹＰＥ ＤＥＮＳＯＭＥＴＥＲ、膜の面積：６４２ｍｍ２（直径２８．６ｍｍ））により測定することができる。 Air permeability is a measure of the permeability of air through a membrane and can be expressed as the number of seconds it takes for a given volume of air to pass through a given area of a membrane under a given pressure difference using the Gurley test machine method. The air permeability of the separator can be measured with a Gurley densometer (for example, manufactured by Yasuda Seiki Co., Ltd., trade name: No. 323 GURLEY TYPE DENSOMETER, membrane area: 642 mm 2 (diameter 28.6 mm)).
セパレータの透気度の合計が５００～２５００ｓｅｃ／１００ｍＬである場合、当該セパレータのうちの少なくとも一つは、０．１～１５０ｓｅｃ／１００ｍＬの透気度を有することが好ましい。この場合、より優れた高率放電性能及び寿命性能が得られやすい。上記セパレータの透気度は、より優れた寿命性能が得られやすい点で、より好ましくは５．０ｓｅｃ／１００ｍＬ以上であり、更に好ましくは４０ｓｅｃ／１００ｍＬ以上であり、特に好ましくは８０ｓｅｃ／１００ｍＬ以上である。上記セパレータの透気度は、より優れた高率放電性能及び寿命性能が得られやすい点で、より好ましくは１４０ｓｅｃ／１００ｍＬ以下であり、更に好ましくは１３０ｓｅｃ／１００ｍＬ以下であり、特に好ましくは１００ｓｅｃ／１００ｍＬ以下である。 When the total air permeability of the separators is 500 to 2500 sec/100 mL, at least one of the separators preferably has an air permeability of 0.1 to 150 sec/100 mL. In this case, better high rate discharge performance and life performance are likely to be obtained. The air permeability of the separator is more preferably 5.0 sec/100 mL or more, still more preferably 40 sec/100 mL or more, and particularly preferably 80 sec/100 mL or more, since superior life performance can be easily obtained. be. The air permeability of the separator is more preferably 140 sec/100 mL or less, still more preferably 130 sec/100 mL or less, and particularly preferably 100 sec/100 mL or less, from the viewpoint of easily obtaining superior high rate discharge performance and life performance. It is 100 mL or less.
隣り合う正極と負極との間に設けられるセパレータの数は、特に限定されないが、３枚であることが好ましい。３枚のセパレータのうち、正極側に位置するセパレータ及び負極側に位置するセパレータが微多孔膜であり、中間に位置するセパレータが不織布であることが好ましい。３枚のセパレータのうち、中間に位置するセパレータは上述した０．１～１５０ｓｅｃ／１００ｍＬの透気度を有するセパレータであることがより好ましい。この場合、正極側に位置するセパレータ及び負極側に位置するセパレータの透気度は、例えば、５００～１０００ｓｅｃ／１００ｍＬであってよい。 The number of separators provided between adjacent positive and negative electrodes is not particularly limited, but is preferably three. Of the three separators, the separator located on the positive electrode side and the separator located on the negative electrode side are preferably microporous membranes, and the separator located in the middle is preferably a nonwoven fabric. Among the three separators, it is more preferable that the separator located in the middle has an air permeability of 0.1 to 150 sec/100 mL as described above. In this case, the air permeability of the separator located on the positive electrode side and the separator located on the negative electrode side may be, for example, 500 to 1000 sec/100 mL.
以上説明したニッケル亜鉛電池の製造方法は、例えば、亜鉛電池の構成部材を得る構成部材製造工程と、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。構成部材製造工程では、少なくとも電極（正極及び負極）を得る。 The method for manufacturing a nickel-zinc battery described above includes, for example, a component manufacturing step for obtaining the component members of the zinc battery, and an assembly step for assembling the component members to obtain the zinc battery. In the component manufacturing process, at least electrodes (a positive electrode and a negative electrode) are obtained.
電極は、例えば、電極材（正極材及び負極材）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ことにより得ることができる。 For example, electrodes are made by adding a solvent (e.g., water) to raw materials for electrode materials (positive electrode material and negative electrode material) and kneading them to obtain an electrode material paste (paste-like electrode material), and then adding the electrode material paste. It can be obtained by forming an electrode material layer using
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（例えば前記結着剤）等が挙げられる。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（例えば前記結着剤）等が挙げられる。 Examples of raw materials for the positive electrode material include raw materials for the positive electrode active material (for example, nickel hydroxide), additives (for example, the above-mentioned binder), and the like. Examples of raw materials for the negative electrode material include raw materials for the negative electrode active material (for example, metal zinc, zinc oxide, and zinc hydroxide), additives (for example, the above-mentioned 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もよい。 Examples of the method for forming the electrode material layer include a method in which the electrode material layer is obtained by applying or filling an electrode material paste onto a current collector and then drying the current collector. The density of the electrode material layer may be increased by pressing or the like, if necessary.
組立工程では、例えば、構成部材製造工程で得られた正極及び負極を、セパレータを介して交互に積層した後、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する。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（ニッケル亜鉛電池）を得る。 In the assembly process, for example, the positive electrodes and negative electrodes obtained in the component manufacturing process are alternately stacked with separators interposed therebetween, and then the positive electrodes and the negative electrodes are connected with straps to produce an electrode group. Next, after placing this electrode group in a battery case, a lid is adhered to the top surface of the battery case to obtain an unformed zinc battery (nickel-zinc battery).
続いて、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（ニッケル亜鉛電池）を得る。化成条件は、電極活物質（正極活物質及び負極活物質）の性状に応じて調整することができる。 Next, the electrolytic solution is injected into the container of the unformed zinc battery, and then left for a certain period of time. Next, a zinc battery (nickel-zinc battery) is obtained by performing chemical conversion by charging under predetermined conditions. The chemical formation conditions can be adjusted depending on the properties of the electrode active materials (positive electrode active material and negative electrode active material).
以上、正極がニッケル電極であるニッケル亜鉛電池（例えばニッケル亜鉛二次電池）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。 Above, an example of a nickel-zinc battery (for example, a nickel-zinc secondary battery) in which the positive electrode is a nickel electrode has been explained, but a zinc battery is also a zinc-air battery (for example, a zinc-air secondary battery) in which the positive electrode is an air electrode. Alternatively, the battery may be a silver-zinc battery (for example, a silver-zinc secondary battery) in which the positive electrode is a silver oxide electrode.
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 for zinc-air batteries 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もよい。空気極における空気極触媒の使用量は、空気極の合計量に対して、５～７０体積％であってもよく、５～６０体積％であってもよく、５～５０体積％であってもよい。 As the air electrode catalyst, one that functions as a positive electrode in a zinc-air battery can be used, and various air electrode catalysts that can use oxygen as a positive electrode active material can be used. Air electrode catalysts include carbon-based materials with redox catalytic functions (graphite, etc.), metal materials with redox catalytic functions (platinum, nickel, etc.), and inorganic oxide materials with redox catalytic functions (perovskite-type oxides). , 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, particulate. The amount of the air electrode catalyst used in the air electrode may be 5 to 70% by volume, may be 5 to 60% by volume, or may be 5 to 50% by volume, based on the total amount of the air electrode. Good too.
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、粒子状であってもよく、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ることが好ましい。例えば、電子伝導性材料は、多孔質材料であってもよい。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もよく、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使用量は、空気極の合計量に対して、１０～８０体積％であってもよく、１５～８０体積％であってもよく、２０～８０体積％であってもよい。 As the electron conductive material, a material that has conductivity and enables electron conduction between the air electrode catalyst and the separator can be used. Examples of electronically conductive materials include carbon blacks such as Ketjen black, acetylene black, channel black, furnace black, lamp black, and thermal black; graphites such as natural graphite such as flaky graphite, artificial graphite, and expanded graphite; Examples include conductive fibers such as carbon fibers and metal fibers; metal powders such as copper, silver, nickel, and aluminum; organic electronic conductive materials such as polyphenylene derivatives; and arbitrary mixtures thereof. The shape of the electron conductive material may be particulate or other shapes. The electron conductive material is preferably used in a form that provides a continuous phase in the thickness direction in the air electrode. For example, the electronically conductive material may be a porous material. Further, the electron conductive material may be in the form of a mixture or composite with the air electrode catalyst, and as described above, the air electrode catalyst may also function as the electron conductive material. The amount of the electron conductive material used in the air electrode may be 10 to 80% by volume, 15 to 80% by volume, or 20 to 80% by volume based on the total amount of the air electrode. It's okay.
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 electrode for the silver-zinc battery, a known silver oxide electrode used for silver-zinc batteries can be used. The silver oxide electrode contains, for example, silver (I) oxide.
以下、本発明の内容を実験例を用いてより詳細に説明するが、本発明は以下の実験例に限定されるものではない。 Hereinafter, the content of the present invention will be explained in more detail using experimental examples, but the present invention is not limited to the following experimental examples.
［不織布の準備］
以下の不織布１～６を用意した。
・不織布１（ニッポン高度紙工業株式会社製、商品名：ＶＬ－１００、透気度：０．３ｓｅｃ／１００ｍＬ）
・不織布２（王子エフテックス株式会社製、透気度：５．４ｓｅｃ／１００ｍＬ）
・不織布３（大王製紙株式会社製、商品名：竜王耐湿、透気度：４６．６ｓｅｃ／１００ｍＬ）
・不織布４（大王製紙株式会社製、商品名：箔用原紙、透気度：８４．３ｓｅｃ／１００ｍＬ）
・不織布５（大王製紙株式会社製、商品名：金鯱、透気度：１３３．６ｓｅｃ／１００ｍＬ）
・不織布６（大王製紙株式会社製、商品名：竜王耐湿ＳＴ、透気度：１４６．２ｓｅｃ／１００ｍＬ）
[Preparation of nonwoven fabric]
The following nonwoven fabrics 1 to 6 were prepared.
・Nonwoven fabric 1 (manufactured by Nippon Kokoshi Kogyo Co., Ltd., product name: VL-100, air permeability: 0.3 sec/100 mL)
・Nonwoven fabric 2 (manufactured by Oji F-Tex Co., Ltd., air permeability: 5.4sec/100mL)
・Nonwoven fabric 3 (manufactured by Daio Paper Co., Ltd., product name: Ryuo moisture resistant, air permeability: 46.6sec/100mL)
・Nonwoven fabric 4 (manufactured by Daio Paper Co., Ltd., product name: base paper for foil, air permeability: 84.3sec/100mL)
・Non-woven fabric 5 (manufactured by Daio Paper Co., Ltd., product name: Kinshachi, air permeability: 133.6sec/100mL)
・Non-woven fabric 6 (manufactured by Daio Paper Co., Ltd., product name: Ryuo Moisture-resistant ST, air permeability: 146.2sec/100mL)
（実験例１）
［電解液の調製］
イオン交換水に、電解質として、水酸化カリウム（ＫＯＨ）及び水酸化ナトリウム（ＮａＯＨ）を加え、混合することにより電解液（水酸化カリウム濃度：１７．６質量％、水酸化ナトリウム濃度：６．０質量％）を調製した。
(Experiment example 1)
[Preparation of electrolyte]
By adding potassium hydroxide (KOH) and sodium hydroxide (NaOH) as electrolytes to ion-exchanged water and mixing them, an electrolytic solution (potassium hydroxide concentration: 17.6% by mass, sodium hydroxide concentration: 6.0 mass%) was prepared.
［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、ＣＭＣ、ＰＴＦＥ、イオン交換水を所定量秤量して混合し、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：ＣＭＣ：ＰＴＦＥ＝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正極材支持部に塗布した後、８０℃で３０分乾燥した。その後、ロールプレスにて加圧成形し、正極材層を有する未化成の正極を得た。
[Preparation of positive electrode]
A lattice made of nickel foam with a porosity of 95% was prepared, and the lattice was pressure-molded to obtain a positive electrode current collector. Next, predetermined amounts of cobalt-coated nickel hydroxide powder, metallic cobalt, cobalt hydroxide, yttrium oxide, CMC, PTFE, and ion-exchanged water were weighed and mixed, and the mixed solution was stirred to prepare a positive electrode material paste. At this time, the solid content mass ratio was set to "nickel hydroxide: metallic cobalt: yttrium oxide: cobalt hydroxide: CMC: PTFE = 88:10.3:1:0.3:0.3:0.1". It was adjusted. 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. Next, the positive electrode material paste was applied to the positive electrode material supporting portion of the positive electrode current collector, and then dried at 80° C. for 30 minutes. Thereafter, pressure molding was performed using a roll press to obtain an unformed positive electrode having a positive electrode material layer.
［負極の作製］
負極集電体として開孔率６０％のスズメッキを施した鋼板パンチングメタルを用意した。次いで、酸化亜鉛、金属亜鉛、ＨＥＣ及びイオン交換水を所定量秤量して混合し、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＝８５：１１．５：３．５」に調整した。ＨＥＣとしては、住友精化株式会社製のＡＶ－１５Ｆ（商品名）を使用した。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上に塗布した後、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）を有する未化成の負極を得た。
[Preparation of negative electrode]
A steel plate punched metal plated with tin and having a porosity of 60% was prepared as a negative electrode current collector. Next, predetermined amounts of zinc oxide, zinc metal, HEC, and ion-exchanged water were weighed and mixed, and the resulting mixed solution was stirred to prepare a negative electrode material paste. At this time, the mass ratio of the solid content was adjusted to "zinc oxide: zinc metal: HEC = 85:11.5:3.5". As the HEC, AV-15F (trade name) manufactured by Sumitomo Seika Chemical Co., Ltd. was used. 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 onto the negative electrode current collector, and then dried at 80° C. for 30 minutes. Thereafter, it was pressure-molded using a roll press to obtain an unformed negative electrode having a negative electrode material (negative electrode material layer).
＜セパレータの準備＞
セパレータには、微多孔膜として、ＵＰ３３５５（宇部興産社製、商品名、透気度：６３８ｓｅｃ／１００ｍＬ）、不織布として、不織布１を、それぞれ用いた。微多孔膜は、電池組立て前に、界面活性剤Ｔｒｉｔｏｎ－Ｘ１００（ダウケミカル株式会社製）で、親水化処理した。親水化処理は、Ｔｒｉｔｏｎ－Ｘ１００が１質量％の量で含まれる水溶液に微多孔膜を２４時間浸漬した後、室温で１時間乾燥する方法で行った。なお、微多孔膜の透気度は親水化処理後の値を示す。さらに、微多孔膜は、所定の大きさに裁断し、それを半分に折り、側面を熱溶着することで袋状に加工した。袋状に加工した微多孔膜に、正極（未化成の正極）及び負極（未化成の負極）のそれぞれを１枚収納した。不織布は、所定の大きさに裁断したものを使用した。
<Preparation of separator>
For the separator, UP3355 (manufactured by Ube Industries, Ltd., trade name, air permeability: 638 sec/100 mL) was used as a microporous membrane, and nonwoven fabric 1 was used as a nonwoven fabric. The microporous membrane was subjected to hydrophilic treatment using a surfactant Triton-X100 (manufactured by Dow Chemical Co., Ltd.) before battery assembly. The hydrophilization treatment was carried out by immersing the microporous membrane in an aqueous solution containing 1% by mass of Triton-X100 for 24 hours, and then drying it at room temperature for 1 hour. Note that the air permeability of the microporous membrane indicates the value after hydrophilization treatment. Furthermore, the microporous membrane was cut into a predetermined size, folded in half, and processed into a bag by thermally welding the sides. One positive electrode (unformed positive electrode) and one negative electrode (unformed negative electrode) were housed in a bag-shaped microporous membrane. The nonwoven fabric used was one cut to a predetermined size.
＜ニッケル亜鉛電池の作製＞
袋状の微多孔膜に収納された正極と、袋状の微多孔膜に収納された負極と、不織布とを積層した後、同極性の極板同士をストラップで連結させて電極群（極板群）を作製した。電極群は、正極１枚及び負極２枚で、正極と負極の間（正極側の微多孔膜と負極側の微多孔膜との間）に不織布を１枚ずつ配置した構成とした。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して未化成のニッケル亜鉛電池を得た。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、６０ｍＡ、１５時間の条件で充電を行い、公称容量が６００ｍＡｈのニッケル亜鉛電池を作製した。
<Production of nickel-zinc battery>
After laminating a positive electrode housed in a bag-shaped microporous membrane, a negative electrode housed in a bag-shaped microporous membrane, and a nonwoven fabric, the plates of the same polarity are connected with a strap to form an electrode group (electrode plate group) was created. The electrode group consisted of one positive electrode and two negative electrodes, with one nonwoven fabric placed between the positive electrode and the negative electrode (between the microporous membrane on the positive electrode side and the microporous membrane on the negative electrode side). After placing this electrode group in a battery case, a lid was adhered to the top surface of the battery case to obtain an unformed nickel-zinc battery. Next, the electrolytic solution was injected into the container of an unformed nickel-zinc battery, and then left for 24 hours. Thereafter, charging was performed at 60 mA for 15 hours to produce a nickel-zinc battery with a nominal capacity of 600 mAh.
（実験例２～５）
電解液の調製において、電解液の組成（電解質の種類及び濃度）が表１に示す組成となるように、電解質の種類及び使用量を変更したこと以外は、実験例１と同様にして電解液を調製した。こうして得られた電解液を用いたこと以外は実験例１と同様にしてニッケル亜鉛電池を作製した。
(Experiment examples 2 to 5)
In preparing the electrolyte, the electrolyte was prepared in the same manner as in Experimental Example 1, except that the type and amount of electrolyte used were changed so that the composition (type and concentration of electrolyte) was as shown in Table 1. was prepared. A nickel-zinc battery was produced in the same manner as in Experimental Example 1 except that the electrolyte thus obtained was used.
＜電池性能評価１＞
実験例１～５のニッケル亜鉛電池のクーロン効率及び放電性能の評価を行った。
<Battery performance evaluation 1>
The coulombic efficiency and discharge performance of the nickel-zinc batteries of Experimental Examples 1 to 5 were evaluated.
（クーロン効率評価）
ＳＯＣが０％であるニッケル亜鉛電池に対し、４０℃、１．８７Ｖの定電圧で２４時間の充電を行い、充電容量（充電電気量）を測定した。次いで、４０℃、１２０ｍＡ（０．２Ｃ）の定電流で１．１Ｖまでニッケル亜鉛電池の放電を行い、０．２Ｃ時の放電容量を測定した。得られた充電容量及び放電容量より、クーロン効率（放電容量／充電容量×１００）を算出した。クーロン効率が高いほど、副反応が抑制されたと判断することができる。
(Coulombic efficiency evaluation)
A nickel-zinc battery with an SOC of 0% was charged at 40° C. and a constant voltage of 1.87 V for 24 hours, and the charging capacity (charging amount of electricity) was measured. Next, the nickel-zinc battery was discharged to 1.1 V at a constant current of 120 mA (0.2 C) at 40° C., and the discharge capacity at 0.2 C was measured. Coulombic efficiency (discharge capacity/charge capacity x 100) was calculated from the obtained charge capacity and discharge capacity. It can be determined that the higher the Coulombic efficiency, the more suppressed the side reactions are.
前記「Ｃ」とは、満充電状態から定格容量を定電流放電するときの電流の大きさを相対的に表したものである。前記「Ｃ」は、“放電電流値（Ａ）／電池容量（Ａｈ）”を意味する。例えば、定格容量を１時間で放電させることができる電流を「１Ｃ」、２時間で放電させることができる電流を「０．５Ｃ」と表現する。 The above "C" is a relative expression of the magnitude of the current when discharging the rated capacity from a fully charged state at a constant current. The above "C" means "discharge current value (A)/battery capacity (Ah)". For example, a current that can discharge the rated capacity in one hour is expressed as "1C", and a current that can discharge the rated capacity in two hours is expressed as "0.5C".
（放電性能評価）
２５℃、６００ｍＡ（１Ｃ）、１．９Ｖの定電圧で、電流値が３０ｍＡ（０．０５Ｃ）に減衰するま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３０ｍＡ（０．０５Ｃ）及び６０００ｍＡ（１０Ｃ）の定電流でニッケル亜鉛電池の放電を行い、放電容量を測定した。０．０５Ｃ時の放電容量に対する１０Ｃ時の放電容量の割合（放電容量比（％））を算出した。結果を表１に示す。
(Discharge performance evaluation)
Charge the nickel-zinc battery at 25°C, 600mA (1C), and a constant voltage of 1.9V until the current value attenuates to 30mA (0.05C), then charge the nickel-zinc battery at 30mA until the battery voltage reaches 1.1V. The nickel-zinc battery was discharged at a constant current of (0.05 C) and 6000 mA (10 C), and the discharge capacity was measured. The ratio of the discharge capacity at 10C to the discharge capacity at 0.05C (discharge capacity ratio (%)) was calculated. The results are shown in Table 1.
（実験例６）
イオン交換水に、電解質として、水酸化カリウム（ＫＯＨ）及び水酸化リチウム（ＬｉＯＨ）を加え、混合することにより電解液（水酸化カリウム濃度：３０．０質量％、水酸化リチウム濃度：１．０質量％）を調製した。得られた電解液を用いたこと以外は実験例１と同様にしてニッケル亜鉛電池を作製した。
(Experiment example 6)
Potassium hydroxide (KOH) and lithium hydroxide (LiOH) are added as electrolytes to ion-exchanged water and mixed to form an electrolytic solution (potassium hydroxide concentration: 30.0% by mass, lithium hydroxide concentration: 1.0 mass%) was prepared. A nickel-zinc battery was produced in the same manner as in Experimental Example 1 except that the obtained electrolyte was used.
（実験例７～１１）
不織布１に代えて不織布２～６をそれぞれ用いたこと以外は、実験例６と同様にして、ニッケル亜鉛電池を作製した。
(Experiment Examples 7 to 11)
A nickel-zinc battery was produced in the same manner as in Experimental Example 6, except that nonwoven fabrics 2 to 6 were used in place of nonwoven fabric 1.
＜電池性能評価２＞
実験例６～１１のニッケル亜鉛電池のサイクル寿命性能及び放電性能の評価を行った。放電性能の評価は、電池性能評価１と同様にして行った。
<Battery performance evaluation 2>
The cycle life performance and discharge performance of the nickel-zinc batteries of Experimental Examples 6 to 11 were evaluated. The discharge performance was evaluated in the same manner as in Battery Performance Evaluation 1.
（サイクル寿命性能評価）
２５℃、６００ｍＡ（１Ｃ）、１．９Ｖの定電圧で、電流値が３０ｍＡ（０．０５Ｃ）に減衰するま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３００ｍＡ（０．５Ｃ）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。放電容量が１サイクル目の放電容量に対して５０％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サイクル寿命性能を評価した。試験終了までに行ったサイクル数を表２に示す。
(Cycle life performance evaluation)
The nickel-zinc battery was charged at 25°C, 600mA (1C), and a constant voltage of 1.9V until the current value attenuated to 30mA (0.05C), and then at 300mA until the battery voltage reached 1.1V. A test was conducted in which one cycle consisted of discharging a nickel-zinc battery at a constant current of (0.5C). The test was terminated when the discharge capacity was less than 50% of the discharge capacity at the first cycle, and cycle life performance was evaluated based on the number of cycles performed until the end of the test. Table 2 shows the number of cycles performed until the end of the test.
Claims (4)
前記一又は複数のセパレータを介して隣り合う正極及び負極と、を更に備える、請求項２に記載の亜鉛電池。 one or more separators having a total air permeability of 500 to 2500 sec/100 mL;
The zinc battery according to claim 2, further comprising a positive electrode and a negative electrode adjacent to each other with the one or more separators interposed therebetween.
The zinc battery according to claim 3, wherein at least one of the one or more separators has an air permeability of 0.1 to 150 sec/100 mL.
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