CN110142039A - A kind of preparation method of catalyst and its application in metal-air battery - Google Patents
A kind of preparation method of catalyst and its application in metal-air battery Download PDFInfo
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- CN110142039A CN110142039A CN201910506500.5A CN201910506500A CN110142039A CN 110142039 A CN110142039 A CN 110142039A CN 201910506500 A CN201910506500 A CN 201910506500A CN 110142039 A CN110142039 A CN 110142039A
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- oxygen reduction
- catalyst
- reduction catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 110
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 150000001875 compounds Chemical class 0.000 claims abstract description 76
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000001301 oxygen Substances 0.000 claims abstract description 60
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 58
- 230000009467 reduction Effects 0.000 claims abstract description 49
- 239000002904 solvent Substances 0.000 claims abstract description 41
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 38
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 19
- 229910052712 strontium Inorganic materials 0.000 claims abstract description 6
- 238000006243 chemical reaction Methods 0.000 claims description 61
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical group OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 53
- 239000000243 solution Substances 0.000 claims description 37
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 29
- 239000011259 mixed solution Substances 0.000 claims description 24
- 239000004094 surface-active agent Substances 0.000 claims description 22
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 18
- 239000004202 carbamide Substances 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- 239000003795 chemical substances by application Substances 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 229910052746 lanthanum Inorganic materials 0.000 claims description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 11
- 239000011572 manganese Substances 0.000 claims description 11
- 229910052684 Cerium Inorganic materials 0.000 claims description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 10
- 239000012018 catalyst precursor Substances 0.000 claims description 10
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 10
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 10
- 239000003792 electrolyte Substances 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 10
- 239000011575 calcium Substances 0.000 claims description 9
- 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 claims description 9
- 239000011148 porous material Substances 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 7
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 6
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical group [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 239000000908 ammonium hydroxide Substances 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- RXSHXLOMRZJCLB-UHFFFAOYSA-L strontium;diacetate Chemical compound [Sr+2].CC([O-])=O.CC([O-])=O RXSHXLOMRZJCLB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 239000002131 composite material Substances 0.000 abstract description 55
- 238000000034 method Methods 0.000 abstract description 22
- 239000000463 material Substances 0.000 abstract description 21
- 230000003197 catalytic effect Effects 0.000 abstract description 19
- 239000011164 primary particle Substances 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 238000006555 catalytic reaction Methods 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 21
- 239000003575 carbonaceous material Substances 0.000 description 19
- 239000007787 solid Substances 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 17
- 239000002002 slurry Substances 0.000 description 17
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 16
- 235000015895 biscuits Nutrition 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 13
- 229910021641 deionized water Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 description 11
- 239000012046 mixed solvent Substances 0.000 description 11
- 229920002451 polyvinyl alcohol Polymers 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 8
- 229910052802 copper Inorganic materials 0.000 description 8
- 239000010949 copper Substances 0.000 description 8
- 239000000839 emulsion Substances 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 7
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 238000011068 loading method Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910001220 stainless steel Inorganic materials 0.000 description 7
- 239000010935 stainless steel Substances 0.000 description 7
- 239000004411 aluminium Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 6
- 238000000576 coating method Methods 0.000 description 6
- 230000001276 controlling effect Effects 0.000 description 6
- 229910002328 LaMnO3 Inorganic materials 0.000 description 5
- ODJZWVFLHZHURI-UHFFFAOYSA-M [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] Chemical compound [Br-].C(CCC)[P+](CCCC)(CCCC)CCCC.[NH4+].[Br-] ODJZWVFLHZHURI-UHFFFAOYSA-M 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000013067 intermediate product Substances 0.000 description 5
- 229910002182 La0.7Sr0.3MnO3 Inorganic materials 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000004698 Polyethylene Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910000473 manganese(VI) oxide Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000004044 response Effects 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910003367 La0.5Sr0.5MnO3 Inorganic materials 0.000 description 2
- 229910002148 La0.6Sr0.4MnO3 Inorganic materials 0.000 description 2
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000001802 infusion Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000013500 performance material Substances 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical group [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/32—Manganese, technetium or rhenium
- B01J23/34—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation method of Ca-Ti ore type compound oxygen reduction catalyst, the present invention program improves solvent heat/hydrothermal synthesis method by a kind of interval substep and is successfully prepared out La1‑ xMxMnO3‑CeO2, M is selected from Sr and/or Ca, the nano combined oxygen reduction catalyst in 0≤x < 1.0.This programme passes through the CeO rich in Lacking oxygen2Material adulterates LaMnO to element M3Base oxygen reduction catalyst carries out the modification of surface Lacking oxygen, realizes and significantly improves the intrinsic electrochemical catalysis performance of composite material, and the composite material is applied in aluminium-air cell.The catalytic composite material primary particle of this method preparation is smaller, is uniformly dispersed, specific surface area with higher；Preparation process is simple, is conducive to large-scale serial production.
Description
Technical field
The invention belongs to battery technology fields, and in particular to the preparation method of a kind of catalyst and its in metal-air battery
In application.
Background technique
In numerous oxygen reduction catalyst types, perovskite type oxygen reduction catalyst has always been considered as very potential your gold of substitution
Belong to one of the catalyst of Pt/C.The electrocatalysis characteristic influence factor of perovskite type oxygen reduction catalyst mainly has crystal structure, table
Face characteristic, oxidation state and Lacking oxygen defect etc..LnMnO comparable for specific surface3The oxidation of (Ln=La system or Y) series perovskite
For object, in alkaline system, oxygen reduction catalytic activity sequence is La > Pr > Nd > Sm > Gd > Y > Dy > Yb；Its catalytic activity with from
Sub- radius has direct relation, LaMnO3Show highest intrinsic oxygen reduction catalytic activity.For LaMnO3The oxidation of based perovskite type
For object, band structure and Mn may be implemented by the perovskite type catalyst that other element portions substitute La3+/Mn4+Chemical valence
Regulation, so as to improve the hydrogen reduction catalytic performance of catalyst；Still further aspect, by improving the oxygen adsorption capacity of catalyst,
It can also realize that the hydrogen reduction catalytic performance of perovskite type catalyst is promoted.It is well known that CeO2It is a kind of oxygen storage haveing excellent performance
Material is deposited, Lacking oxygen quickly can be formed and be disappeared, to effectively promote the local oxygen vacancy concentration of catalyst.
Existing preparation method 1: oxide composite catalyst generally carries out object by the way of multicomponent ball milling or grinding
Reason mixing.But this method can only realize physical mixed of the various ingredients under macro-scale, cannot be formed between multicomponent
Stronger interaction especially cannot effectively adjust Mn-O-Ce bond energy.
Existing preparation method 2: an one step hydro thermal method/step solvent-thermal method/infusion process/coprecipitation prepares composite oxides
Material.Under normal circumstances, material prepared by one step hydro thermal method/step solvent-thermal method is a kind of powder of irregular pattern
Grain, or even the impurity containing large amount of complex multi-element composite material, it is also possible to will affect the electro catalytic activity of catalyst；Dipping
Method/coprecipitation preparation oxide precursor, needs further high-temperature calcination that could obtain target composite catalyst.And high temperature
Calcining will will lead to oxidic catalyst particles and grow up, reunite seriously, have lower specific surface area；To reduce active site
Exposure, the catalytic performance of electro-catalysis is greatly lowered.Crystal form is also resulted in into Xiang Bujia, or even simple oxide can only be prepared
Composite material.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of Ca-Ti ore type compound oxygen reduction catalyst
Preparation method and its application in metal-air battery, Ca-Ti ore type compound oxygen reduction catalyst dispersion provided by the invention are equal
It is even, specific surface area with higher and catalytic performance.
The present invention provides a kind of preparation methods of Ca-Ti ore type compound oxygen reduction catalyst, comprising the following steps:
A solvent is carried out in confined conditions after) mixing cerium source compound, acid-base buffer agent, surfactant and solvent
Thermal response obtains reaction solution；
B lanthanum source compound, manganese source compound and the compound containing M element) are added in Xiang Suoshu reaction solution, obtains mixing molten
Liquid after the pH value for adjusting the mixed solution, carries out hydro-thermal reaction, obtains catalyst precursor；
C) catalyst precursor is calcined, obtains Ca-Ti ore type compound oxygen reduction catalyst, the perovskite
The chemical formula of type compound oxygen reduction catalyst is La1-xMxMnO3-CeO2, M is selected from Sr and/or Ca, 0≤x < 1.0.
Preferably, the cerium source compound is selected from cerous nitrate and/or cerous acetate；
The lanthanum source compound is selected from lanthanum nitrate and/or lanthanum acetate；
Compound containing M element is selected from one of strontium nitrate, strontium acetate, calcium nitrate and calcium acetate or a variety of；
The manganese source compound is selected from manganese nitrate and/or manganese acetate；
The acid-base buffer agent is selected from urea, ammonium chloride or ammonium carbonate；
The surfactant is selected from tetrabutylammonium bromide；
The solvent is selected from ethylene glycol.
Preferably, the temperature of the solvent thermal reaction is 80~250 DEG C, and the time of the solvent thermal reaction is 0.5~40
Hour.
Preferably, the pH adjusting agent for adjusting the pH value of the mixed solution is selected from sodium hydroxide, potassium hydroxide or ammonium hydroxide, adjusts
PH value is saved to 6~14.
Preferably, the temperature of the hydro-thermal reaction is 80~350 DEG C, and the time of the hydro-thermal reaction is 0.5~40 hour.
Preferably, the temperature of the calcining is 200~900 DEG C, and the time of the calcining is 10~250min.
It is described the present invention also provides a kind of Ca-Ti ore type compound oxygen reduction catalyst that above-mentioned preparation method is prepared
The chemical formula of Ca-Ti ore type compound oxygen reduction catalyst is La1-xMxMnO3-CeO2, for M selected from Sr and/or Ca, 0≤x < 1.0 are described
The partial size of Ca-Ti ore type compound oxygen reduction catalyst is 30~500nm, specific surface area 29.9cm-2g-1, pore volume is
0.093cm3g-1。
The present invention also provides a kind of air cathode, Ca-Ti ore type compound oxygen reduction prepared by the preparation method
Catalyst preparation obtains.
The present invention also provides a kind of metal-air battery, including air cathode, metal anode and electrolyte, the skies
Gas cathode is above-mentioned air cathode.
Compared with prior art, the present invention provides a kind of preparation method of Ca-Ti ore type compound oxygen reduction catalyst,
Be characterized in that, comprising the following steps: A) by cerium source compound, acid-base buffer agent, surfactant and solvent mix after closed
Under the conditions of carry out solvent thermal reaction, obtain reaction solution；B lanthanum source compound, manganese source compound) are added in Xiang Suoshu reaction solution and contains
The compound of M element, obtains mixed solution, after the pH value for adjusting the mixed solution, hydro-thermal reaction is carried out, before obtaining catalyst
Drive body；C) catalyst precursor is calcined, obtains Ca-Ti ore type compound oxygen reduction catalyst, the Ca-Ti ore type is multiple
The chemical formula for closing oxygen reduction catalyst is La1-xMxMnO3-CeO2, M is selected from Sr and/or Ca, 0≤x < 1.0.The present invention program passes through
A kind of interval substep improves solvent heat/hydrothermal synthesis method and is successfully prepared out La1-xMxMnO3-CeO2, M be selected from Sr and/or Ca, 0
The nano combined oxygen reduction catalyst in≤x < 1.0.This programme passes through the CeO rich in Lacking oxygen2Material adulterates LaMnO to element M3Base
Oxygen reduction catalyst carries out the modification of surface Lacking oxygen, realizes and significantly improves the intrinsic electrochemical catalysis of composite material
Can, and the composite material is applied in aluminium-air cell.The catalytic composite material primary particle of this method preparation is smaller, point
It dissipates uniformly, specific surface area with higher；Preparation process is simple, is conducive to large-scale serial production.
Detailed description of the invention
Fig. 1 is Ca-Ti ore type compound oxygen reduction catalyst preparation process flow diagram；
Fig. 2 is the TEM shape appearance figure of catalyst prepared by embodiment 1；
Fig. 3 is the TEM shape appearance figure of catalyst prepared by embodiment 1；
Fig. 4 is the adsorption desorption curve of catalyst prepared by embodiment 1；
Fig. 5 is the XRD test result of catalyst prepared by embodiment 1；
Fig. 6 is the electrochemical tests of catalyst prepared by embodiment 1；
Fig. 7 is the aluminium-air cell performance of catalyst preparation prepared by embodiment 1；
Fig. 8 is the TEM shape appearance figure of the catalyst of comparative example preparation；
Fig. 9 is the XRD test result of the catalyst of comparative example preparation；
Figure 10 is the electrochemical tests of the catalyst of comparative example preparation；
Figure 11 is the aluminium-air cell performance of the catalyst preparation of comparative example preparation.
Specific embodiment
The present invention provides a kind of preparation methods of Ca-Ti ore type compound oxygen reduction catalyst, comprising the following steps:
A solvent is carried out in confined conditions after) mixing cerium source compound, acid-base buffer agent, surfactant and solvent
Thermal response obtains reaction solution；
B lanthanum source compound, manganese source compound and the compound containing M element) are added in Xiang Suoshu reaction solution, obtains mixing molten
Liquid after the pH value for adjusting the mixed solution, carries out hydro-thermal reaction, obtains catalyst precursor；
C) catalyst precursor is calcined, obtains Ca-Ti ore type compound oxygen reduction catalyst, the perovskite
The chemical formula of type compound oxygen reduction catalyst is La1-xMxMnO3-CeO2, M is selected from Sr and/or Ca, 0≤x < 1.0.
The present invention first by cerium source compound, acid-base buffer agent, surfactant and solvent mix after in confined conditions
Solvent thermal reaction is carried out, reaction solution is obtained.
Wherein, the cerium source compound is selected from cerous nitrate and/or cerous acetate；The acid-base buffer agent is selected from urea, chlorination
Ammonium or ammonium carbonate, preferably urea；The surfactant is selected from tetrabutylammonium bromide；The solvent is selected from ethylene glycol.
Specifically, according to CeO2Amount cerium source compound is dissolved in solvent, wherein control La1-xMxMnO3-CeO2In
CeO2Range of solid content be 0.5~40%, preferably 2~20%, further preferably 3~15%.
Then surfactant is added into above-mentioned solution again, and a certain amount of acid-base buffer agent is added, system is mixed
Obtain mixed solution.
Wherein, the concentration range of surfactant in the solution is 0.001mmol/L~2mmol/L, preferably
0.005mmol/L~1mmol/L, further preferably 0.01mmol/L~0.2mmol/L；Acid-base buffer agent and CeO2Molar ratio is
(0.05~10): 1, preferably (0.1~1): 1, further preferably (0.2~0.8): 1.
Above-mentioned mixed solution is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, at a certain temperature solvent heat
Reaction.
The temperature of the solvent thermal reaction are as follows: 80~250 DEG C, preferably 85~200 DEG C are further preferably 90~150 DEG C；It is molten
The time of agent thermal response is 0.5~40 hour, preferably 1~30 hour, further preferably 2~20 hours；It after reaction, will be above-mentioned anti-
It answers kettle to be reduced to room temperature, obtains reaction solution.In the present invention, room temperature is defined as 25 ± 5 DEG C.
Then, lanthanum source compound, manganese source compound and the compound containing M element are added in Xiang Suoshu reaction solution, is mixed
Solution is closed, after the pH value for adjusting the mixed solution, hydro-thermal reaction is carried out, obtains catalyst precursor.
The lanthanum source compound is selected from lanthanum nitrate and/or lanthanum acetate；Compound containing M element be selected from strontium nitrate, strontium acetate,
One of calcium nitrate and calcium acetate are a variety of；The manganese source compound is selected from manganese nitrate and/or manganese acetate.
Specifically, at room temperature, being added in Xiang Shangshu reaction solution according to La1-xMxMnO3(0≤x < 1.0, M are selected from Sr
And/or Ca) stoichiometric ratio lanthanum source compound, manganese source compound and the compound containing M element, wherein lanthanum source compound, manganese
Source compound and compound containing M element are added in form of an aqueous solutions into the reaction solution, forming step A) it solvent and goes
The mixed solvent of ionized water.
Step A) solvent and water volume ratio range: (10~0.1): 1, preferably (5~0.2): 1, further preferably (2~
0.5): 1.
By be added pH adjusting agent adjust reaction kettle in mixed solvent pH value, the pH adjusting agent be selected from sodium hydroxide,
Potassium hydroxide or ammonium hydroxide, adjust pH value to 6~14, preferably 7~12, and further preferably 8~10).
After regulating pH value, then reaction kettle is subjected to hydro-thermal reaction at a certain temperature, the temperature of the hydro-thermal reaction is
80~350 DEG C, preferably 100~300 DEG C are further preferably 120~250 DEG C；The time range of the hydro-thermal reaction: 0.5~40
Hour, preferably 1~35 hour, be further preferably 2~30 hours.After reaction, it is naturally cooling to room temperature, reaction is obtained and produces
Object.
Finally, by after reaction product filtering in reaction kettle, after deionized water and ethyl alcohol are alternately and repeatedly cleaned repeatedly, then
Catalyst precursor is obtained after drying in 80~120 DEG C of baking ovens；
The catalyst precursor is calcined at a certain temperature and obtains catalytic composite material, the temperature of the calcining is
200~900 DEG C, preferably 300~800 DEG C are further preferably 400~700 DEG C；The time of the calcining is 10~250 minutes, excellent
It is selected as 30~200 minutes, is further preferably 60~150 minutes.
In certain specific embodiments of the invention, the doped chemical M is strontium element, Ca-Ti ore type compound oxygen reduction
The preparation method of catalyst is the preparation process flow schematic diagram of Ca-Ti ore type compound oxygen reduction catalyst referring to Fig. 1, Fig. 1.
Cerous nitrate is dissolved in ethylene glycol, tetrabutylammonium bromide and urea mixing is then added, in closed container
Carry out solvent thermal reaction；
Then lanthanum nitrate, manganese nitrate and strontium nitrate aqueous solution is added, after adjusting pH value of solution with lye, carries out hydro-thermal reaction,
Obtain reaction solution；
Reaction product in reaction solution is separated, is calcined after washing and drying, is obtained Ca-Ti ore type compound oxygen reduction and urge
Agent.
The present invention also provides a kind of preparation methods as described in claim 1~6 any one claim to be prepared into
The Ca-Ti ore type compound oxygen reduction catalyst arrived, the chemical formula of the Ca-Ti ore type compound oxygen reduction catalyst are La1-xMxMnO3-
CeO2, M is 30~500nm selected from Sr and/or Ca, 0≤x < 1.0, the partial size of the Ca-Ti ore type compound oxygen reduction catalyst, than
Surface area is 29.9cm-2g-1, pore volume 0.093cm3g-1。
The present invention also provides a kind of air cathode, Ca-Ti ore type compound oxygen reduction prepared by the preparation method
Catalyst preparation obtains.
The present invention is to the preparation method of the air cathode there is no specifically limited, and well known to a person skilled in the art methods
?.
In the present invention, it is preferred to be prepared as follows:
Solvent is added in above-mentioned Ca-Ti ore type compound oxygen reduction catalyst and conductive material under conditions of being stirred continuously, so
After add ptfe emulsion and polyvinyl alcohol water solution, obtain air cathode catalyst pulp；
Wherein, the mass ratio of the Ca-Ti ore type compound oxygen reduction catalyst and conductive material is (0.1~9): 1, preferably
(0.2~5): 1, further preferably (0.5~2): 1.
The solvent is selected from ethyl alcohol.The amount that the solvent is added is to make Ca-Ti ore type compound oxygen reduction catalyst and conduction material
The solid content of material is 1wt%~90wt%, preferably 5wt%~70wt%, further preferably 10wt%~50wt%.
The 60wt% of the ptfe emulsion (abbreviation PTFE).
The Ca-Ti ore type compound oxygen reduction catalyst and conductive carbon material gross mass and PTFE mass ratio be (0.1~
3): 1, preferably (0.2~2): 1, further preferably (0.5~1.5): 1.
The concentration of the polyvinyl alcohol water solution is 10wt%, or PVP or PVB water-soluble high-molecular material is water-soluble
Liquid.
Then, obtained air cathode catalyst pulp is compound in acquisition air cathode biscuit in metal support.Its
In, loading range: 0.1mg/cm2~100mg/cm2, preferably 0.5mg/cm2~80mg/cm2, further preferably 1mg/cm2~60mg/
cm2。
The compound method is rubbing method, infusion process or filtration method.
The metal support is selected from copper mesh, nickel screen, stainless (steel) wire, foam copper or nickel foam.
Then, air cathode biscuit roasts at a certain temperature obtains air cathode.The sintering temperature is 200~500
DEG C, preferably 220~450 DEG C, be further preferably 250~400 DEG C；The sintering time be 10~400 minutes, preferably 20~300
Minute, further preferably 30~200 minutes.
The present invention also provides a kind of metal-air battery, including air cathode, metal anode and electrolyte, the skies
Gas cathode is above-mentioned air cathode.
The metal anode is selected from aluminum metal anode, and the electrolyte is preferably KOH aqueous solution.
Solvent heat/hydrothermal synthesis method, which is improved, by a kind of interval substep has prepared La1-xMxMnO3-CeO2It is nano combined to urge
Agent is rich in the CeO of Lacking oxygen with surface2Material is to LaMnO3Based perovskite oxygen reduction catalyst carries out the modification of surface Lacking oxygen,
The electrocatalysis characteristic of composite material is significantly improved, and the composite catalyst is applied in the cathode of aluminium-air cell.
Using the solution of the present invention, two kinds of finely dispersed composite catalysts of component can be obtained, and Effective Regulation is multiple
The Mn-O-Ce bond energy for closing catalyst surface active site, significantly improves the oxygen adsorption capacity and oxygen on composite catalyst surface
Adsorption capacity inherently improves the electrocatalysis characteristic of Ca-Ti ore type compound oxygen reduction catalyst.
The catalytic composite material primary particle of this method preparation is smaller, and pattern is uniform, specific surface area with higher；System
Standby simple process is conducive to large-scale serial production.
For a further understanding of the present invention, Ca-Ti ore type compound oxygen reduction provided by the invention is urged below with reference to embodiment
The preparation method of agent and its application in metal-air battery are illustrated, and protection scope of the present invention is not by following implementation
The limitation of example.
Embodiment 1
Firstly, according to CeO2Amount cerous nitrate is dissolved in ethylene glycol, control CeO2Solid content is 10%；Again to above-mentioned solution
Middle that suitable tetrabutyl phosphonium bromide ammonium surfactant is added, control surfactant concentration is 0.1mmol/L；And it is added a certain amount of
Urea, control urea/CeO2Molar ratio 0.4 is thoroughly mixed uniformly obtained mixed solution.Above-mentioned mixed solution is shifted
Into the stainless steel cauldron of polytetrafluoroethyllining lining, the solvent thermal reaction 6 hours at a temperature of certain 180 DEG C；By above-mentioned reaction
Kettle is reduced to room temperature, obtains first step intermediate products.
At room temperature, it is added in Xiang Shangshu first step reaction kettle according to La0.7Sr0.3MnO3The lanthanum nitrate of stoichiometric ratio,
The aqueous solution of strontium nitrate, manganese nitrate controls CeO2/La0.7Sr0.3MnO3Proportion is 2/3；And form ethylene glycol and deionized water
Mixed solvent, control glycol/water ratio are 1；Sodium hydroxide solution by the way that 0.1mol/L is added adjusts above-mentioned mixed solvent
PH value pH value be then naturally cooling to room temperature solvent thermal reaction 6 hours at a temperature of 180 DEG C to 9, then by reaction kettle.So
Afterwards, dry after deionized water and ethyl alcohol alternately and repeatedly clean 3 times, then in 80 DEG C of baking ovens after product in reaction kettle being filtered
After obtain composite catalyst presoma；By above-mentioned presoma in 600 DEG C of temperature lower calcinations, 120 minutes acquisition composite catalyst materials
Material；Prepared catalytic composite material primary particle about 200 ± 30nm, about 3 ± 0.5 μm of second particle；Specific surface area is
29.9m2/ g, pore volume 0.093cm3/g.Obtained composite catalyst pattern, crystal form and electrochemical tests such as Fig. 2~
Shown in 6.
Take above-mentioned prepared composite catalyst powder and VXC-72 conductive carbon material, control composite catalyst/lead carbon materials
Expect that ratio is 1；It in the case where being stirred continuously, is added in ethyl alcohol, control solid content is 40%, is stirred evenly；Add one
Quantitative solid content is the ptfe emulsion of 60wt%, control composite catalyst and conductive carbon material gross mass/PTFE matter
Measuring ratio is 1, and is constantly stirred evenly；The polyvinyl alcohol water that configured mass content is 10% is added into above-mentioned slurry again
Solution, the mass percent for controlling polyvinyl alcohol is 2%, is stirred continuously, is uniformly dispersed, obtains air cathode catalyst pulp；
Above-mentioned slurry is coated by rubbing method and obtains air cathode biscuit on copper mesh supporter again, control coating loading is 50mg/
cm2；By above-mentioned air cathode biscuit in 300 DEG C of roasting temperatures, 120 minutes acquisition finished product air cathodes.
Finally, by air cathode piece and high purity aluminium metal anode assembling at monocell, in the KOH that electrolyte is 4mol/L
Electric discharge performance.The maximum power density of the aluminium-air cell tested out is 261.6mW/cm2, specific test result is as schemed
Shown in 7.
Embodiment 2
Firstly, according to CeO2Amount cerous nitrate is dissolved in ethylene glycol, control CeO2Solid content is 3%；Again into above-mentioned solution
Suitable tetrabutyl phosphonium bromide ammonium surfactant is added, control surfactant concentration is 0.01mmol/L；And it is added a certain amount of
Urea, control urea/CeO2Molar ratio 0.2 is thoroughly mixed uniformly obtained mixed solution.Above-mentioned mixed solution is shifted
Into the stainless steel cauldron of polytetrafluoroethyllining lining, the solvent thermal reaction 2 hours at a temperature of certain 85 DEG C；By aforesaid reaction vessel
It is reduced to room temperature, obtains first step intermediate products.
At room temperature, it is added in Xiang Shangshu first step reaction kettle according to LaMnO3Lanthanum nitrate, the manganese nitrate of stoichiometric ratio
Aqueous solution, control CeO2/LaMnO3Proportion is 0.1；And the mixed solvent of ethylene glycol and deionized water is formed, control ethylene glycol/
Water ratio is 2；Sodium hydroxide solution by the way that 0.1mol/L is added adjusts the pH value pH value of above-mentioned mixed solvent to 8, then will
Reaction kettle is then naturally cooling to room temperature solvent thermal reaction 2 hours at a temperature of 120 DEG C.Then, product in reaction kettle is filtered
Afterwards, composite catalyst forerunner is obtained after deionized water and ethyl alcohol alternately and repeatedly clean 3 times, then after drying in 120 DEG C of baking ovens
Body；By above-mentioned presoma in 400 DEG C of temperature lower calcinations, 60 minutes acquisition catalytic composite materials.；Prepared composite catalyst
Material primary particle about 180 ± 15nm, about 2 ± 0.1 μm of second particle；Specific surface area is 35.6m2/ g, pore volume are
0.098cm3/g
Take above-mentioned prepared composite catalyst powder and VXC-72 conductive carbon material, control composite catalyst/lead carbon materials
Expect that ratio is 0.5；It in the case where being stirred continuously, is added in ethyl alcohol, control solid content is 10%, is stirred evenly；It adds
A certain amount of solid content is the ptfe emulsion of 60wt%, control composite catalyst and conductive carbon material gross mass/PTFE
Mass values are 0.5, and constantly stir evenly；The polyethylene that configured mass content is 10% is added into above-mentioned slurry again
Alcohol solution, the mass percent for controlling polyvinyl alcohol is 1%, is stirred continuously, is uniformly dispersed, obtains air cathode catalyst slurry
Material；Above-mentioned slurry is coated by rubbing method and obtains air cathode biscuit on copper mesh supporter again, control coating loading is
5mg/cm2；By above-mentioned air cathode biscuit in 250 DEG C of roasting temperatures, 30 minutes acquisition finished product air cathodes.
Finally, by air cathode piece and high purity aluminium metal anode assembling at monocell, in the KOH that electrolyte is 4mol/L
Electric discharge performance.The maximum power density of the aluminium-air cell tested out is 220.5mW/cm2。
Embodiment 3
Firstly, according to CeO2Amount cerous nitrate is dissolved in ethylene glycol, control CeO2Solid content is 15%；Again to above-mentioned solution
Middle that suitable tetrabutyl phosphonium bromide ammonium surfactant is added, control surfactant concentration is 0.2mmol/L；And it is added a certain amount of
Urea, control urea/CeO2Molar ratio 0.8 is thoroughly mixed uniformly obtained mixed solution.Above-mentioned mixed solution is shifted
Into the stainless steel cauldron of polytetrafluoroethyllining lining, the solvent thermal reaction 20 hours at a temperature of certain 200 DEG C；By above-mentioned reaction
Kettle is reduced to room temperature, obtains first step intermediate products.
At room temperature, it is added in Xiang Shangshu first step reaction kettle according to La0.3Sr0.7MnO3The lanthanum nitrate of stoichiometric ratio,
The aqueous solution of strontium nitrate, manganese nitrate controls CeO2/La0.3Sr0.7MnO3Proportion is 2；And form the mixed of ethylene glycol and deionized water
Bonding solvent, control glycol/water ratio are 2；Sodium hydroxide solution by the way that 0.1mol/L is added adjusts above-mentioned mixed solvent
PH value pH value is then naturally cooling to room temperature solvent thermal reaction 30 hours at a temperature of 250 DEG C to 10, then by reaction kettle.So
Afterwards, dry after deionized water and ethyl alcohol alternately and repeatedly clean 3 times, then in 120 DEG C of baking ovens after product in reaction kettle being filtered
After obtain composite catalyst presoma；By above-mentioned presoma in 700 DEG C of temperature lower calcinations, 150 minutes acquisition composite catalyst materials
Material；Prepared catalytic composite material primary particle about 300 ± 30nm, about 4 ± 0.5 μm of second particle；Specific surface area is
22.5m2/ g, pore volume 0.055cm3/g。
Take above-mentioned prepared composite catalyst powder and VXC-72 conductive carbon material, control composite catalyst/lead carbon materials
Expect that ratio is 2；It in the case where being stirred continuously, is added in ethyl alcohol, control solid content is 50%, is stirred evenly；Add one
Quantitative solid content is the ptfe emulsion of 60wt%, control composite catalyst and conductive carbon material gross mass/PTFE matter
Measuring ratio is 1.5, and is constantly stirred evenly；The polyethylene that configured mass content is 10wt% is added into above-mentioned slurry again
Alcohol solution, the mass percent for controlling polyvinyl alcohol is 5%, is stirred continuously, is uniformly dispersed, obtains air cathode catalyst slurry
Material；Above-mentioned slurry is coated by rubbing method and obtains air cathode biscuit on copper mesh supporter again, control coating loading is
60mg/cm2；By above-mentioned air cathode biscuit in 400 DEG C of roasting temperatures, 200 minutes acquisition finished product air cathodes.
Finally, by air cathode piece and high purity aluminium metal anode assembling at monocell, in the KOH that electrolyte is 4mol/L
Electric discharge performance.The maximum power density of the aluminium-air cell tested out is 245.3mW/cm2。
Embodiment 4
Firstly, according to CeO2Amount cerous nitrate is dissolved in ethylene glycol, control CeO2Solid content is 12%；Again to above-mentioned solution
Middle that suitable tetrabutyl phosphonium bromide ammonium surfactant is added, control surfactant concentration is 0.15mmol/L；And it is added certain
The urea of amount controls urea/CeO2Molar ratio 0.5 is thoroughly mixed uniformly obtained mixed solution.Above-mentioned mixed solution is turned
It moves on in the stainless steel cauldron of polytetrafluoroethyllining lining, the solvent thermal reaction 4 hours at a temperature of certain 200 DEG C；It will be above-mentioned anti-
It answers kettle to be reduced to room temperature, obtains first step intermediate products.
At room temperature, it is added in Xiang Shangshu first step reaction kettle according to La0.5Sr0.5MnO3The lanthanum nitrate of stoichiometric ratio,
The aqueous solution of strontium nitrate, manganese nitrate controls CeO2/La0.5Sr0.5MnO3Proportion is 1；And form the mixed of ethylene glycol and deionized water
Bonding solvent, control glycol/water ratio are 0.8；Sodium hydroxide solution by the way that 0.1mol/L is added adjusts above-mentioned mixed solvent
PH value pH value be then naturally cooling to room temperature solvent thermal reaction 16 hours at a temperature of 190 DEG C to 9, then by reaction kettle.So
Afterwards, dry after deionized water and ethyl alcohol alternately and repeatedly clean 3 times, then in 110 DEG C of baking ovens after product in reaction kettle being filtered
After obtain composite catalyst presoma；By above-mentioned presoma in 650 DEG C of temperature lower calcinations, 150 minutes acquisition composite catalyst materials
Material, prepared catalytic composite material primary particle about 250 ± 20nm, about 3 ± 0.2 μm of second particle；Specific surface area is
26.8m2/ g, pore volume 0.073cm3/g。
Take above-mentioned prepared composite catalyst powder and VXC-72 conductive carbon material, control composite catalyst/lead carbon materials
Expect that ratio is 1.5；It in the case where being stirred continuously, is added in ethyl alcohol, control solid content is 45%, is stirred evenly；It adds
A certain amount of solid content is the ptfe emulsion of 60wt%, control composite catalyst and conductive carbon material gross mass/PTFE
Mass values are 1.5, and constantly stir evenly；The polyethylene that configured mass content is 10% is added into above-mentioned slurry again
Alcohol solution, the mass percent for controlling polyvinyl alcohol is 2.5%, is stirred continuously, is uniformly dispersed, obtains air cathode catalyst
Slurry；Above-mentioned slurry is coated by rubbing method and obtains air cathode biscuit on copper mesh supporter again, control coating loading is
75mg/cm2；By above-mentioned air cathode biscuit in 280 DEG C of roasting temperatures, 100 minutes acquisition finished product air cathodes.
Finally, by air cathode piece and high purity aluminium metal anode assembling at monocell, in the KOH that electrolyte is 4mol/L
Electric discharge performance.The maximum power density of the aluminium-air cell tested out is 241.8mW/cm2。
Embodiment 5
Firstly, according to CeO2Amount cerous nitrate is dissolved in ethylene glycol, control CeO2Solid content is 8%；Again into above-mentioned solution
Suitable tetrabutyl phosphonium bromide ammonium surfactant is added, control surfactant concentration is 0.2mmol/L；And it is added a certain amount of
Urea controls urea/CeO2Molar ratio 0.5 is thoroughly mixed uniformly obtained mixed solution.Above-mentioned mixed solution is transferred to
In the stainless steel cauldron of polytetrafluoroethyllining lining, the solvent thermal reaction 5 hours at a temperature of certain 150 DEG C；By aforesaid reaction vessel
It is reduced to room temperature, obtains first step intermediate products.
At room temperature, it is added in Xiang Shangshu first step reaction kettle according to La0.6Sr0.4MnO3The lanthanum nitrate of stoichiometric ratio,
The aqueous solution of strontium nitrate, manganese nitrate controls CeO2/La0.6Sr0.4MnO3Proportion is 0.5；And form ethylene glycol and deionized water
Mixed solvent, control glycol/water ratio are 2；Sodium hydroxide solution by the way that 0.1mol/L is added adjusts above-mentioned mixed solvent
PH value pH value be then naturally cooling to room temperature solvent thermal reaction 5 hours at a temperature of 220 DEG C to 10, then by reaction kettle.So
Afterwards, dry after deionized water and ethyl alcohol alternately and repeatedly clean 3 times, then in 110 DEG C of baking ovens after product in reaction kettle being filtered
After obtain composite catalyst presoma；By above-mentioned presoma in 680 DEG C of temperature lower calcinations, 100 minutes acquisition composite catalyst materials
Material, prepared catalytic composite material primary particle about 280 ± 30nm, about 3 ± 0.2 μm of second particle；Specific surface area is
24.3m2/ g, pore volume 0.068cm3/g。
Take above-mentioned prepared composite catalyst powder and VXC-72 conductive carbon material, control composite catalyst/lead carbon materials
Expect that ratio is 1.5；It in the case where being stirred continuously, is added in ethyl alcohol, control solid content is 35%, is stirred evenly；It adds
A certain amount of solid content is the ptfe emulsion of 60wt%, control composite catalyst and conductive carbon material gross mass/PTFE
Mass values are 2, and constantly stir evenly；The polyvinyl alcohol that configured mass content is 10% is added into above-mentioned slurry again
Aqueous solution, the mass percent for controlling polyvinyl alcohol is 2.5%, is stirred continuously, is uniformly dispersed, obtains air cathode catalyst slurry
Material；Above-mentioned slurry is coated by rubbing method and obtains air cathode biscuit on copper mesh supporter again, control coating loading is
55mg/cm2；By above-mentioned air cathode biscuit in 280 DEG C of roasting temperatures, 150 minutes acquisition finished product air cathodes.
Finally, by air cathode piece and high purity aluminium metal anode assembling at monocell, in the KOH that electrolyte is 4mol/L
Electric discharge performance.The maximum power density of the aluminium-air cell tested out is 233.4mW/cm2。
Comparative example
Firstly, according to CeO2/La0.7Sr0.3MnO3Amount (CeO2/La0.7Sr0.3MnO3Proportion is 2/3) by cerous nitrate, nitre
Sour lanthanum, strontium nitrate, manganese nitrate are dissolved in deionized water；Then suitable tetrabutylammonium bromide is added into above-mentioned solution again (referred to as
TBAB) surfactant, control surfactant concentration are 0.1mmol/L；And a certain amount of urea is added, control urea/
CeO2Molar ratio 0.4 is thoroughly mixed uniformly obtained mixed solution.Sodium hydroxide solution by the way that 0.1mol/L is added is adjusted
The pH value pH value of above-mentioned mixed solvent is to 9；Above-mentioned mixed solution is transferred to the stainless steel cauldron of polytetrafluoroethyllining lining
In；By reaction kettle at 180 DEG C hydro-thermal reaction 6 hours, be then naturally cooling to room temperature.Then, product in reaction kettle is filtered
Afterwards, composite catalyst forerunner is obtained after deionized water and ethyl alcohol alternately and repeatedly clean 3 times, then after drying in 80 DEG C of baking ovens
Body；By above-mentioned presoma in 600 DEG C of temperature lower calcinations, 120 minutes acquisition catalytic composite materials.Obtained composite catalyst
Pattern, crystal form and electrochemical tests are as shown in figs. 8-10.Prepared catalytic composite material particle size is very uneven
Even, size is between 5~500nm；Second particle is reunited seriously, and about 6 ± 3 μm；Specific surface area is 15m2/ g, pore volume are
0.055cm3/g
Take above-mentioned prepared composite catalyst powder and VXC-72 conductive carbon material, control composite catalyst/lead carbon materials
Expect that ratio is 1；It in the case where being stirred continuously, is added in ethyl alcohol, control solid content is 40wt%, is stirred evenly；It adds
A certain amount of solid content is the ptfe emulsion of 60Wt%, control composite catalyst and conductive carbon material gross mass/PTFE
Mass values are 1, and constantly stir evenly；The polyvinyl alcohol that configured mass content is 10% is added into above-mentioned slurry again
Aqueous solution, the mass percent for controlling polyvinyl alcohol is 2%, is stirred continuously, is uniformly dispersed, obtains air cathode catalyst slurry
Material；Above-mentioned slurry is coated by rubbing method and obtains air cathode biscuit on copper mesh supporter again, control coating loading is
80mg/cm2；By above-mentioned air cathode biscuit in 200 DEG C of roasting temperatures, 120 minutes acquisition finished product air cathodes.
Finally, by air cathode piece and high purity aluminium metal anode assembling at monocell, in the KOH that electrolyte is 4mol/L
Electric discharge performance.The maximum power density of the aluminium-air cell tested out is 198.6mW/cm2, specific test result is as schemed
Shown in 11.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (9)
1. a kind of preparation method of Ca-Ti ore type compound oxygen reduction catalyst, which comprises the following steps:
A it is anti-that solvent heat is carried out in confined conditions after) mixing cerium source compound, acid-base buffer agent, surfactant and solvent
It answers, obtains reaction solution；
B lanthanum source compound, manganese source compound and the compound containing M element) are added in Xiang Suoshu reaction solution, obtains mixed solution,
After the pH value for adjusting the mixed solution, hydro-thermal reaction is carried out, catalyst precursor is obtained；
C) catalyst precursor is calcined, obtains Ca-Ti ore type compound oxygen reduction catalyst, the Ca-Ti ore type is multiple
The chemical formula for closing oxygen reduction catalyst is La1-xMxMnO3-CeO2, M is selected from Sr and/or Ca, 0≤x < 1.0.
2. preparation method according to claim 1, which is characterized in that the cerium source compound is selected from cerous nitrate and/or second
Sour cerium；
The lanthanum source compound is selected from lanthanum nitrate and/or lanthanum acetate；
Compound containing M element is selected from one of strontium nitrate, strontium acetate, calcium nitrate and calcium acetate or a variety of；
The manganese source compound is selected from manganese nitrate and/or manganese acetate；
The acid-base buffer agent is selected from urea, ammonium chloride or ammonium carbonate；
The surfactant is selected from tetrabutylammonium bromide；
The solvent is selected from ethylene glycol.
3. preparation method according to claim 1, which is characterized in that the temperature of the solvent thermal reaction is 80~250 DEG C,
The time of the solvent thermal reaction is 0.5~40 hour.
4. preparation method according to claim 1, which is characterized in that adjust the pH adjusting agent of the pH value of the mixed solution
Selected from sodium hydroxide, potassium hydroxide or ammonium hydroxide, pH value is adjusted to 6~14.
5. preparation method according to claim 1, which is characterized in that the temperature of the hydro-thermal reaction is 80~350 DEG C, institute
The time for stating hydro-thermal reaction is 0.5~40 hour.
6. preparation method according to claim 1, which is characterized in that the temperature of the calcining is 200~900 DEG C, described
The time of calcining is 10~250min.
7. a kind of Ca-Ti ore type that the preparation method as described in claim 1~6 any one claim is prepared is compound
Oxygen reduction catalyst, the chemical formula of the Ca-Ti ore type compound oxygen reduction catalyst are La1-xMxMnO3-CeO2, M be selected from Sr and/
Or Ca, 0≤x < 1.0, the partial size of the Ca-Ti ore type compound oxygen reduction catalyst are 30~500nm, specific surface area 29.9cm- 2g-1, pore volume 0.093cm3g-1。
8. a kind of air cathode, which is characterized in that the preparation method system as described in claim 1~6 any one claim
Standby obtained Ca-Ti ore type compound oxygen reduction catalyst preparation obtains.
9. a kind of metal-air battery, which is characterized in that including air cathode, metal anode and electrolyte, the air yin
Air cathode extremely according to any one of claims 8.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110911699A (en) * | 2019-12-06 | 2020-03-24 | 中国科学院宁波材料技术与工程研究所 | Bifunctional catalyst, preparation method thereof and application thereof in zinc-air battery |
| CN111604045A (en) * | 2020-04-13 | 2020-09-01 | 清华大学 | Nickel-based oxygen vacancy carrier catalyst and preparation method and application thereof |
| CN111769297A (en) * | 2020-07-17 | 2020-10-13 | 郑州佛光发电设备有限公司 | Cathode catalyst of aluminum-air battery and preparation method thereof |
| CN111900419A (en) * | 2020-09-07 | 2020-11-06 | 重庆新申世纪新材料科技有限公司 | Preparation method of manganese oxide in-situ composite air electrode |
| CN114005999A (en) * | 2021-09-06 | 2022-02-01 | 中国地质大学(武汉)浙江研究院 | Bifunctional electrocatalyst and preparation method and application thereof |
| CN114068949A (en) * | 2021-11-19 | 2022-02-18 | 四川大学 | High-performance titanium-based low-platinum catalyst, preparation method thereof and application thereof in fuel cell |
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| CN111604045B (en) * | 2020-04-13 | 2021-04-02 | 清华大学 | Nickel-based oxygen vacancy carrier catalyst and preparation method and application thereof |
| CN111769297A (en) * | 2020-07-17 | 2020-10-13 | 郑州佛光发电设备有限公司 | Cathode catalyst of aluminum-air battery and preparation method thereof |
| CN111900419A (en) * | 2020-09-07 | 2020-11-06 | 重庆新申世纪新材料科技有限公司 | Preparation method of manganese oxide in-situ composite air electrode |
| CN114005999A (en) * | 2021-09-06 | 2022-02-01 | 中国地质大学(武汉)浙江研究院 | Bifunctional electrocatalyst and preparation method and application thereof |
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| CN114068949A (en) * | 2021-11-19 | 2022-02-18 | 四川大学 | High-performance titanium-based low-platinum catalyst, preparation method thereof and application thereof in fuel cell |
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