CN102068993A - Method for preparing metallic oxide catalyst by using urea combustion-supporting method - Google Patents
Method for preparing metallic oxide catalyst by using urea combustion-supporting method Download PDFInfo
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- CN102068993A CN102068993A CN2010105464790A CN201010546479A CN102068993A CN 102068993 A CN102068993 A CN 102068993A CN 2010105464790 A CN2010105464790 A CN 2010105464790A CN 201010546479 A CN201010546479 A CN 201010546479A CN 102068993 A CN102068993 A CN 102068993A
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- nitric acid
- urea
- transition metal
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000004202 carbamide Substances 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 title claims abstract description 18
- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 14
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 13
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 9
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 8
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 229910052788 barium Inorganic materials 0.000 claims abstract description 3
- 229910052790 beryllium Inorganic materials 0.000 claims abstract description 3
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 3
- 239000000843 powder Substances 0.000 claims description 19
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 229910052593 corundum Inorganic materials 0.000 claims description 12
- 239000010431 corundum Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 150000003624 transition metals Chemical class 0.000 claims description 10
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 238000009835 boiling Methods 0.000 claims description 7
- 239000013078 crystal Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000001354 calcination Methods 0.000 abstract description 2
- 150000002823 nitrates Chemical class 0.000 abstract 4
- 239000000203 mixture Substances 0.000 abstract 2
- 238000007873 sieving Methods 0.000 abstract 2
- 229910052777 Praseodymium Inorganic materials 0.000 abstract 1
- 238000004821 distillation Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000005265 energy consumption Methods 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 229910052705 radium Inorganic materials 0.000 abstract 1
- 229910052719 titanium Inorganic materials 0.000 abstract 1
- 229910052727 yttrium Inorganic materials 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- 239000011572 manganese Substances 0.000 description 14
- 239000000126 substance Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 239000012528 membrane Substances 0.000 description 5
- 238000007747 plating Methods 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000003860 storage Methods 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a method for preparing a metallic oxide catalyst by using a urea combustion-supporting method, which belongs to the field of zinc-air batteries. According to the preparation method of the catalyst in the invention, the general formula of the prepared catalyst is AxA'1-xByB'1-yO3, wherein A comprises Y, La and Pr; A' comprises Sr, Ca, Ba, Be and Ra; B and B' refer to transition metal elements, such as Ni, Fe, Co, Cu, Mn and Ti; and x is equal to (0.1 to 0.9), and y is equal to (0.1 to 0.9). The method disclosed by the invention comprises the following steps of: completely dissolving rare-earth element (REE) nitrates A, REE nitrates A', transition metal element nitrates B, transition metal element nitrates B' and urea into deionized water; heating the obtained mixture; drying the mixture by distillation; sequentially burning and grinding the obtained product; sieving the obtained object; and finally, calcining the obtained particles subjected to sieving so as to obtain the catalyst disclosed by the invention. The method disclosed by the invention is simple in process, short in procedure, less in energy consumption, and lower in cost, and the prepared catalyst has a good catalytic property, therefore, the method provided by the invention is suitable for the high current discharge of the zinc-air batteries.
Description
Technical field
The present invention relates to a kind of RE perovskite type metal oxide catalyst that is applied to the zinc-air battery air electrode, this Preparation of catalysts method and use this catalyst to be used for the manufacture method of air electrode belongs to the zinc-air battery technical field.
Background technology
Zinc-air battery has that capacity is big, specific energy is high, can reach 1350Wh/Kg in theory, reached in fact 200～400Wh/Kg, stable operating voltage, raw material be easy to get, cheap, pollution-free, recyclable, do not have advantages such as particular difficulty and safety when using.
But the discharge current density of zinc-air battery is little, and for improving discharge current density, seek the good catalyst of catalytic performance is researcher's common objective always.Gold, silver are desirable catalyst, but cost is too high, can not realize industrialization; Metallo-chelate making complexity and kind are few, limit its development; The manganese compound cost is low, but catalytic performance is not high, and the discharge current density of unit are is too little, can't satisfy the requirement than great-power electronic electrical work electric current commonly used; Though spinel structure metal oxide initial catalytic activity is higher, its chemical stability is bad, after gained battery storage a period of time, the degree of polarization of discharge obviously increases, and working life is shorter, therefore, it is low that the researcher seeks cost, the perovskite type metal oxide that catalytic performance is high.CN1529374A discloses a kind of " zinc-air battery eelctro-catalyst and preparation method thereof ".But the operation of traditional preparation process RE perovskite type metal oxide catalyst is rigorous, complex process, and operating process is loaded down with trivial details, influences catalytic performance easily, and heat time heating time is also long, power consumption.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art, a kind of novel preparation method of RE perovskite type metal oxide catalyst is provided.With the catalyst of the inventive method preparation, its prices of raw and semifnished materials are cheap, catalytic activity is high, can improve the discharge current density of zinc-air battery.
The combustion-supporting legal system of urea of the present invention is equipped with the method for metal oxide catalyst, and the general formula of said catalyst is: A
xA '
1-xB
yB '
1-yO
3, crystal structure is a perovskite type crystal structure, it is characterized in that: in the general formula of said catalyst, A is a kind of among rare earth element y, La, the Pr, A ' is a kind of among Sr, Ca, Ba, Be, the Ra; B and B ' are a kind of among transition metal Ni, Fe, Co, Cu, Mn and the Ti, but B and B ' can not be with a kind of element simultaneously in a kind of catalyst, x=0.1 in the formula ~ 0.9, y=0.1 ~ 0.9; Its concrete preparation section is as follows:
A, rare earth element nitric acid A salt, nitric acid A ' salt, transition metal nitric acid B salt, transition metal nitric acid B ' salt and urea are poured in the corundum crucible or rustless steel container of the same 200ml of being equipped with deionized water, wherein the stoichiometry mol ratio of rare earth element nitric acid A salt, nitric acid A ' salt, transition metal nitric acid B salt, transition metal nitric acid B ' salt and urea is n
A: n
A ': n
B: n
B ': n
Urea=0.1 ~ 0.9: 0.9 ~ 0.1: 0.1 ~ 0.9: 0.9 ~ 0.1: 14 ~ 18; Stir then, it fully dissolved, obtain clear solution, place half an hour after, place on the common electric furnace and heat, stirred once every one minute during heating,, continue heating up to boiling, solution is evaporate to dryness gradually, burns, and obtains the foam-like powder of perovskite type crystal structure;
Grind after the foam-like powder that B, operation A obtain is cooled to room temperature, cross 300～500 purposes sieve, put in the Muffle furnace, calcine 1～3h down, promptly get catalyst of the present invention at 600～1000 ℃.
The present invention's superior part compared with prior art is that experimental technique is easy and simple to handle, and technology is simple, and flow process is short, equipment requires low, and heat time heating time is short, and it is little to consume energy, cost-saved, and the catalyst of preparation has good catalytic performance, the heavy-current discharge of suitable zinc-air battery.
Description of drawings
Fig. 1 is a zinc-air battery catalyst polarization curve,
Among the figure: a is the zinc-air battery air electrode; B is the zinc-air battery air electrode; C is the zinc-air battery air electrode.
The specific embodiment
With embodiment the present invention is further described below, but embodiments of the present invention have more than and be limited to this, its protection domain is as the criterion with claim.
Embodiment 1
Preparation Y
0.8Ba
0.2Mn
0.6Ni
0.4O
3Catalyst, its step is as follows:
(1), according to the present invention x, 1-x, y, 1-y stoichiometric proportion principle, take by weighing Y (NO respectively according to 0.8,0.2,0.4,0.6
3)
3.6H
2O, Ba (N
3)
2, Ni (NO
3)
2.6H
2O, contain 50% Mn (NO
3)
2Solution is poured in the corundum crucible of the same 200mL of being equipped with deionized water, stirs, and it is fully dissolved; Be 18 parts of amount of substance of above-mentioned four kinds of samples according to the amount of substance of urea again, take by weighing urea, pour in the corundum crucible, stir, it is fully dissolved.
(2), place half an hour after, place on the common electric furnace and heat, stirred once every one minute during heating, up to boiling; Continue heating, solution is evaporate to dryness gradually, and burning obtains the foam-like powder; After being cooled to room temperature powder was ground 500 mesh sieves,, promptly got catalyst Y of the present invention at 850 ℃ of calcining 2h
0.8Ba
0.2Mn
0.6Ni
0.1O
3
(3), successively Catalytic Layer, nickel plating stainless steel currect collecting net, waterproof ventilated membrane are folded, on powder compressing machine, be pressed into air electrode a.
Embodiment 2
Preparation Y
0.9Ba
0.1Mn
0.5Ni
0.5O
3Catalyst, its step is as follows:
(1), according to the present invention x, 1-x, y, 1-y stoichiometric proportion principle, take by weighing Y (NO respectively according to 0.9,0.1,0.5,0.5
3)
3.6H
2O, Ba (NO
3)
2, Ni (NO
3)
2, 6H
2O, contain 50% Mn (NO
3)
2Solution is poured in the same corundum crucible that appropriate amount of deionized water is housed, and stirs, and it is fully dissolved; Be 14 parts of amount of substance of above-mentioned four kinds of samples according to the amount of substance of urea again, take by weighing urea, pour in the corundum crucible, stir, it is fully dissolved.
(2), place half an hour after, place on the common electric furnace and heat, stirred once every one minute during heating, up to boiling; Continue heating, solution is evaporate to dryness gradually, and burning obtains the foam-like powder; Powder was ground 400 mesh sieves, calcined 1h down, promptly got catalyst Y of the present invention at 600 ℃
0.9Ba
0.1Mn
0.5Ni
0.5O
3
(3), successively Catalytic Layer, nickel plating stainless steel currect collecting net, waterproof ventilated membrane are folded, on powder compressing machine, be pressed into air electrode b.
Embodiment 3
Preparation Y
0.7Ba
0.3Mn
0.3Ni
0.7O
3Catalyst, its step is as follows:
(1), according to the present invention x, 1-x, y, 1-y stoichiometric proportion principle, take by weighing Y (NO respectively according to 0.7,0.3,0.7,0.3
3)
3.6H
2O, Ba (NO
3)
2, Ni (NO
3)
2.6H
2O, contain 50% Mn (NO
3)
2Solution is poured in the same corundum crucible that appropriate amount of deionized water is housed, and stirs, and it is fully dissolved; Be 16 parts of amount of substance of above-mentioned four kinds of samples according to the amount of substance of urea again, take by weighing urea, pour in the corundum crucible, stir, it is fully dissolved.
(2), place half an hour after, place on the common electric furnace and heat, stirred once every one minute during heating, up to boiling; Continue heating, solution is evaporate to dryness gradually, and burning obtains the foam-like powder; Powder was ground 300 mesh sieves, calcined 3h down, promptly got catalyst Y of the present invention at 1000 ℃
0.7Ba
0.3Mn
0.3Ni
0.7O
3
(3) successively Catalytic Layer, nickel plating stainless steel currect collecting net, waterproof ventilated membrane are folded, on powder compressing machine, be pressed into air electrode c.
Embodiment 4
Preparation La
0.1Sr
0.9Co
0.1Fe
0.9O
3Catalyst. its step is as follows:
(1), according to the present invention x, 1-x, y, 1-y stoichiometric proportion principle, take by weighing La (NO respectively according to 0.1,0.9,0.9,0.1
3)
3.6H
2O, Sr (NO
3)
2, Fe (NO
3)
3.6H
2O, Co (NO
3)
2.6H
2O pours in the corundum crucible of the same 200mL of being equipped with deionized water, stirs, and it is fully dissolved; Be 15 parts of amount of substance of above-mentioned four kinds of samples according to the amount of substance of urea again, take by weighing urea, pour in the corundum crucible, stir, it is fully dissolved.
(2), place half an hour after, place on the common electric furnace and heat, stirred once every one minute during heating, up to boiling; Continue heating, solution is evaporate to dryness gradually, and burning obtains the foam-like powder; After being cooled to room temperature powder was ground 500 mesh sieves, calcined 2h down, promptly got catalyst La of the present invention at 850 ℃
0.1Sr
0.9Fe
0.9Co
0.1O
3
(3), successively Catalytic Layer, nickel plating stainless steel currect collecting net, waterproof ventilated membrane are folded, on powder compressing machine, be pressed into air electrode e.
Embodiment 5
Preparation Pr
0.5Ca
0.5Cu
0.6Ti
0.4O
3Catalyst, its step is as follows:
(1), according to the present invention x, 1-x, y, 1-y stoichiometric proportion principle, take by weighing respectively according to 0.5,0.5,0.6,0.4
Pr (NO
3)
3.6H
2O, Ca (NO
3)
2, Cu (NO
3)
2.3H
2O, Ti (NO
3)
4, pour in the corundum crucible of the same 200mL of being equipped with deionized water, stir, it is fully dissolved; Be 16 parts of amount of substance of above-mentioned four kinds of samples according to the amount of substance of urea again, take by weighing urea, pour in the corundum crucible, stir, it is fully dissolved.
(2), place half an hour after, place on the common electric furnace and heat, stirred once every one minute during heating, up to boiling; Continue heating, solution is evaporate to dryness gradually, and burning obtains the foam-like powder; After being cooled to room temperature powder was ground 500 mesh sieves, calcined 2h down, promptly got catalyst P r of the present invention at 850 ℃
0.5Ca
0.5Cu
0.6Ti
0.4O
3
(3), successively Catalytic Layer, nickel plating stainless steel currect collecting net, waterproof ventilated membrane are folded, on powder compressing machine, be pressed into air electrode f.
The test of steady-state current-voltage polarizing curve map: at normal temperatures and pressures, the CHI660b type electrochemical workstation of marine products in the employing, with the air diffusion electrode is working electrode, the Hg/HgO electrode is a reference electrode, nickel screen is a comparison electrode, the NaOH aqueous solution of 6mol/L is electrolyte, with three electrode test systems the catalytic activity of air diffusion electrode eelctro-catalyst is carried out steady-state current-voltage polarizing curve test.Test result by steady-state current-voltage polarizing curve is estimated the electro catalytic activity of eelctro-catalyst.Result by Fig. 2 shows, the current density of the air diffusion electrode of surveying under-0.6v (Hg/HgO is a reference electrode) polarization potential be 200mA.cm
-2
Embodiment 6
Situation and embodiment 1 are basic identical, just at Y
0.8Ba
0.2Mn
0.6Ni
0.4O
3In the catalyst, change Ba into Be, change the nitrate of Ba the nitrate of Be into, other situation is identical with embodiment 1, at last catalyst Y of the present invention
0.8Be
0.2Mn
0.6Ni
0.4O
3, and make air electrode g.
Embodiment 7
Situation and embodiment 1 are basic identical, just at Y
0.8Ba
0.2Mn
0.6Ni
0.4O
3In the catalyst, change Ba into Ra, change the nitrate of Ba the nitrate of Ra into, other situation is identical with embodiment 1, at last catalyst Y of the present invention
0.8Ra
0.2Mn
0.6Ni
0.4O
3, and make air electrode h.
As mentioned above, can realize the present invention preferably.
Claims (1)
1. the combustion-supporting legal system of urea is equipped with the method for metal oxide catalyst, and the general formula of said catalyst is: A
xA '
1-xB
yB '
1-yO
3, crystal structure is a perovskite type crystal structure, it is characterized in that: in the general formula of said catalyst, A is a kind of among rare earth element y, La, the Pr, A ' is a kind of among Sr, Ca, Ba, Be, the Ra; B and B ' are a kind of among transition metal Ni, Fe, Co, Cu, Mn and the Ti, but B and B ' can not be with a kind of element simultaneously in a kind of catalyst, x=0.1 in the formula ~ 0.9, y=0.1 ~ 0.9; Its concrete preparation section is as follows:
A, rare earth element nitric acid A salt, nitric acid A ' salt, transition metal nitric acid B salt, transition metal nitric acid B ' salt and urea are poured in the corundum crucible or rustless steel container of the same 200ml of being equipped with deionized water, wherein the stoichiometry mol ratio of rare earth element nitric acid A salt, nitric acid A ' salt, transition metal nitric acid B salt, transition metal nitric acid B ' salt and urea is n
A: n
A ': n
B: n
B ': n
Urea=0.1 ~ 0.9: 0.9 ~ 0.1: 0.1 ~ 0.9: 0.9 ~ 0.1: 14 ~ 18; Stir then, it fully dissolved, obtain clear solution, place half an hour after, place on the common electric furnace and heat, stirred once every one minute during heating,, continue heating up to boiling, solution is evaporate to dryness gradually, burns, and obtains the foam-like powder of perovskite type crystal structure;
Grind after the foam-like powder that B, operation A obtain is cooled to room temperature, cross 300～500 purposes sieve, put in the Muffle furnace, calcine 1～3h down, promptly get catalyst of the present invention at 600～1000 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105464790A CN102068993A (en) | 2010-11-17 | 2010-11-17 | Method for preparing metallic oxide catalyst by using urea combustion-supporting method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010105464790A CN102068993A (en) | 2010-11-17 | 2010-11-17 | Method for preparing metallic oxide catalyst by using urea combustion-supporting method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102068993A true CN102068993A (en) | 2011-05-25 |
Family
ID=44027873
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|---|---|---|---|
| CN2010105464790A Pending CN102068993A (en) | 2010-11-17 | 2010-11-17 | Method for preparing metallic oxide catalyst by using urea combustion-supporting method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104557022A (en) * | 2015-01-23 | 2015-04-29 | 西安交通大学 | Highly nonlinear low loss double perovskite composite ceramic and preparation method thereof |
| CN105609794A (en) * | 2016-01-18 | 2016-05-25 | 湖南众麒能源科技有限责任公司 | Air electrode catalyst for zinc-air battery and preparation method of air electrode catalyst |
| EP3101718A4 (en) * | 2014-01-31 | 2017-07-26 | National University Corporation Hokkaido University | Catalyst for air electrode for metal/air secondary battery, and air electrode |
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| CN101222045A (en) * | 2007-12-27 | 2008-07-16 | 南京工业大学 | Method for synthesizing nano-scale lithium ion power battery cathode material by micro-reactor spontaneous combustion method |
| CN101711944A (en) * | 2008-10-03 | 2010-05-26 | 通用汽车环球科技运作公司 | Method and architecture for oxidizing nitric oxide in exhaust gas from hydrocarbon fuel source with a fuel lean combustion mixture |
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2010
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|---|
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3101718A4 (en) * | 2014-01-31 | 2017-07-26 | National University Corporation Hokkaido University | Catalyst for air electrode for metal/air secondary battery, and air electrode |
| US10693145B2 (en) | 2014-01-31 | 2020-06-23 | National University Corporation Hokkaid University | Catalyst for air electrode for metal-air secondary battery and air electrode |
| CN104557022A (en) * | 2015-01-23 | 2015-04-29 | 西安交通大学 | Highly nonlinear low loss double perovskite composite ceramic and preparation method thereof |
| CN105609794A (en) * | 2016-01-18 | 2016-05-25 | 湖南众麒能源科技有限责任公司 | Air electrode catalyst for zinc-air battery and preparation method of air electrode catalyst |
| CN105609794B (en) * | 2016-01-18 | 2018-12-21 | 长沙锦锋新能源科技有限公司 | A kind of air electrode catalyst of zinc-air battery and preparation method thereof |
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Application publication date: 20110525 |