JP7307961B2 - アルカリ性および中性の塩水分解用の高度に持続性の電極および電解液 - Google Patents
アルカリ性および中性の塩水分解用の高度に持続性の電極および電解液 Download PDFInfo
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- JP7307961B2 JP7307961B2 JP2020543057A JP2020543057A JP7307961B2 JP 7307961 B2 JP7307961 B2 JP 7307961B2 JP 2020543057 A JP2020543057 A JP 2020543057A JP 2020543057 A JP2020543057 A JP 2020543057A JP 7307961 B2 JP7307961 B2 JP 7307961B2
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- nickel
- foam
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- 239000003792 electrolyte Substances 0.000 title description 107
- 230000007935 neutral effect Effects 0.000 title description 14
- 230000002085 persistent effect Effects 0.000 title description 3
- 239000012267 brine Substances 0.000 title description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 title description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 306
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 173
- 150000001450 anions Chemical class 0.000 claims description 127
- 239000010411 electrocatalyst Substances 0.000 claims description 112
- 239000011780 sodium chloride Substances 0.000 claims description 86
- 239000013535 sea water Substances 0.000 claims description 77
- 239000002184 metal Substances 0.000 claims description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 60
- 229910052751 metal Inorganic materials 0.000 claims description 59
- 239000000758 substrate Substances 0.000 claims description 57
- 238000002161 passivation Methods 0.000 claims description 55
- 238000000034 method Methods 0.000 claims description 53
- 238000005868 electrolysis reaction Methods 0.000 claims description 42
- 229910052759 nickel Inorganic materials 0.000 claims description 42
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 40
- 239000011248 coating agent Substances 0.000 claims description 40
- 238000000576 coating method Methods 0.000 claims description 40
- 239000001301 oxygen Substances 0.000 claims description 40
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- 238000006243 chemical reaction Methods 0.000 claims description 33
- 125000000129 anionic group Chemical group 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 26
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 20
- 239000011888 foil Substances 0.000 claims description 13
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 12
- 229910000000 metal hydroxide Inorganic materials 0.000 claims description 12
- 150000004692 metal hydroxides Chemical class 0.000 claims description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 10
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
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- 239000011593 sulfur Substances 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 7
- 239000011574 phosphorus Substances 0.000 claims description 7
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- FRWHRIRADSHXLL-UHFFFAOYSA-N iron(3+);nickel(2+);tetrasulfide Chemical compound [S-2].[S-2].[S-2].[S-2].[Fe+3].[Ni+2].[Ni+2].[Ni+2].[Ni+2] FRWHRIRADSHXLL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 claims description 3
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims description 3
- 150000003841 chloride salts Chemical class 0.000 claims 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 306
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- 230000004913 activation Effects 0.000 description 9
- 238000002048 anodisation reaction Methods 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 150000001805 chlorine compounds Chemical class 0.000 description 9
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 9
- 239000011736 potassium bicarbonate Substances 0.000 description 9
- 235000015497 potassium bicarbonate Nutrition 0.000 description 9
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 9
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 8
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- KGWWEXORQXHJJQ-UHFFFAOYSA-N [Fe].[Co].[Ni] Chemical compound [Fe].[Co].[Ni] KGWWEXORQXHJJQ-UHFFFAOYSA-N 0.000 description 8
- JYYOBHFYCIDXHH-UHFFFAOYSA-N carbonic acid;hydrate Chemical compound O.OC(O)=O JYYOBHFYCIDXHH-UHFFFAOYSA-N 0.000 description 8
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 7
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- 229910052799 carbon Inorganic materials 0.000 description 7
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 7
- 235000015320 potassium carbonate Nutrition 0.000 description 7
- 229910000027 potassium carbonate Inorganic materials 0.000 description 7
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 7
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- YGHCWPXPAHSSNA-UHFFFAOYSA-N nickel subsulfide Chemical compound [Ni].[Ni]=S.[Ni]=S YGHCWPXPAHSSNA-UHFFFAOYSA-N 0.000 description 6
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- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 229910052795 boron group element Inorganic materials 0.000 description 1
- 238000004177 carbon cycle Methods 0.000 description 1
- 229910052800 carbon group element Inorganic materials 0.000 description 1
- 125000005587 carbonate group Chemical group 0.000 description 1
- NMGSERJNPJZFFC-UHFFFAOYSA-N carbonic acid;sulfuric acid Chemical class OC(O)=O.OS(O)(=O)=O NMGSERJNPJZFFC-UHFFFAOYSA-N 0.000 description 1
- NKCVNYJQLIWBHK-UHFFFAOYSA-N carbonodiperoxoic acid Chemical compound OOC(=O)OO NKCVNYJQLIWBHK-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 159000000006 cesium salts Chemical class 0.000 description 1
- PBAYDYUZOSNJGU-UHFFFAOYSA-N chelidonic acid Natural products OC(=O)C1=CC(=O)C=C(C(O)=O)O1 PBAYDYUZOSNJGU-UHFFFAOYSA-N 0.000 description 1
- 231100000481 chemical toxicant Toxicity 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000003843 chloralkali process Methods 0.000 description 1
- 239000000788 chromium alloy Substances 0.000 description 1
- OLFCLHDBKGQITG-UHFFFAOYSA-N chromium(3+) nickel(2+) oxygen(2-) Chemical compound [Ni+2].[O-2].[Cr+3] OLFCLHDBKGQITG-UHFFFAOYSA-N 0.000 description 1
- MYRJPMMFCARPLB-UHFFFAOYSA-K cobalt(2+);iron(2+);carbonate;hydroxide Chemical compound [OH-].[Fe+2].[Co+2].[O-]C([O-])=O MYRJPMMFCARPLB-UHFFFAOYSA-K 0.000 description 1
- HSQIWKNMXNBSTL-UHFFFAOYSA-J cobalt(2+);iron(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Co+2] HSQIWKNMXNBSTL-UHFFFAOYSA-J 0.000 description 1
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 description 1
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- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
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- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
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- 230000000977 initiatory effect Effects 0.000 description 1
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- 230000037431 insertion Effects 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- LHSUWQLPGKNVCP-UHFFFAOYSA-K manganese(2+);nickel(2+);carbonate;hydroxide Chemical compound [OH-].[Mn+2].[Ni+2].[O-]C([O-])=O LHSUWQLPGKNVCP-UHFFFAOYSA-K 0.000 description 1
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
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- 229910001120 nichrome Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- BBTOTXQDQDXXHB-UHFFFAOYSA-L nickel(2+) carbonate dihydrate Chemical class [OH-].[OH-].[Ni++].OC(O)=O BBTOTXQDQDXXHB-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000623 nickel–chromium alloy Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010606 normalization Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000002459 porosimetry Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000008213 purified water Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000008261 resistance mechanism Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 239000011833 salt mixture Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 238000000859 sublimation Methods 0.000 description 1
- 230000008022 sublimation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 238000005987 sulfurization reaction Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 230000005469 synchrotron radiation Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 238000002525 ultrasonication Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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Description
本願は、2018年2月14日付で出願された米国仮出願第62/630,599号の利益を主張し、その内容は参照によりその全文が本明細書に組み込まれる。
この発明は、米国エネルギー省から授与された契約DE-SC0016165に基づく政府の支援を受けて行われた。政府は本発明に一定の権利を有する。
水素燃料を生成するための水の電気分解は、魅力的な再生可能エネルギー貯蔵ソリューションである。しかし、グリッドスケールの淡水の電気分解は、重要な水資源に大きな負担をかけることになる。塩化物腐食なく海水分解を維持することができる安価な電解触媒、電極、および電解液を開発することにより、水不足の問題に対処することができる。
一部の実施形態では、塩化物を含む水中での酸素発生反応用の耐食性アノードが提供され、それには、(1)基層(substrate);(2)基層をコーティングするパッシベーション層;および(3)パッシベーション層をコーティングする電解触媒層が含まれ、該パッシベーション層は、少なくとも1つの金属の硫化物を含む。
本開示の実施形態は、実用的な電流密度および温度、例えば工業用水の電気分解で使用される条件下などで、塩化物アニオンを除去せずに、塩水を酸素と水素に直接変換するように動作することができる電気化学セルに関する。本開示の実施形態は、高度に持続的な水分解のための、電極、電解質、およびそれらの製造方法を含む、そのような電気化学セルの構成要素にも関する。
実施例1
高度に持続性でエネルギー効率の良い海水分解
2H2O(l)→O2(g)+4H+(aq)+4e- NHEに対してE0=1.23V-0.059*pH(1)
2Cl-(aq)→Cl2(g)+2e- NHEに対してE0=1.36V、pH非依存性(2)
Cl-(aq)+2OH-(aq)→OCl-(aq)+2e- NHEに対してE0=1.72V-0.059*pH(3)
4OH-(aq)→O2(g)+2H2O(l)+4e- NHEに対してE0=1.23V-0.059*pH(4)
Cl-(aq)+ClO-(aq)+H2O(l)→Cl2(g)+2OH-(aq)(5)
実施例2
塩分の多いアルカリ性および中性の水分解用の高度に持続性のアノードおよび電解液
例えば、本発明は、以下の項目を提供する。
(項目1)
塩化物を含む水中での酸素発生反応のためのアノードであって、
基層と;
前記基層をコーティングするパッシベーション層と;
前記パッシベーション層をコーティングする電解触媒層とを備え、
前記パッシベーション層は、少なくとも1つの金属の硫化物を含む、アノード。
(項目2)
前記パッシベーション層が、硫化ニッケルまたはニッケル鉄硫化物を含む、項目1に記載のアノード。
(項目3)
前記パッシベーション層と前記電解触媒層との間に配置されたアニオン層をさらに含む、項目2に記載のアノード。
(項目4)
前記アニオン層が硫黄のアニオン性酸化物を含む、項目3に記載のアノード。
(項目5)
塩化物を含む水中での酸素発生反応のためのアノードであって、
基層と;
前記基層をコーティングするパッシベーション層と;
前記パッシベーション層をコーティングする電解触媒層とを備え、
前記パッシベーション層は、少なくとも1つの金属のリン化物を含む、アノード。
(項目6)
前記パッシベーション層が、リン化ニッケルまたはニッケル鉄リン化物を含む、項目5に記載のアノード。
(項目7)
前記パッシベーション層と前記電解触媒層との間に配置されたアニオン層をさらに含む、項目6に記載のアノード。
(項目8)
前記アニオン層がリンのアニオン性酸化物を含む、項目7に記載のアノード。
(項目9)
塩化物を含む水中での酸素発生反応のためのアノードであって、
基層と;
前記基層をコーティングする電解触媒層と;
前記基層と前記電解触媒層との間に配置されたアニオン層とを備える、アノード。
(項目10)
前記アニオン層が、炭酸塩、硫酸塩、リン酸塩、またはそれらの2またはそれを超える組み合わせを含む多原子アニオンを含む、項目9に記載のアノード。
(項目11)
前記多原子アニオンが、硫黄のアニオン性酸化物を含む、項目10に記載のアノード。
(項目12)
前記多原子アニオンが、リンのアニオン性酸化物を含む、項目10に記載のアノード。
(項目13)
前記多原子アニオンが、炭酸塩;モリブデン、タングステン、バナジウム、クロム、ホウ素、または炭素のアニオン性酸化物;あるいはそれらの組合せを含む、項目10に記載のアノード。
(項目14)
前記電解触媒層が、金属水酸化物、混合金属水酸化物、金属層状複水酸化物、混合金属層状複水酸化物、金属酸化物、または混合金属酸化物を含む、項目1、5、および9のいずれか一項に記載のアノード。
(項目15)
塩化物を含む水中での酸素発生反応のためのアノードであって、
基層と;
前記基層をコーティングする電解触媒層とを含み、
前記電解触媒層がアニオンを含む、アノード。
(項目16)
前記アニオンが、前記電解触媒層内、および前記電解触媒層と前記基層との間の界面に挿入されている、項目15に記載のアノード。
(項目17)
前記電解触媒層が、アニオンもしくは混合アニオンを挿入した金属水酸化物、アニオンもしくは混合アニオンを挿入した混合金属水酸化物、アニオンもしくは混合アニオンを挿入した金属層状複水酸化物、アニオンもしくは混合アニオンを挿入した混合金属層状複水酸化物、アニオンもしくは混合アニオンを挿入した金属酸化物、あるいは、アニオンもしくは混合アニオンを挿入した混合金属酸化物を含む、項目16に記載のアノード。
(項目18)
前記アニオンが、炭酸塩、硫酸塩、リン酸塩、またはそれらの2またはそれを超える組み合わせを含む多原子アニオンを含む、項目15に記載のアノード。
(項目19)
前記多原子アニオンが、硫黄、リン、または炭素のアニオン性酸化物を含む、項目18に記載のアノード。
(項目20)
前記基層が、金属のフォーム、箔、またはメッシュである、項目1、5、9および15のいずれか一項に記載のアノード。
(項目21)
前記基層が、ニッケルを含む、項目1、5、9および15のいずれか一項に記載のアノード。
(項目22)
項目1、5、9および15のいずれか一項に記載の前記アノードを含む、水電解槽。
(項目23)
塩化ナトリウムを含む水から酸素と水素を生成することを含む、項目22に記載の前記水電解槽を操作する方法。
(項目24)
前記水が、pHが7を超えるアルカリ性の海水である、項目23に記載の方法。
(項目25)
電解液から酸素と水素を生成することを含む、水電解槽を操作する方法であって、前記電解液が、アルカリ性に調整した海水と、前記アルカリ性に調整した海水中に分散し、沈殿したアルカリ土類イオンおよび重金属イオンを濾過で除去した多原子アニオンとを含み、前記電解液中の前記多原子アニオンの濃度が0.05M~8Mの範囲である、方法。
(項目26)
前記多原子アニオンが、CO 3 2- 、HCO 3 - 、SO 4 2- 、SO 3 2- 、PO 4 3- 、H 2 PO 4 - 、HPO 4 2- 、あるいはそれらの2またはそれを超える組合せを含む、項目25に記載の方法。
(項目27)
前記多原子アニオンの前記濃度が、0.05M~2Mである、項目25に記載の方法。
(項目28)
酸素発生反応用のアノードを製造する方法であって、
基層を提供するステップと;
前記基層をコーティングするパッシベーション層を形成するステップと;
前記パッシベーション層をコーティングする電解触媒層を形成するステップであって、それにより前記基層、前記パッシベーション層、および前記電解触媒層を含む前記アノードを形成するステップとを含む方法。
(項目29)
電流を前記基層に印加して、前記パッシベーション層と前記電解触媒層との間に配置されたアニオン層を形成することをさらに含む、項目28に記載の方法。
(項目30)
酸素発生反応用のアノードを製造する方法であって、
遷移金属を含む基層を提供するステップと;
前記基層をコーティングする電解触媒層を形成するステップと;
電流を前記基層に印加して、前記基層と前記電解触媒層との間に配置されたアニオン層を形成するステップであって、前記アニオン層が前記遷移金属のアニオン性酸化物を含むステップとを含む、方法。
(項目31)
酸素発生反応用のアノードを製造する方法であって、
基層を提供するステップと;
前記基層をコーティングする電解触媒層を形成し、それにより前記基層および前記電解触媒層を含む前記アノードを形成するステップとを含み、
前記電解触媒層を形成するステップが、アニオンを含む電解液溶液の存在下であり、前記アニオンが前記電解触媒層内に組み込まれている、方法。
(項目32)
前記アニオンが、硫酸塩、リン酸塩、炭酸塩、またはそれらの2またはそれを超える組み合わせを含む、項目31に記載の方法。
(項目33)
前記電解触媒層を形成するステップが、前記電解液溶液の存在下で前記基層を陽極酸化処理することによって実施される、項目31に記載の方法。
(項目34)
前記基層が遷移金属を含み、前記電解触媒層を形成するステップが、アニオンを挿入した遷移金属水酸化物またはアニオンを挿入した遷移金属層状複水酸化物を形成することを含む、項目31に記載の方法。
(項目35)
酸素発生反応用のアノードを製造する方法であって、
基層を提供するステップと;
前記基層をコーティングする前駆体層を形成するステップと;
前記前駆体層から、前記基層をコーティングする電解触媒層を形成し、それにより前記基層および前記電解触媒層を含む前記アノードを形成するステップとを含み、
前記電解触媒層を形成するステップが、アニオンを含む電解液溶液の存在下であり、前記アニオンが前記電解触媒層内に組み込まれている、方法。
(項目36)
前記基層が、第1の金属を含み、前記前駆体層を形成するステップが、前記第1の金属とは異なる少なくとも1つの第2の金属を含む前駆体溶液に前記基層を曝すことを含む、項目35に記載の方法。
(項目37)
前記第1の金属がニッケルであり、前記第2の金属が鉄、マンガン、クロム、またはコバルトである、項目36に記載の方法。
(項目38)
前記前駆体層が、前記第1の金属と前記第2の金属の混合金属カチオン層である、項目36に記載の方法。
(項目39)
前記アニオンが、硫酸塩、リン酸塩、炭酸塩、またはそれらの2またはそれを超える組み合わせを含む、項目35に記載の方法。
(項目40)
前記電解触媒層を形成するステップが、前記電解液溶液の存在下で前記基層を陽極酸化処理することによって実施される、項目35に記載の方法。
(項目41)
酸素発生反応用のアノードを製造する方法であって、
基層を提供するステップと;
電解触媒粒子を前記基層に付着させるステップとを含み、
前記電解触媒粒子が多原子アニオンを含む、方法。
(項目42)
前記電解触媒粒子が、多原子アニオンを挿入した金属水酸化物、多原子アニオンを挿入した混合金属水酸化物、多原子アニオンを挿入した金属層状複水酸化物、または多原子アニオンを挿入した混合金属層状複水酸化物を含む、項目41に記載の方法。
Claims (14)
- 塩化物を含む水中での酸素発生反応のためのアノードであって、
基層と;
前記基層をコーティングするパッシベーション層と;
前記パッシベーション層をコーティングする電解触媒層とを備え、
前記パッシベーション層は、少なくとも1つの金属の硫化物を含む、アノード。 - 前記パッシベーション層が、硫化ニッケルまたはニッケル鉄硫化物を含む、請求項1に記載のアノード。
- 前記パッシベーション層と前記電解触媒層との間に配置されたアニオン層をさらに含む、請求項2に記載のアノード。
- 前記アニオン層が硫黄のアニオン性酸化物を含む、請求項3に記載のアノード。
- 塩化物を含む水中での酸素発生反応のためのアノードであって、
基層と;
前記基層をコーティングするパッシベーション層と;
前記パッシベーション層をコーティングする電解触媒層とを備え、
前記パッシベーション層は、少なくとも1つの金属のリン化物を含む、アノード。 - 前記パッシベーション層が、リン化ニッケルまたはニッケル鉄リン化物を含む、請求項5に記載のアノード。
- 前記パッシベーション層と前記電解触媒層との間に配置されたアニオン層をさらに含む、請求項6に記載のアノード。
- 前記アニオン層がリンのアニオン性酸化物を含む、請求項7に記載のアノード。
- 前記電解触媒層が、金属水酸化物、混合金属水酸化物、金属層状複水酸化物、混合金属層状複水酸化物、金属酸化物、または混合金属酸化物を含む、請求項1または5に記載のアノード。
- 前記基層が、金属のフォーム、箔、またはメッシュである、請求項1または5に記載のアノード。
- 前記基層が、ニッケルを含む、請求項1または5に記載のアノード。
- 請求項1または5に記載の前記アノードを含む、水電解槽。
- 塩化ナトリウムを含む水から酸素と水素を生成することを含む、請求項12に記載の前記水電解槽を操作する方法。
- 前記水が、pHが7を超えるアルカリ性の海水である、請求項13に記載の方法。
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JP2019507240A (ja) | 2015-12-23 | 2019-03-14 | レプソル,エス.エー. | 基板−電極(se)界面照射型光電極および光電気化学電池 |
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