JP2021185559A - 亜鉛電池用負極及び亜鉛電池 - Google Patents
亜鉛電池用負極及び亜鉛電池 Download PDFInfo
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- JP2021185559A JP2021185559A JP2020090383A JP2020090383A JP2021185559A JP 2021185559 A JP2021185559 A JP 2021185559A JP 2020090383 A JP2020090383 A JP 2020090383A JP 2020090383 A JP2020090383 A JP 2020090383A JP 2021185559 A JP2021185559 A JP 2021185559A
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- Prior art keywords
- negative electrode
- zinc
- zinc battery
- mass
- positive electrode
- Prior art date
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- 239000011701 zinc Substances 0.000 title claims abstract description 76
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 72
- 239000007773 negative electrode material Substances 0.000 claims abstract description 53
- 229910052751 metal Inorganic materials 0.000 claims abstract description 44
- 239000002184 metal Substances 0.000 claims abstract description 44
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 22
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 claims description 8
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- VDZMENNHPJNJPP-UHFFFAOYSA-N boranylidyneniobium Chemical compound [Nb]#B VDZMENNHPJNJPP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 description 30
- 239000000463 material Substances 0.000 description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 22
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 16
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 15
- 239000008151 electrolyte solution Substances 0.000 description 15
- 238000000034 method Methods 0.000 description 15
- 239000003054 catalyst Substances 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 12
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- 239000000126 substance Substances 0.000 description 11
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- 239000007772 electrode material Substances 0.000 description 9
- 239000011230 binding agent Substances 0.000 description 8
- 208000028659 discharge Diseases 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
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- 238000007086 side reaction Methods 0.000 description 4
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- 239000002904 solvent Substances 0.000 description 4
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- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
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- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
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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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
Description
(正極)2NiOOH+2H2O+2e− → 2Ni(OH)2+2OH−
(負極)Zn+2OH− → Zn(OH)2+2e−
(実施例1)
負極集電体として、スズめっきを施した銅板パンチングメタル(開孔率:55体積%)を用意した。
次いで、酸化亜鉛(ZnO)、金属亜鉛(Zn)、二ホウ化チタン(TiB2)、及び、ヒドロキシエチルセルロース(HEC、住友精化株式会社製、商品名:AV−15F)を所定量秤量した。これらの成分をイオン交換水と混合することにより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。各成分の質量比(固形分)は「酸化亜鉛:金属亜鉛:二ホウ化チタン:HEC=80:11.5:5:3.5」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。
続いて、負極材ペーストを負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することにより、負極材(負極材層)を有する未化成の負極を得た。
二ホウ化チタンを二ホウ化ジルコニウム(ZrB2)に変更したこと以外は実施例1と同様にして負極を得た。
二ホウ化チタンを二ホウ化ニオブ(NbB2)に変更したこと以外は実施例1と同様にして負極を得た。
二ホウ化チタンを三酸化ビスマス(Bi2O3)に変更したこと以外は実施例1と同様にして負極を得た。
二ホウ化チタンを三酸化インジウム(In2O3)に変更したこと以外は実施例1と同様にして負極を得た。
発泡ニッケル(気孔率:95体積%)からなる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(CMC)、ポリテトラフルオロエチレン(PTFE)、及び、イオン交換水を所定量秤量した。これらの各成分を混合し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。各成分の質量比(固形分)は「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。
続いて、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することにより、正極材(正極材層)を有する未化成の正極を得た。
イオン交換水に水酸化カリウム(KOH)及び水酸化リチウム(LiOH)を混合することにより電解液(水酸化カリウム濃度:30質量%、水酸化リチウム濃度:1質量%)を調製した。
セパレータとして、微多孔膜であるCelgard2500(POLYPORE International,Inc.製)、不織布であるVL100(ニッポン高度紙工業製)を準備した。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、25℃で1時間乾燥する方法で行った。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。袋状の微多孔膜に正極(未化成の正極)を1枚収納し、同様に、袋状の微多孔膜に負極(未化成の負極)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。
袋状の微多孔膜にそれぞれ収納された2枚の上述の正極と、袋状の微多孔膜にそれぞれ収納された3枚の上述の負極とを交互に積層し、上述の不織布を正極と負極との間に挟み、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。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、25mA、15時間の条件で充電を行い、公称容量が320mAhのニッケル亜鉛電池を作製した。
25℃、320mA(1C)、1.9Vの定電圧で、電流値が16mA(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1280mA(4C)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80%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は、実施例1において112回であり、実施例2において104回であり、実施例3において95回であり、比較例1において78回であり、比較例2において82回であった。
Claims (6)
- 負極集電体と、当該負極集電体に支持された負極材と、を有し、
前記負極材が、亜鉛を含む負極活物質と、金属ホウ化物と、を含有する、亜鉛電池用負極。 - 前記金属ホウ化物が、ホウ化チタン、ホウ化ジルコニウム及びホウ化ニオブからなる群より選ばれる少なくとも一種を含む、請求項1に記載の亜鉛電池用負極。
- 前記金属ホウ化物における化学式MxBy(M:金属元素、B:ホウ素)のy/xが2である、請求項1又は2に記載の亜鉛電池用負極。
- 前記金属ホウ化物の含有量が、前記負極活物質100質量部に対して0.5〜10質量部である、請求項1〜3のいずれか一項に記載の亜鉛電池用負極。
- 請求項1〜4のいずれか一項に記載の亜鉛電池用負極と、正極と、を備える、亜鉛電池。
- ニッケル亜鉛電池である、請求項5に記載の亜鉛電池。
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