CN102658185B - Catalyst for secondary reversible air electrode and preparation method thereof - Google Patents
Catalyst for secondary reversible air electrode and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 47
- 230000002441 reversible effect Effects 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000011068 loading method Methods 0.000 claims abstract description 8
- 239000000126 substance Substances 0.000 claims abstract description 7
- 239000011575 calcium Substances 0.000 claims description 22
- 239000000843 powder Substances 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 14
- 239000011259 mixed solution Substances 0.000 claims description 13
- 239000000243 solution Substances 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052791 calcium Inorganic materials 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000010941 cobalt Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims description 9
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 238000001704 evaporation Methods 0.000 claims description 6
- 230000008020 evaporation Effects 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 239000012467 final product Substances 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 159000000007 calcium salts Chemical class 0.000 claims description 4
- 150000001868 cobalt Chemical class 0.000 claims description 4
- 150000002603 lanthanum Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000005245 sintering Methods 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 8
- 239000003575 carbonaceous material Substances 0.000 abstract 2
- 230000000694 effects Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000009776 industrial production Methods 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910002129 La0.6Ca0.4CoO3 Inorganic materials 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000012216 screening Methods 0.000 description 5
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 229940097267 cobaltous chloride Drugs 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material 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
- 238000004458 analytical method Methods 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010325 electrochemical charging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 229910052712 strontium Inorganic materials 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
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a catalyst for a secondary reversible air electrode and a preparation method thereof, in particular to a load type perovskite type catalyst for the secondary reversible air electrode. The chemical formula of the catalyst is LaxCa (1-x) CoO3/ TiC or LaxCa (1-x) CoO3/ TiN, wherein 0.5≤x≤0.7, and the loading quantity of LaxCa (1-x) CoO3 is 5wt%-80wt%. The catalyst is capable of resolving the problem that structure of a carbon material is easy to damage when the carbon material serves as a carrier, simultaneously improves circulation performance of a battery, is simple in preparation method, adopts a direct heating method without adding other materials, is high in purity, is evenly dispersed on the carrier, and is capable of well improving catalyst effect and suitable for industrial production.
Description
Technical field
The present invention relates to a kind of secondary reversible air electrode catalyst, specifically relate to a kind of secondary reversible air
Electrode support type perovskite type catalyst；The invention still further relates to the preparation method of this catalyst.
Background technology
With the increasingly reduction of Fossil fuel, seek new regenerative resource and have become as world today's solution energy crisis
Important Action.Various fuel cells arise at the historic moment as potential alternative energy source, and wherein, metal-air battery is that a class is special
Fuel cell, available metal has zinc, aluminum, magnesium etc., and these metallic elements rich content on earth, using rear recyclable
Recycle, and during use, non-toxic by-products generate.Therefore, metal-air battery has low cost, nontoxic, pollution-free, ratio
The advantages of energy is high.
Air electrode, as negative electrode, is the important component part of metal-air battery, the performance of catalyst in air electrode
And the life-span then become restriction metal-air battery can business-like key factor.Traditional irreversible air electrode makes gold
Belong to air cell and be unable to making active materials for use in secondary electrochemical charging, limit the application of metal-air battery.In recent years, secondary reversible air electrode
Development, promoted the extensive application of metal-air battery.For secondary reversible air electrode, its Catalytic Layer not only can
There is the reduction reaction of oxygen, and the evolution reaction of oxygen can occur.The reaction potential of analysis oxygen is compared with redox reactions
Height, and the generation of active oxygen atom, when oxygen evolution reaction can be made to occur, air-electrode catalyst layer has high galvano-cautery and oxidation
Property.At present, common secondary reversible air electrode catalyst mostly is perovskite material ABO3, wherein A represent metal have La,
Ca, Sr, Ba etc.；The metal that B represents has Co, Fe, Mn etc..Perovskite has the structure of oxide, and electric conductivity is poor, is often carried on
To increase the electric conductivity of air electrode on material with carbon element, but the high potential corrosivity of oxygen evolution reaction and high oxidative can destroy carbon
The structure of material, limits perovskite as the application of secondary reversible air electrode catalyst.
Content of the invention
The present invention provides a kind of secondary reversible air electrode catalyst, when can effectively solve the problem that material with carbon element as carrier,
The problem that its structure is easily destroyed, can also improve the cycle performance of battery simultaneously；Its preparation method is simple, using directly adding
, without other materials, made catalyst purity is high and is uniformly dispersed on carrier, preferably can improve catalytic effect for full-boiled process,
It is suitable to industrialized production.
For solving above-mentioned technical problem, technical solution of the present invention is as follows：
A kind of secondary reversible air electrode catalyst, its chemical formula is LaxCa(1-x)CoO3/ TiC or LaxCa(1-x)CoO3/
TiN, wherein, 0.5≤x≤0.7, LaxCa(1-x)CoO3Loading be 5wt%-80wt%, preferably 12.5wt%-
60wt%.
The preparation method of above-mentioned secondary reversible air electrode catalyst is：It is (2.5- by the mol ratio of lanthanum, calcium and cobalt
3.5): (1.5-2.5): 5 prepare the mixed solution of lanthanum salt, calcium salt and cobalt salt, and the preferably mol ratio according to lanthanum, calcium and cobalt is 3: 2:
5.
Add pretreated TiC or TiN support powder in above-mentioned mixed solution, be sufficiently stirred in a heated state mixing
Close until stirring and cannot continue after vapor evaporation, this heated condition is preferably and heats at 60-90 DEG C.By mixture after drying
High temperature sintering 2-5h, sinters at preferably 700-1000 DEG C, is immediately placed in afterwards in cold water and carries out quickly cooling process, mixture is sunk
Shallow lake is dried, grinding obtains final product LaxCa(1-x)CoO3/ TiC or LaxCa(1-x)CoO3/ TiN powder body, obtains even-grained urging after screening
Agent powder.Wherein, described cold water is preferably not higher than 10 DEG C and the deionized water not frozen.
Described lanthanum salt, calcium salt and cobalt salt can be selected from respectively one of nitrate or chloride of lanthanum, calcium and cobalt etc. or
Both mixture.
Bulk catalyst La deserved in theory after reacting in described mixed solutionxCa(1-x)CoO3With TiC or TiN carrier
Mass ratio be about 1: 19-4: 1, that is, in above-mentioned mixed solution add TiC or TiN carrier when preferably in this ratio.
The preprocessing process of described support powder is preferably after TiC or TiN powder sieve and is placed in 5wt%-30wt%'s
In the solution such as nitric acid or hydrochloric acid, after 50-80 DEG C of stirring 3-8h, after removing filtrate, deionized water is rinsed repeatedly, until pH=7
Till, TiC or TiN powder are dried and obtained.
In sum, the secondary reversible air electrode catalyst that the present invention provides, by using through special pre-treatment
Carrier material and snead process, can effectively solve the problem that the problem that material with carbon element is easily destroyed as its structure during carrier,
The cycle performance of battery can also be improved simultaneously；Its preparation method is simple, using snead process without other materials, made urges
Agent purity is high and is uniformly dispersed on carrier, preferably can improve catalytic effect, be suitable to industrialized production.
Brief description
Fig. 1 is that the catalyst of the present invention is applied to the cathodic polarization curve figure of auxiliary air electrode.
Specific embodiment
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Embodiment 1
A kind of secondary reversible air electrode catalyst, its chemical formula is La0.6Ca0.4CoO3/ TiC, wherein
La0.6Ca0.4CoO3Loading be 50wt%.
The preparation method of above-mentioned secondary reversible air electrode catalyst is：
It is placed in after TiC powder is sieved in the salpeter solution of 10wt%, after stirring 6h at 60 DEG C, spend after removing filtrate
Ionized water rinses repeatedly, till pH=7, by the TiC powder dry for standby of this pretreatment.
It is 3: 2: 5 mixed solutions preparing Lanthanum (III) nitrate, calcium nitrate and cobalt nitrate by the mol ratio of lanthanum, calcium and cobalt.According to mixed
Close in solution and be computed bulk catalyst La deserved after the reaction0.6Ca0.4CoO3Will be upper for 1: 1 with the mass ratio of TiC carrier
State standby TiC powder and add this mixed solution.
Then, it is thoroughly mixed at 80 DEG C until stirring and cannot continue after vapor evaporation；Will after drying at 70 DEG C
Mixture sinters 2h at 900 DEG C, is immediately placed in afterwards in 0 DEG C of deionized water and carries out quickly cooling process, mixture precipitation is dried
Dry, grinding obtains final product La0.6Ca0.4CoO3/ TiC powder, obtains even-grained catalyst fines after screening.
Using described catalyst, using activated carbon as conductive agent, PTFE is binding agent, prepares rechargeable catalysis
Film.Air electrode, cathodic polarization curve such as Fig. 1 of auxiliary air electrode is prepared by the way of waterproof membrane-conductive mesh-catalytic membrane
Shown.Every time between test cathodic polarization curve, the saturation that air electrode is carried out with 480min charges.As seen from Figure 1, secondary can
, compared with the 1st electric discharge polarization, decay is considerably less for electric discharge polarization performance after 6 times are charged for the charging air electrode.Air electricity
Pole will not make electric discharge polarization degradation with the increase of charging times, and phenomenon that performance go up sometimes even occurs.
Embodiment 2
A kind of secondary reversible air electrode catalyst, its chemical formula is La0.5Ca0.5CoO3/ TiC, wherein
La0.5Ca0.5CoO3Loading be 5wt%.
The preparation method of above-mentioned secondary reversible air electrode catalyst is：
It is placed in after TiC powder is sieved in the salpeter solution of 5wt%, after stirring 8h at 50 DEG C, spend after removing filtrate
Ionized water rinses repeatedly, till pH=7, by the TiC powder dry for standby of this pretreatment.
It is 1: 1: 2 mixed solution preparing Lanthanum (III) nitrate, calcium nitrate and cobalt nitrate by the mol ratio of lanthanum, calcium and cobalt.According to mixed
Close in solution and be computed bulk catalyst La deserved after the reaction0.5Ca0.5CoO3Will be upper for 1: 19 with the mass ratio of TiC carrier
State standby TiC powder and add this mixed solution.
Then, it is thoroughly mixed at 60 DEG C until stirring and cannot continue after vapor evaporation；Will after drying at 70 DEG C
Mixture sinters 5h at 700 DEG C, is immediately placed in afterwards in 5 DEG C of deionized water and carries out quickly cooling process, mixture precipitation is dried
Dry, grinding obtains final product La0.5Ca0.5CoO3/ TiC powder, obtains even-grained catalyst fines after screening.
Embodiment 3
A kind of secondary reversible air electrode catalyst, its chemical formula is La0.7Ca0.3CoO3/ TiC, wherein
La0.7Ca0.3CoO3Loading be 80wt%.
The preparation method of above-mentioned secondary reversible air electrode catalyst is：
It is placed in after TiC powder is sieved in the hydrochloric acid solution of 30wt%, after stirring 3h at 80 DEG C, spend after removing filtrate
Ionized water rinses repeatedly, till pH=7, by the TiC powder dry for standby of this pretreatment.
It is 7: 3: 10 mixed solutions preparing lanthanum chloride, calcium chloride and cobaltous chloride by the mol ratio of lanthanum, calcium and cobalt.According to mixed
Close in solution and be computed bulk catalyst La deserved after the reaction0.7Ca0.3CoO3Will be upper for 4: 1 with the mass ratio of TiC carrier
State standby TiC powder and add this mixed solution.
Then, it is thoroughly mixed at 90 DEG C until stirring and cannot continue after vapor evaporation；Will after drying at 70 DEG C
Mixture sinters 3h at 1000 DEG C, is immediately placed in afterwards in 10 DEG C of deionized water and carries out quickly cooling process, by mixture precipitation
Dry, grinding obtains final product La0.7Ca0.3CoO3/ TiC powder, obtains even-grained catalyst fines after screening.
Embodiment 4
A kind of secondary reversible air electrode catalyst, its chemical formula is La0.6Ca0.4CoO3/ TiN, wherein
La0.6Ca0.4CoO3Loading be 30wt%.
The preparation method of above-mentioned secondary reversible air electrode catalyst is：
It is placed in after TiN powder is sieved in the hydrochloric acid solution of 10wt%, after stirring 3h at 80 DEG C, spend after removing filtrate
Ionized water rinses repeatedly, till pH=7, by the TiN powder dry for standby of this pretreatment.
It is 3: 2: 5 mixed solutions preparing lanthanum chloride, calcium chloride and cobaltous chloride by the mol ratio of lanthanum, calcium and cobalt.According to mixed
Close in solution and be computed bulk catalyst La deserved after the reaction0.6Ca0.4CoO3Will be upper for 3: 7 with the mass ratio of TiN carrier
State standby TiN powder and add this mixed solution.
Then, it is thoroughly mixed at 65 DEG C until stirring and cannot continue after vapor evaporation；Will after drying at 70 DEG C
Mixture sinters 3h at 900 DEG C, is immediately placed in afterwards in 0 DEG C of deionized water and carries out quickly cooling process, mixture precipitation is dried
Dry, grinding obtains final product La0.6Ca0.4CoO3/ TiN powder body, obtains even-grained catalyst fines after screening.
Claims (8)
1. a kind of preparation method of secondary reversible air electrode catalyst is it is characterised in that the mol ratio by lanthanum, calcium and cobalt is
(2.5-3.5):(1.5-2.5):5 mixed solutions preparing lanthanum salt, calcium salt and cobalt salt, add pretreated TiC or TiN carrier
Powder, is thoroughly mixed in a heated state, by after mixture high temperature sintering 2-5h after drying, is immediately placed in cold water and carries out
Quickly cooling is processed, and mixture precipitation is dried, grinds and obtain final product LaxCa(1-x)CoO3/ TiC or LaxCa(1-x)CoO3/ TiN powder body is catalyzed
Agent；
The pretreatment of wherein said TiC or TiN support powder be TiC or TiN powder are sieved after be placed in 5wt%-30wt% nitre
In acid or hydrochloric acid solution, after 50-80 DEG C of stirring 3-8h, after removing filtrate, deionized water is rinsed repeatedly, until pH=7 is
Only, then dry.
2. the preparation method of secondary reversible air electrode catalyst according to claim 1 is it is characterised in that described lanthanum
Salt, calcium salt and cobalt salt are respectively nitrate or/and the chloride of lanthanum, calcium and cobalt.
3. the preparation method of secondary reversible air electrode catalyst according to claim 1 is it is characterised in that described mix
Close theoretical deserved La after solution reactionxCa(1-x)CoO3Mass ratio with TiC or TiN carrier is 1:19-4:1.
4. secondary reversible air electrode catalyst according to claim 1 preparation method it is characterised in that described
It is thoroughly mixed under heated condition, heat at wherein heated condition is 60-90 DEG C；It is sufficiently stirred for referring to be stirred continuously until water
After evaporation of vapours, stirring cannot continue.
5. the preparation method of secondary reversible air electrode catalyst according to claim 1 is it is characterised in that described height
The temperature of temperature sintering is 700-1000 DEG C.
6. the preparation method of secondary reversible air electrode catalyst according to claim 1 is it is characterised in that described cold
Water is not higher than 10 DEG C and the deionized water not frozen.
7. a kind of secondary reversible air electrode catalyst, is characterised by that described secondary reversible air electrode catalyst is basis
Method preparation described in claim 1-6 any one, its chemical formula is LaxCa(1-x)CoO3/ TiC or LaxCa(1-x)CoO3/
TiN；Wherein, 0.5≤x≤0.7, LaxCa(1-x)CoO3Loading be 5wt%-80wt%.
8. secondary reversible air electrode catalyst according to claim 7 is it is characterised in that described LaxCa(1-x)CoO3's
Loading is 12.5wt%-60wt%.
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| JP5755624B2 (en) * | 2012-10-15 | 2015-07-29 | トヨタ自動車株式会社 | Air electrode for air battery and air battery |
| CN109786718B (en) * | 2019-01-30 | 2022-01-28 | 合肥国轩高科动力能源有限公司 | Preparation method of inorganic perovskite coated MXene two-dimensional layered negative electrode material |
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| CN101380594A (en) * | 2008-09-05 | 2009-03-11 | 南京师范大学 | Titanium nitride carrier of catalyst of fuel batter with proton exchange film or titanium nitride and carbon carrier mixing carrier |
| CN101694880A (en) * | 2009-10-22 | 2010-04-14 | 复旦大学 | Electrode catalyst of fuel cell |
| CN101820087B (en) * | 2010-03-26 | 2013-06-12 | 瑞科稀土冶金及功能材料国家工程研究中心有限公司 | Combined double-effect oxygen catalyst and electrode and battery containing same |
| JP5115603B2 (en) * | 2010-08-17 | 2013-01-09 | トヨタ自動車株式会社 | Air electrode for metal-air battery, and metal-air battery including the air electrode |
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