JP2005243462A - ニッケル水素蓄電池用セパレータ及び該セパレータを用いたニッケル水素蓄電池 - Google Patents
ニッケル水素蓄電池用セパレータ及び該セパレータを用いたニッケル水素蓄電池 Download PDFInfo
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- JP2005243462A JP2005243462A JP2004052358A JP2004052358A JP2005243462A JP 2005243462 A JP2005243462 A JP 2005243462A JP 2004052358 A JP2004052358 A JP 2004052358A JP 2004052358 A JP2004052358 A JP 2004052358A JP 2005243462 A JP2005243462 A JP 2005243462A
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- Prior art keywords
- separator
- storage battery
- nickel
- ammonia
- metal hydride
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 238000003860 storage Methods 0.000 title claims abstract description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 27
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title abstract description 20
- 239000001257 hydrogen Substances 0.000 title abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 title abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 67
- -1 nitrate ions Chemical class 0.000 claims abstract description 61
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 35
- 229920000098 polyolefin Polymers 0.000 claims abstract description 29
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 25
- 239000003792 electrolyte Substances 0.000 claims abstract description 13
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 13
- 229910052987 metal hydride Inorganic materials 0.000 claims description 38
- 239000008151 electrolyte solution Substances 0.000 claims description 11
- 230000002829 reductive effect Effects 0.000 claims description 10
- 229910000652 nickel hydride Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 abstract description 15
- 230000000052 comparative effect Effects 0.000 description 14
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 14
- 239000007788 liquid Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000001994 activation Methods 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 7
- 235000010333 potassium nitrate Nutrition 0.000 description 7
- 239000004323 potassium nitrate Substances 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 239000000835 fiber Substances 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000009825 accumulation Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- 125000001174 sulfone group Chemical group 0.000 description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- 229920002125 Sokalan® Polymers 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- 229910018007 MmNi Inorganic materials 0.000 description 1
- IOVCWXUNBOPUCH-UHFFFAOYSA-N Nitrous acid Chemical class ON=O IOVCWXUNBOPUCH-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- CVTZKFWZDBJAHE-UHFFFAOYSA-N [N].N Chemical compound [N].N CVTZKFWZDBJAHE-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- PRORZGWHZXZQMV-UHFFFAOYSA-N azane;nitric acid Chemical compound N.O[N+]([O-])=O PRORZGWHZXZQMV-UHFFFAOYSA-N 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229940005654 nitrite ion Drugs 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
Landscapes
- Cell Separators (AREA)
- Secondary Cells (AREA)
Abstract
【解決手段】スルホン化処理ポリオレフィンセパレータを使用したニッケル水素蓄電池において、前記セパレータにアンモニアが結合しており、かつ、前記セパレータ中のアンモニア含有量がセパレータ1g当たり窒素量換算で600μg以上であるスルホン化セパレータを用いる。この場合、組立時に電解液中に硝酸化合物又は亜硝酸化合物を含有させることにより、自己放電により硝酸イオン又は亜硝酸イオンをアンモニアに変えてスルホン化処理ポリオレフィンセパレータに捕捉させることもできる。
【選択図】なし
Description
陰極
NO3 −+MHX → MHX−2+ NO2 − +H2O (1)
NO2 −+MHX → MHX−6+ NH4OH + OH− (2)
又は、
NO2 −+MHX → MHX−6 + NH3+ H2O + OH− (2’)
電解液
NH4OH ←→ NH3+ H2O (3)
陽極
NH3+6NiOOH+H2O+OH−→6Ni(OH)2+ NO2 − (4)
NO2 −+2NiOOH+H2O →2Ni(OH)2+ NO3 − (5)
硝酸イオン ←→ 亜硝酸イオン ←→ アンモニア
と酸化還元反応を繰り返すために起こる、いわゆるシャトル効果を利用するものである。
600μg≦MA≦MB
を満足する量であることを特徴とする。
<ニッケル水素蓄電池の製造工程>
正極としては硝酸コバルトと硝酸亜鉛とを加えた硝酸ニッケル水溶液を、多孔度85%のニッケル焼結基板に化学含浸法により含浸させて作製した焼結式ニッケル極を使用した。また、組成式MmNi3.2Co1.0Al0.2Mn0.6(Mm:ミッシュメタル)で表される平均粒径50μmになった水素吸蔵合金粉末100質量部に対して、結着剤としてポリエチレンオキシドを1.0質量部加えると共に、これらを混合してペーストを調製し、このペーストをニッケルメッキしたパンチングメタルの両面に均一に塗布し、これを乾燥させた後、圧延して水素吸蔵合金電極を作製し、負極とした。
上記のようにして作製したニッケル水素蓄電池を、25℃にて600mAで16時間充電した後、60℃にて24時間放置し、25℃にて600mAで1.0Vまで放電する充放電活性化工程を2サイクル行った電池を比較例1の電池とした。また、上記サイクルを5サイクル行った電池を比較例2の電池とした。
次に、組立時に水酸化カリウム電解液中に硝酸カリウムを10mg(実施例5)、20mg(実施例6)、30mg(実施例7)、50mg(実施例8)、70mg(実施例9)及び90mg(実施例10)添加した以外は比較例1と同様にしてニッケル水素蓄電池を作製した。この実施例5〜10のニッケル水素蓄電池について、前記実施例1〜実施例4及び比較例1〜2の場合と同様にしてセパレータ中の窒素量及び含液量を調べ、含液量については比較例2の電池の場合を100%として相対値を求めた。
Claims (5)
- スルホン化処理ポリオレフィンセパレータにアンモニアが結合しており、かつ、前記セパレータ中のアンモニア含有量がセパレータ1g当たり窒素量換算で600μg以上であることを特徴とするニッケル水素蓄電池用スルホン化処理ポリオレフィンセパレータ。
- スルホン化処理ポリオレフィンセパレータを使用したニッケル水素蓄電池において、前記セパレータにアンモニアが結合しており、かつ、前記セパレータ中のアンモニア含有量がセパレータ1g当たり窒素量換算で600μg以上であることを特徴とするスルホン化セパレータを用いたニッケル水素蓄電池。
- 電解液中に硝酸化合物又は亜硝酸化合物を含有させたことを特徴とする請求項2に記載のニッケル水素蓄電池。
- 前記電解液中に含有させた硝酸化合物又は亜硝酸化合物含有量が、負極でアンモニア化合物に還元されてセパレータに捕捉されるアンモニア量をセパレータ1g当たり窒素量換算でMA、前記セパレータが捕捉し得るアンモニア化合物量をセパレータ1g当たり窒素量換算でMBとしたとき、
600μg≦MA≦MB
を満足する量であることを特徴とする請求項3に記載のニッケル水素蓄電池。 - 前記硝酸化合物又は亜硝酸化合物は、Li、K、Naの少なくとも1種の塩であることを特徴とする請求項3又は4に記載のニッケル水素蓄電池。
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JP2004052358A JP4919584B2 (ja) | 2004-02-26 | 2004-02-26 | ニッケル水素蓄電池 |
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JP2004052358A JP4919584B2 (ja) | 2004-02-26 | 2004-02-26 | ニッケル水素蓄電池 |
Publications (2)
Publication Number | Publication Date |
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JP2005243462A true JP2005243462A (ja) | 2005-09-08 |
JP4919584B2 JP4919584B2 (ja) | 2012-04-18 |
Family
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JP2004052358A Expired - Lifetime JP4919584B2 (ja) | 2004-02-26 | 2004-02-26 | ニッケル水素蓄電池 |
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JP (1) | JP4919584B2 (ja) |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000123814A (ja) * | 1998-10-09 | 2000-04-28 | Toyobo Co Ltd | アルカリ電池用セパレータ及びその製造方法 |
JP2000294217A (ja) * | 1999-04-02 | 2000-10-20 | Toyobo Co Ltd | アルカリ電池用セパレータ |
JP2002260721A (ja) * | 2001-03-06 | 2002-09-13 | Toshiba Battery Co Ltd | ニッケル・水素二次電池 |
JP2003151523A (ja) * | 2001-06-04 | 2003-05-23 | Komatsu Seiren Co Ltd | 電池用セパレータ及びその製造方法 |
JP2003151524A (ja) * | 2001-11-12 | 2003-05-23 | Sekisui Chem Co Ltd | アルカリ電解質型二次電池用セパレーター、その製造方法及びそれを用いたアルカリ電解質型二次電池 |
-
2004
- 2004-02-26 JP JP2004052358A patent/JP4919584B2/ja not_active Expired - Lifetime
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000123814A (ja) * | 1998-10-09 | 2000-04-28 | Toyobo Co Ltd | アルカリ電池用セパレータ及びその製造方法 |
JP2000294217A (ja) * | 1999-04-02 | 2000-10-20 | Toyobo Co Ltd | アルカリ電池用セパレータ |
JP2002260721A (ja) * | 2001-03-06 | 2002-09-13 | Toshiba Battery Co Ltd | ニッケル・水素二次電池 |
JP2003151523A (ja) * | 2001-06-04 | 2003-05-23 | Komatsu Seiren Co Ltd | 電池用セパレータ及びその製造方法 |
JP2003151524A (ja) * | 2001-11-12 | 2003-05-23 | Sekisui Chem Co Ltd | アルカリ電解質型二次電池用セパレーター、その製造方法及びそれを用いたアルカリ電解質型二次電池 |
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