CN107293760A - A kind of preparation method of metal-air battery perovskite type catalyst - Google Patents
A kind of preparation method of metal-air battery perovskite type catalyst Download PDFInfo
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- CN107293760A CN107293760A CN201710430210.8A CN201710430210A CN107293760A CN 107293760 A CN107293760 A CN 107293760A CN 201710430210 A CN201710430210 A CN 201710430210A CN 107293760 A CN107293760 A CN 107293760A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/08—Hybrid cells; Manufacture thereof composed of a half-cell of a fuel-cell type and a half-cell of the secondary-cell type
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- 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
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Abstract
The present invention relates to a kind of preparation method of metal-air battery perovskite type catalyst, the chemical formula of the perovskite type catalyst is：LaxY(1‑x)ZO3；In formula, 0 ＜ x ＜ 1, Y is Sr or Co, Z are Mn or Fe；It comprises the following steps：(a) lanthanum nitrate, nitric acid Y and nitric acid Z are weighed for x: 1 x: l in molar ratio, it is soluble in water respectively, add ethylene glycol formation mixed solution；(b) complexing agent is added into the mixed solution, its pH value is adjusted with ammoniacal liquor to 6~7, complexing is stirred；It is subsequently moved to stirring in thermostat water bath and grinds to form powder to after forming gel, re-dry；(c) powder is calcined at 250~500 DEG C.High-temperature roasting without carrying out more than 500 DEG C, simplifies preparation technology and difficulty, reduces cost.
Description
Technical field
The invention belongs to metal-air battery field, it is related to a kind of catalyst, and in particular to a kind of metal-air battery is used
The preparation method of perovskite type catalyst.
Background technology
At present, the increasingly increase to energy demand have stimulated to efficient, low cost and environmentally friendly replacement energy conversion
With the research and development of stocking system.Hydrogen reduction (ORR) and oxygen evolution reaction (OER) they are the cores of important renewable energy technologies, including
Fuel cell, lithium-air/oxygen battery and water decomposition.If the oxygen in inexhaustible air is used continuously to provide appearance
Amount, the theoretical energy density of lithium-air battery be about 11140 watt-hours/kilogram, far above other energy storage devices.But
It is, to this class lithium-air battery, because using nonaqueous solution electrolysis liquid, the undissolved discharging product in organic electrolyte
Li2O2Porous air electrode can gradually be blocked.Therefore, battery performance can decline drop with discharge time.
In order that lithium-air battery commercial applications, presently, there are many problems needs to solve, including the electrolyte of difference is steady
It is qualitative, the charge/discharge efficiency of cathod catalyst difference, high rate performance and cycle life etc..In these problems one it is critical
Challenge is slow oxygen reduction reaction (ORR) (discharge process) and oxygen evolution reaction (OER) (charging process) dynamics.Use at present
The cathod catalyst of catalytic air reaction is usually carbon or carbon supported noble metal catalyst, but its is expensive.Therefore, in order to set
Lithium-air battery, lithium-air-fuel battery and hydrogen based on polymer dielectric film of the meter with high-performance and long-time stability
Gas/air-fuel battery, it is also very desirable to developing low-cost, efficient bifunctional electrocatalyst.
The content of the invention
A kind of metal-air battery is provided and urged with Ca-Ti ore type the invention aims to overcome the deficiencies in the prior art
The preparation method of agent.
To reach above-mentioned purpose, the technical solution adopted by the present invention is：A kind of metal-air battery is catalyzed with Ca-Ti ore type
The preparation method of agent, the chemical formula of the perovskite type catalyst is：LaxY(1-x)ZO3；In formula, 0 ＜ x ＜ 1, Y is Sr or Co, Z
For Mn or Fe；It comprises the following steps：
(a) lanthanum nitrate, nitric acid Y and nitric acid Z are weighed for x: 1-x: 1 in molar ratio, it is soluble in water respectively, add ethylene glycol
Form mixed solution；
(b) complexing agent is added into the mixed solution, its pH value is adjusted with ammoniacal liquor to 6~7, complexing is stirred；With
After move in thermostat water bath stirring and grind to form powder to after forming gel, re-dry；
(c) powder is calcined at 250~500 DEG C.
Optimally, in step (a), the volume ratio of the water and ethylene glycol is 1~10: 1.
Further, the mol ratio of the complexing agent and La, Y and Z total ion concentration is 1: 1~3.
The preferred scheme of the present invention is that the chemical formula of the perovskite type catalyst is：LaxSr(1-x)MnO3, 0.5
＜ x ＜ 1；The complexing agent that it is used is citric acid；In step (c), the powder carries out calcining 5~10 hours at 350~500 DEG C
.
Another preferred scheme of the present invention is that the chemical formula of the perovskite type catalyst is：LaxCo(1-x)FeO3,
0.5 ＜ x ＜ 1.Its complexing agent is preferably one kind in 1- ethyl-3-methylimidazole halogeno salts, preferably villaumite；Step (c)
In, the powder only need to carry out calcining 3~5 hours at 250~350 DEG C.
Optimally, in step (b), the time of the stirring complexing is 2~3 hours.
Because above-mentioned technical proposal is used, the present invention has following advantages compared with prior art：Metal-air of the present invention
The preparation method of battery perovskite type catalyst, only calcining need to be carried out under 250~500 DEG C of lower temperature can be prepared by calcium
Titanium ore type catalyst, the high-temperature roasting without carrying out more than 500 DEG C, simplifies preparation technology and difficulty, reduces cost.
Embodiment
The preparation method of metal-air battery perovskite type catalyst of the present invention, the chemistry of the perovskite type catalyst
Formula is：LaxY(1-x)ZO3；In formula, 0 ＜ x ＜ 1, Y is Sr or Co, Z are Mn or Fe；It comprises the following steps：(a) it is in molar ratio
Weigh lanthanum nitrate, nitric acid Y and nitric acid Z at x: 1-x: 1, soluble in water respectively, adds ethylene glycol formation mixed solution；(b) to institute
State and complexing agent is added in mixed solution, its pH value is adjusted with ammoniacal liquor to 6~7, complexing is stirred；It is subsequently moved to thermostat water bath
Middle stirring grinds to form powder to after forming gel, re-dry；(c) powder is calcined at 250~500 DEG C.And
More than 500 DEG C of high-temperature roasting need not be carried out, preparation technology and difficulty is simplified, reduces cost.
In step (a), the volume ratio of the water and ethylene glycol is 1~10: 1.The complexing agent and La, Y and Z total ion concentration
Mol ratio be 1: 1~3, and stir complexing time be 2~3 hours, to ensure that complexing agent is fully complexed.
The chemical formula of the perovskite type catalyst is preferably：LaxSr(1-x)MnO3, 0.5 ＜ x ＜ 1 are now adapted to it
Complexing agent be citric acid, therefore will correspondence powder 350~500 DEG C carry out calcining 5~10 hours.The Ca-Ti ore type
The chemical formula of catalyst is also preferably：LaxCo(1-x)FeO3, 0.5 ＜ x ＜ 1, the complexing agent being adapted to it is 1- ethyl -3- methyl
One kind in imidazoles halogeno salt, now carries out calcining 3~5 hours at 250~350 DEG C by powder, significantly reduces powder
The temperature and time of body calcining.
The present invention is further described below in conjunction with embodiment.
Embodiment 1
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, Ca-Ti ore type catalysis
The chemical formula of agent is：La0.6Sr0.4MnO3, it comprises the following steps：
(a) 0.6mol lanthanum nitrates, 0.4mol strontium nitrates and 1mol manganese nitrates are weighed, is dissolved in respectively in 1000ml water, then is added
Enter 1000ml ethylene glycol formation mixed solution；
(b) 2mol citric acids are added into mixed solution, its pH value is adjusted with ammoniacal liquor to 6~7, complexing is stirred；With
After move in thermostat water bath 90 DEG C stirring to formed gel, then by gel be placed in 150 DEG C of drying box dry after grind
Wear into powder；
(c) powder is subjected to calcining 10 hours at 350 DEG C.
Embodiment 2
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, its preparation process and reality
Apply basically identical in example 1, unlike：In step (a), that weigh is 0.4mol lanthanum nitrates, 0.6mol strontium nitrates and 1mol
Manganese nitrate, finally gives catalyst for La0.4Sr0.6MnO3。
Embodiment 3
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, its preparation process and reality
Apply basically identical in example 1, unlike：In step (a), that weigh is 0.8mol lanthanum nitrates, 0.2mol strontium nitrates and 1mol
Manganese nitrate, finally gives catalyst for La0.8Sr0.2MnO3。
Embodiment 4
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, its preparation process and reality
Apply basically identical in example 1, unlike：In step (a), the ethylene glycol of addition is 100ml.
Embodiment 5
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, its preparation process and reality
Apply basically identical in example 1, unlike：In step (a), the ethylene glycol of addition is 500ml.
Embodiment 6
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, its preparation process and reality
Apply basically identical in example 1, unlike：In step (c), powder is subjected to calcining 5 hours at 500 DEG C.
Embodiment 7
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, Ca-Ti ore type catalysis
The chemical formula of agent is：La0.6Co0.4FeO3, it comprises the following steps：
(a) 0.6mol lanthanum nitrates, 0.4mol cobalt nitrates and 1mol ferric nitrates are weighed, is dissolved in respectively in 1000ml water, then is added
Enter 1000ml ethylene glycol formation mixed solution；
(b) 2mol 1- ethyl-3-methylimidazole chlorates are added into mixed solution, adjusted with ammoniacal liquor its pH value to 6~
7, it is stirred complexing；It is subsequently moved in thermostat water bath in 90 DEG C of stirrings to gel is formed, gel is then placed in 150 DEG C
Powder is ground to form after being dried in drying box；
(c) powder is subjected to calcining 3 hours at 350 DEG C.
Embodiment 8
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, its preparation process and reality
Apply basically identical in example 6, unlike：In step (b), citric acid is used.
Embodiment 9
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, its preparation process and reality
Apply basically identical in example 6, unlike：In step (c), powder is subjected to calcining 5 hours at 250 DEG C.
Comparative example 1
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, its preparation process and reality
Apply basically identical in example 7, the difference is that not adding 1000ml ethylene glycol.
Comparative example 2
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, its preparation process and reality
Apply basically identical in example 7, the difference is that not adding citric acid.
Comparative example 3
The present embodiment provides a kind of preparation method of metal-air battery perovskite type catalyst, its preparation process and reality
Apply basically identical in example 7, unlike：Calcining 10 hours is carried out at 950 DEG C.
Perovskite type catalyst made from embodiment 1-8, comparative example 1-3 is dispersed in Nafion solution, usually taken
5% in 5% Nafion solution of 95 microlitres of 10mg catalyst addition, and 350 microlitres of ethanol are added, then take 7 microlitres of drop drops
To disk electrode, it is placed in 6M KOH solution and carries out electro-chemical test, -0.3V polarized current densities is respectively 0.075Acm-2、0.065Acm-2、0.070Acm-2、0.075Acm-2、0.075Acm-2、0.078Acm-2、0.092Acm-2、0.058Acm-2、
0.088Acm-2、0.049Acm-2、0Acm-2、0.045Acm-2；Above-mentioned each perovskite type catalyst is subjected to cyclical stability survey
Examination, to circulate 10000 after-polarization current density retention be respectively 99%, 90%, 92%, 95%, 95%, 96%, 99%,
85%th, 92%, 80%, 0,75%.
The above embodiments merely illustrate the technical concept and features of the present invention, and its object is to allow person skilled in the art
Scholar can understand present disclosure and implement according to this, and it is not intended to limit the scope of the present invention, all according to the present invention
The equivalent change or modification that Spirit Essence is made, should all be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of metal-air battery perovskite type catalyst, the chemical formula of the perovskite type catalyst
For：LaxY(1-x)ZO3；In formula, 0 ＜ x ＜ 1, Y is Sr or Co, Z are Mn or Fe；Characterized in that, it comprises the following steps：
(a) lanthanum nitrate, nitric acid Y and nitric acid Z are weighed for x: 1-x: 1 in molar ratio, it is soluble in water respectively, add ethylene glycol and formed
Mixed solution；
(b) complexing agent is added into the mixed solution, its pH value is adjusted with ammoniacal liquor to 6~7, complexing is stirred；Then move
Into thermostat water bath, stirring grinds to form powder to after forming gel, re-dry；
(c) powder is calcined at 250~500 DEG C.
2. the preparation method of metal-air battery perovskite type catalyst according to claim 1, it is characterised in that：Step
(a) in, the volume ratio of the water and ethylene glycol is 1~10: 1.
3. the preparation method of metal-air battery perovskite type catalyst according to claim 2, it is characterised in that：It is described
The mol ratio of complexing agent and La, Y and Z total ion concentration is 1: 1~3.
4. the preparation method of metal-air battery perovskite type catalyst according to claim 3, it is characterised in that described
The chemical formula of perovskite type catalyst is：LaxSr(1-x)MnO3, 0.5 ＜ x ＜ 1.
5. the preparation method of metal-air battery perovskite type catalyst according to claim 4, it is characterised in that：It is described
Complexing agent is citric acid.
6. the preparation method of metal-air battery perovskite type catalyst according to claim 5, it is characterised in that：It is described
Powder carries out calcining 5~10 hours at 350~500 DEG C.
7. the preparation method of metal-air battery perovskite type catalyst according to claim 3, it is characterised in that described
The chemical formula of perovskite type catalyst is：LaxCo(1-x)FeO3, 0.5 ＜ x ＜ 1.
8. the preparation method of metal-air battery perovskite type catalyst according to claim 7, it is characterised in that：It is described
Complexing agent is one kind in 1- ethyl-3-methylimidazole halogeno salts.
9. the preparation method of metal-air battery perovskite type catalyst according to claim 8, it is characterised in that：It is described
Powder carries out calcining 3~5 hours at 250~350 DEG C.
10. the preparation method of metal-air battery perovskite type catalyst according to claim 1, it is characterised in that：Step
Suddenly in (b), the time of the stirring complexing is 2~3 hours.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1529374A (en) * | 2003-10-08 | 2004-09-15 | 华南理工大学 | Zinc-air battery electrocatalyst and preparation method thereof |
| CN101845306A (en) * | 2010-03-31 | 2010-09-29 | 天津大学 | Preparation method and application of Lal-xSrxCoO3 perovskite catalyst |
| CN103831097A (en) * | 2014-03-26 | 2014-06-04 | 苏州绿电能源科技有限公司 | Nano-catalyst-lanthanum strontium manganese oxygen material, and preparation method and application of nano-catalyst-lanthanum strontium manganese oxygen material |
| CN106410226A (en) * | 2016-12-08 | 2017-02-15 | 深圳大学 | Graphene-doped modified nano-perovskite-type La(1-x)SrxMnO3 composite material as well as preparation method and application of composite material |
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2017
- 2017-06-03 CN CN201710430210.8A patent/CN107293760B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1529374A (en) * | 2003-10-08 | 2004-09-15 | 华南理工大学 | Zinc-air battery electrocatalyst and preparation method thereof |
| CN101845306A (en) * | 2010-03-31 | 2010-09-29 | 天津大学 | Preparation method and application of Lal-xSrxCoO3 perovskite catalyst |
| CN103831097A (en) * | 2014-03-26 | 2014-06-04 | 苏州绿电能源科技有限公司 | Nano-catalyst-lanthanum strontium manganese oxygen material, and preparation method and application of nano-catalyst-lanthanum strontium manganese oxygen material |
| CN106410226A (en) * | 2016-12-08 | 2017-02-15 | 深圳大学 | Graphene-doped modified nano-perovskite-type La(1-x)SrxMnO3 composite material as well as preparation method and application of composite material |
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Effective date of registration: 20230920 Address after: First floor, No. 2300 Yangshupu Road, Yangpu District, Shanghai, 200000 (centralized registration location) Patentee after: Hydrogen New (Shanghai) New Energy Technology Co.,Ltd. Address before: 200090 B05-18 room 4B, No. 2300, Yang Shu Pu Road, Shanghai Patentee before: SHANGHAI BOXUAN ENERGY TECHNOLOGY CO.,LTD. |