JP5739831B2 - 空気電池用材料及びこれを用いた全固体空気電池 - Google Patents
空気電池用材料及びこれを用いた全固体空気電池 Download PDFInfo
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- JP5739831B2 JP5739831B2 JP2012082837A JP2012082837A JP5739831B2 JP 5739831 B2 JP5739831 B2 JP 5739831B2 JP 2012082837 A JP2012082837 A JP 2012082837A JP 2012082837 A JP2012082837 A JP 2012082837A JP 5739831 B2 JP5739831 B2 JP 5739831B2
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- oxide
- air battery
- hydroxide
- iron
- electrolyte
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- 239000000463 material Substances 0.000 title claims description 32
- 239000007787 solid Substances 0.000 title 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 78
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 34
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 32
- 239000002245 particle Substances 0.000 claims description 26
- 239000007784 solid electrolyte Substances 0.000 claims description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 239000004020 conductor Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 7
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 31
- 239000003792 electrolyte Substances 0.000 description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 229910052742 iron Inorganic materials 0.000 description 11
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 9
- 238000003917 TEM image Methods 0.000 description 8
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 6
- 150000004703 alkoxides Chemical class 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002001 electrolyte material Substances 0.000 description 5
- 230000000737 periodic effect Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000010408 film Substances 0.000 description 3
- 239000011245 gel electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229920000620 organic polymer Polymers 0.000 description 3
- 238000003825 pressing Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 235000019445 benzyl alcohol Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000013507 mapping Methods 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000000851 scanning transmission electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- FIPWRIJSWJWJAI-UHFFFAOYSA-N Butyl carbitol 6-propylpiperonyl ether Chemical compound C1=C(CCC)C(COCCOCCOCCCC)=CC2=C1OCO2 FIPWRIJSWJWJAI-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- HHFAWKCIHAUFRX-UHFFFAOYSA-N ethoxide Chemical compound CC[O-] HHFAWKCIHAUFRX-UHFFFAOYSA-N 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- -1 hydroxide ions Chemical class 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 238000002847 impedance measurement Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011244 liquid electrolyte Substances 0.000 description 1
- NBTOZLQBSIZIKS-UHFFFAOYSA-N methoxide Chemical compound [O-]C NBTOZLQBSIZIKS-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229960005235 piperonyl butoxide Drugs 0.000 description 1
- 239000012254 powdered material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- IKNCGYCHMGNBCP-UHFFFAOYSA-N propan-1-olate Chemical compound CCC[O-] IKNCGYCHMGNBCP-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 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
- Hybrid Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Description
前記導体としては、例えば導電性炭素が挙げられる。また、炭素から構成される正極は、炭素以外の他の成分を含んでいてもよく、例えばPtやMnO2などの、酸素の還元反応を促進可能な触媒を含んでいることが好ましい。
テトラ−n−ブトキシジルコニウム(Zr(n−OBu)4)にエタノールと水酸化カリウム水溶液を加え、攪拌してゾルを調製した。なお、原料のモル比は、テトラ−n−ブトキシジルコニウム:エタノール:水:水酸化カリウム=1:10:3:1であった。得られたゾルを60℃で10日保持し、続いて800℃で5時間熱処理することによって、水酸化カリウムを含むジルコニア(KOH−ZrO2)ゲル粉末を作製した。
ポイント1(粒子内):
O:34.7at%、K:0.4at%、Zr:64.9at%
ポイント2(粒子界面):
O:32.8at%、K:2.2at%、Zr:65.0at%
実施例1における、酸化鉄を担持させる前のKOH−ZrO2電解質、鉄粉、カーボン粉末を混合して、実施例1と同様の条件でプレスし、空気電池を作成した。なお、KOH−ZrO2電解質とカーボン粉末との混合比は質量比(前者/後者)で、12:1であった。
Claims (7)
- Zr、Al及びSiから選択される少なくとも1種の酸化物と塩基性水酸化物を含み、
前記酸化物は、Zr、Al及びSiから選択される少なくとも1種の元素と酸素の結合がネットワークを形成してゲル状化物になっていると共に、粒状で存在しており、
前記塩基性水酸化物は、アルカリ金属水酸化物又は水酸化アンモニウム塩であると共に、前記酸化物の表面に存在しており、
前記酸化物に酸化鉄が担持されており、
前記酸化鉄が負極として作用し、前記酸化物及び前記塩基性水酸化物が固体電解質として作用する空気電池用材料。 - 前記酸化物の内接円の直径が1nm以上10μm以下であり、かつこの所定の大きさの酸化物の表面には前記塩基性水酸化物及び/又は前記酸化鉄が付着している請求項1に記載の空気電池用材料。
- 前記酸化物がZr酸化物である請求項1又は2に記載の空気電池用材料。
- 前記塩基性水酸化物はアルカリ金属水酸化物である請求項1〜3のいずれかに記載の空気電池用材料。
- 前記酸化鉄は、Fe3O4である請求項1〜4のいずれかに記載の空気電池用材料。
- 塩基性水酸化物の存在下、酸化物に鉄アセチルアセトナートの溶液を含浸させた後、熱処理することによって製造される請求項1〜5のいずれかに記載の空気電池用材料。
- 炭素から構成される正極と、
導体及び請求項1〜6のいずれかに記載の空気電池用材料とから構成されることを特徴とする全固体空気電池。
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JP5739831B2 true JP5739831B2 (ja) | 2015-06-24 |
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Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2014150056A (ja) * | 2013-01-08 | 2014-08-21 | Kobe Steel Ltd | 金属−空気全固体二次電池用複合負極材料、およびこれを用いた金属−空気全固体二次電池 |
JP6033208B2 (ja) * | 2013-12-06 | 2016-11-30 | 株式会社神戸製鋼所 | 二次電池用電解質膜、接合体、金属−空気全固体二次電池、及びその接合体の製造方法 |
JP7141809B2 (ja) * | 2017-04-12 | 2022-09-26 | 株式会社三徳 | 負極材料、負極、及び鉄空気電池 |
CN111653790B (zh) * | 2020-06-18 | 2021-12-03 | 中国科学院上海应用物理研究所 | 一种全固态铁空电池 |
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JPH10214639A (ja) * | 1997-01-31 | 1998-08-11 | Toshiba Battery Co Ltd | 電池の製造方法 |
JP3848882B2 (ja) * | 2002-02-13 | 2006-11-22 | ニッポン高度紙工業株式会社 | 高イオン伝導性固体電解質及び該固体電解質を使用した電気化学システム |
JP4871225B2 (ja) * | 2007-07-02 | 2012-02-08 | ニッポン高度紙工業株式会社 | 高イオン伝導性固体電解質及びその製造方法並びに該固体電解質を使用した電気化学システム |
CN103026545A (zh) * | 2010-05-28 | 2013-04-03 | 丰田自动车株式会社 | 用于可充电金属空气电池的阴极催化剂和可充电金属空气电池 |
JP5952540B2 (ja) * | 2010-09-02 | 2016-07-13 | 株式会社神戸製鋼所 | 固体電解質材料およびこれを用いた金属−空気全固体二次電池 |
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