CN113363514B - Carbon aerogel supported cobalt monoatomic catalyst for metal air battery, preparation method and application thereof - Google Patents
Carbon aerogel supported cobalt monoatomic catalyst for metal air battery, preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 93
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 79
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 73
- 239000010941 cobalt Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 title claims description 22
- 239000002184 metal Substances 0.000 title claims description 22
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 14
- 125000004429 atom Chemical group 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 229920001661 Chitosan Polymers 0.000 claims description 96
- 239000007864 aqueous solution Substances 0.000 claims description 68
- 238000003756 stirring Methods 0.000 claims description 57
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 45
- 239000004964 aerogel Substances 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 31
- 239000000017 hydrogel Substances 0.000 claims description 26
- 238000009210 therapy by ultrasound Methods 0.000 claims description 26
- 238000001035 drying Methods 0.000 claims description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 19
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 15
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000009467 reduction Effects 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 12
- 238000003763 carbonization Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 7
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 6
- 239000000377 silicon dioxide Substances 0.000 claims description 6
- 235000012239 silicon dioxide Nutrition 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 238000009792 diffusion process Methods 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000002639 sodium chloride Nutrition 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- FDJOLVPMNUYSCM-WZHZPDAFSA-L cobalt(3+);[(2r,3s,4r,5s)-5-(5,6-dimethylbenzimidazol-1-yl)-4-hydroxy-2-(hydroxymethyl)oxolan-3-yl] [(2r)-1-[3-[(1r,2r,3r,4z,7s,9z,12s,13s,14z,17s,18s,19r)-2,13,18-tris(2-amino-2-oxoethyl)-7,12,17-tris(3-amino-3-oxopropyl)-3,5,8,8,13,15,18,19-octamethyl-2 Chemical compound [Co+3].N#[C-].N([C@@H]([C@]1(C)[N-]\C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C(\C)/C1=N/C([C@H]([C@@]1(CC(N)=O)C)CCC(N)=O)=C\C1=N\C([C@H](C1(C)C)CCC(N)=O)=C/1C)[C@@H]2CC(N)=O)=C\1[C@]2(C)CCC(=O)NC[C@@H](C)OP([O-])(=O)O[C@H]1[C@@H](O)[C@@H](N2C3=CC(C)=C(C)C=C3N=C2)O[C@@H]1CO FDJOLVPMNUYSCM-WZHZPDAFSA-L 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229930003779 Vitamin B12 Natural products 0.000 claims description 2
- NVJHHSJKESILSZ-UHFFFAOYSA-N [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 Chemical compound [Co].N1C(C=C2N=C(C=C3NC(=C4)C=C3)C=C2)=CC=C1C=C1C=CC4=N1 NVJHHSJKESILSZ-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 235000010216 calcium carbonate Nutrition 0.000 claims description 2
- 238000010000 carbonizing Methods 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- OEZXFVMHAJJKKK-UHFFFAOYSA-N cobalt;1,10-phenanthroline Chemical compound [Co].C1=CN=C2C3=NC=CC=C3C=CC2=C1 OEZXFVMHAJJKKK-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 239000002608 ionic liquid Substances 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 238000003786 synthesis reaction Methods 0.000 claims description 2
- 239000011715 vitamin B12 Substances 0.000 claims description 2
- 235000019163 vitamin B12 Nutrition 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims 1
- 238000007710 freezing Methods 0.000 claims 1
- 230000008014 freezing Effects 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 3
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 description 14
- 239000010411 electrocatalyst Substances 0.000 description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 11
- 238000000967 suction filtration Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 230000006196 deacetylation Effects 0.000 description 9
- 238000003381 deacetylation reaction Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 5
- 239000004202 carbamide Substances 0.000 description 5
- 229910052725 zinc Inorganic materials 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 2
- 239000004472 Lysine Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 2
- 235000018417 cysteine Nutrition 0.000 description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011245 gel electrolyte Substances 0.000 description 2
- 239000004220 glutamic acid Substances 0.000 description 2
- 235000013922 glutamic acid Nutrition 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 description 2
- 239000004246 zinc acetate Substances 0.000 description 2
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- KDXKERNSBIXSRK-YFKPBYRVSA-N L-lysine Chemical compound NCCCC[C@H](N)C(O)=O KDXKERNSBIXSRK-YFKPBYRVSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000011865 Pt-based catalyst Substances 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- -1 cobalt macrocyclic compound Chemical class 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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
- H01M4/9008—Organic or organo-metallic compounds
-
- 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
- H01M4/88—Processes of manufacture
-
- 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a carbon aerogel supported cobalt monoatomic catalyst for a metal-air battery, and belongs to the technical field of metal-air batteries. The catalyst carrier is porous carbon aerogel, the specific surface area of the porous carbon aerogel is 100-800 m 2g‑1, the pore diameter is 2-100 nm, the pore volume is 0.05-1.0 cm 3g‑1, and the active component is cobalt monoatoms which are uniformly distributed on the surface of the porous carbon aerogel and coordinate with hetero atoms; the composition of the catalyst is as follows: the content of the porous carbon aerogel is 67-95.95 wt%, the content of cobalt single atoms is 0.05-8.0 wt%, and the content of hetero atoms is 4-25 wt%. The catalyst of the invention has high content of cobalt single atoms, uniform dispersion and stable physical and chemical structure. The preparation method is green and simple and has low cost; the catalyst is applied to metal-air batteries, has excellent charge-discharge efficiency and cycle life, and has better performance than commercial Pt/C catalysts.
Description
Technical Field
The invention belongs to the technical field of metal air batteries, and particularly relates to a carbon aerogel supported cobalt monoatomic catalyst for a metal air battery, a preparation method and application thereof.
Background
With the increasing global energy and environmental crisis, the development of environmentally friendly energy conversion and storage devices has received increasing attention. Among them, metal-air batteries are attracting attention because of environmental friendliness, abundant resources, high safety, and high energy density. However, the metal-air battery has problems of slow Oxygen Reduction Reaction (ORR) kinetics during discharge, resulting in short cycle life, low energy efficiency, high overpotential, and the like. It is well known that noble metal Pt-based nanocatalysts have excellent electrocatalytic ORR activity, but are scarce in reserves, costly, poor in methanol resistance, and particularly poor in stability, severely hampering their practical use. Therefore, it is critical and significant to develop efficient, economical and stable non-noble metal catalysts for electrocatalytic ORR instead of Pt-based catalysts.
In order to solve the above problems, transition metal oxide particles have been developed in the prior art as ORR electrocatalysts. For example, nano catalysts represented by Co, fe, ni and the like reported in Chinese patent CN 107308977A, CN 111785977A and CN 106450357A are low in price, rich in reserves and excellent in ORR catalytic activity. However, when the transition metal nanoparticles are used as ORR electrocatalysts, the defects of low metal atom utilization rate, small specific surface area, poor conductivity and the like still exist. Compared with the transition metal nano particles and nano clusters, the transition metal monoatomic catalyst has absolute advantages in the electrocatalytic ORR due to the characteristics of high atom utilization rate, high catalytic efficiency, uniform active sites and the like. The transition metal single atom is loaded on a carbon-based carrier with excellent conductivity (such as graphene, carbon nano tube, graphite carbon, carbon aerogel and the like), so that the problem of poor catalyst conductivity can be solved, and the stability of the transition metal atom and the specific surface area of the composite catalyst can be improved. Therefore, research on the carbon-based carrier-supported transition metal monoatomic catalyst is of great significance in developing a high-efficiency ORR electrocatalyst. The carbon aerogel has good conductivity, large specific surface area and good chemical stability, and is a good carrier of the metal monoatomic catalyst.
Chitosan is a biomass resource with rich natural reserves, can be regenerated and degraded, can form hydrogel when meeting metal ions, and can form chitosan-metal ion aerogel after freeze drying, and the aerogel is an excellent carbon aerogel precursor. At present, journals at home and abroad report a plurality of preparation methods for preparing carbon aerogel supported cobalt-based catalysts by taking chitosan and inorganic cobalt salt (CoCl 2、Co(NO3)2) as precursors and electrocatalytic oxygen reduction application thereof, but heat treatment of chitosan-cobalt ion aerogel at high temperature causes cobalt atoms to agglomerate to form cobalt sulfide or cobalt oxide nano particles and the like, so that single cobalt atom active sites are difficult to generate. According to reference, research on preparing a carbon aerogel loaded cobalt monoatom as an ORR catalyst by taking chitosan and cobalt macrocyclic compound or cobalt-organic ligand complex as a carbon source and a cobalt source has not been reported, and the catalyst is expected to be applied to metal-air batteries.
Disclosure of Invention
In view of the above-mentioned current situation, an object of the present invention is to provide a carbon aerogel supported cobalt single-atom catalyst for metal-air batteries, which can improve the utilization rate and mass transfer capability of cobalt atoms, and the single cobalt atoms can exist stably on a porous carbon aerogel carrier, and has high catalytic efficiency and good catalytic stability. Meanwhile, the invention also provides a preparation method of the catalyst, which fully utilizes biomass chitosan with wide sources as a carbon source and cobalt with rich content as a raw material, has low cost, can realize large-scale preparation of the cobalt monoatomic catalyst, and has simple operation process.
The invention is realized by the following technical scheme:
the carbon aerogel supported cobalt monoatomic catalyst for the metal air battery is characterized in that a catalyst carrier is porous carbon aerogel, the specific surface area of the porous carbon aerogel is 100-800 m 2g-1, the pore diameter is 2-100 nm, the pore volume is 0.05-1.0 cm 3g-1, and active components are cobalt monoatoms which are uniformly distributed on the surface of the porous carbon aerogel and coordinate with hetero atoms; the composition of the catalyst is as follows: the content of the porous carbon aerogel is 67-wt% -95.95 wt%, the content of cobalt single atoms is 0.05-wt% -8.0 wt%, and the content of hetero atoms is 4-wt% -25 wt%.
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) Synthesis of chitosan hybrid hydrogel: dissolving chitosan in an acetic acid aqueous solution, uniformly stirring to obtain a chitosan aqueous solution, then adding a pore-forming agent into the chitosan aqueous solution, uniformly stirring and mixing, sequentially slowly dropwise adding a heteroatom-containing precursor solution and a cobalt precursor solution into a uniformly mixed system under stirring, uniformly stirring, and performing ultrasonic treatment until chitosan hybrid hydrogel is obtained;
(2) Performing vacuum freeze drying on the chitosan hybrid hydrogel prepared in the step (1) to obtain chitosan hybrid aerogel;
(3) Carbonizing the chitosan hybrid aerogel obtained in the step (2) at a high temperature under the protection of inert atmosphere to enable cobalt atoms and nitrogen atoms to carry out coordination reaction in a high-temperature environment;
(4) And (3) soaking in an acid solution to remove the pore-forming agent, repeatedly carrying out suction filtration and washing with deionized water to neutrality, and finally drying to obtain the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery.
As a preferable technical scheme, for the preparation method, in the step (1), the mass fraction of the chitosan aqueous solution is 1% -3%; the acetic acid aqueous solution is 2% -5% acetic acid aqueous solution in percentage by mass; the heteroatom precursor comprises one or more of lysine, cysteine, urea, thiourea, ethylenediamine, dicyandiamide, melamine and glutamic acid; the heteroatom-containing precursor solution is an aqueous solution or an organic solution with a mass percentage concentration of 15% -25%.
As a preferred technical scheme, for the preparation method, in the step (1), the cobalt precursor comprises one or more of cobalt-based ionic liquid, vitamin B12 (also called cobalamin), cobalt porphyrin, cobalt phthalocyanine, porphyrin-cobalt acetate complex, cobalt-phenanthroline complex and sulfonated cobalt phthalocyanine; the cobalt precursor solution is an aqueous solution or an organic solution with the mass percentage concentration of 4% -14%.
As a preferred technical scheme, for the preparation method, in the step (1), the pore-forming agent comprises one or more of silicon dioxide, calcium carbonate, sodium carbonate, zinc chloride and sodium chloride; the mass fraction of the pore-forming agent is 1% -5%.
As a preferred technical scheme, for the preparation method, in the step (2), the chitosan hybrid aerogel is composed of the following precursors in mass fraction:
chitosan: 1 wt to 5wt percent,
Pore-forming agent: 1 wt to 5wt percent,
Heteroatom-containing precursors: 77 weight percent to 95 wt percent,
Cobalt precursor: 3 wt% -13% wt%.
As a preferable technical scheme, for the preparation method, in the step (3), the inert atmosphere is high-purity nitrogen or high-purity argon; the high-temperature carbonization comprises the following steps: the first step: heating from room temperature to T, wherein T is 700-1000 ℃, the heating rate is 4-8 ℃/min, and the second step: keeping the temperature T for 1-3 h at constant temperature, and performing a third step: and cooling from T to room temperature at a cooling rate of 4-10 ℃/min.
As a preferable technical scheme, for the preparation method, in the step (4), the acid solution is at least one of hydrofluoric acid aqueous solution, hydrochloric acid aqueous solution, nitric acid aqueous solution and sulfuric acid aqueous solution; the acid solution is 0.5-2 mol/L acid solution, the acid soaking time is 12-24 h, and the acid soaking temperature is 60-100 ℃.
Preferably, for the preparation method, in the step (1), the stirring mode is mechanical stirring or magnetic stirring, and the stirring temperature is 5-30 ℃; the ultrasonic treatment temperature is 5-40 ℃, the ultrasonic treatment time is 2-5 h, and the ultrasonic treatment frequency is 100-1200W.
Preferably, for the preparation method, in the step (2), the vacuum freeze-drying step is that the vacuum freeze-drying step is carried out for 5-12 hours at-25 to-55 ℃ and then the vacuum freeze-drying step is carried out for 24-48 hours under the vacuum environment of 0.0-10 Mpa.
Preferably, in the preparation method, in the step (4), the drying mode is freeze drying or vacuum drying, the pressure is 0.0-10 Mpa, the drying temperature is-25 to-55 ℃, the drying time is 24-48 h, the pressure is-0.5 to-1 Mpa, the drying temperature is 60-120 ℃ and the drying time is 8-12 h during freeze drying.
The preparation method provided by the invention is simple to operate, the raw materials such as chitosan, sulfonated cobalt phthalocyanine and urea are cheap and easy to obtain, the preparation conditions are mild, the mass production can be realized, and the method is easy to be applied and popularized in actual industry.
The carbon aerogel supported cobalt monoatomic catalyst for the metal air battery, which is prepared by the invention, has the advantages that the cobalt monoatoms and the nitrogen atoms are coordinated and uniformly and stably distributed on the porous carbon aerogel carrier, so that the utilization rate and stability of the cobalt monoatoms can be improved.
The carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery, which is prepared by the invention, can realize the accurate and effective regulation and control of the coordination structure between cobalt monoatoms and hetero atoms (nitrogen atoms), and can realize the effective regulation and control of the electron density around the cobalt monoatoms.
Furthermore, the invention also provides application of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery in electrocatalytic oxygen reduction.
Furthermore, the invention also provides a metal-air battery, which comprises an air positive electrode, a diaphragm, electrolyte and a metal negative electrode, wherein the air positive electrode comprises a gas diffusion layer, a current collector layer and a catalyst layer, and the catalyst adopts the carbon aerogel-supported cobalt single-atom catalyst for the metal-air battery, which is better than a commercial Pt/C catalyst in performance and can meet the requirements of industrial production and application.
The metal-air battery as described above, in particular, provides a zinc-air battery having excellent charge-discharge efficiency and cycle life. The zinc air cell tests include, but are not limited to: the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery is used as an air anode catalyst, the anode is a metal zinc sheet, and the electrolyte is an aqueous solution of 6 mol/L KOH+0.2 mol/L zinc acetate or a gel electrolyte thereof.
The beneficial effects of the invention are as follows:
(1) According to the carbon aerogel supported cobalt monoatomic catalyst for the metal air battery, the cobalt monoatoms and the nitrogen atoms are coordinately anchored on the porous carbon aerogel carrier, so that the catalyst has a stable physical and chemical structure, and the cobalt monoatoms are uniformly dispersed and high in content, so that the utilization rate of the cobalt atoms and the catalytic stability are improved.
(2) The carbon aerogel supported cobalt single-atom catalyst for the metal air battery has the advantages that the preparation method is simple, and the strategy of synergistic protection of sulfonated cobalt phthalocyanine, nitrogen atoms and chitosan hydrogel is used, so that the aggregation of cobalt atoms in the high-temperature carbonization process is avoided, and the monodispersion position falling of the cobalt atoms is realized.
(3) According to the carbon aerogel supported cobalt monoatomic catalyst for the metal air battery, the pore-forming agent is used for regulating and controlling the specific surface area and the pore diameter structure of the carbon aerogel during preparation, and the porous carbon aerogel is used as a carrier of cobalt monoatoms, so that the catalyst has a rich multi-stage pore structure, the mass transfer capacity is improved, the specific surface area of the catalyst is larger, the number of active sites is increased, and the catalytic activity is improved.
(4) The carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery can be applied to the metal-air battery, such as a zinc-air battery, and has excellent charge and discharge efficiency and cycle life.
Drawings
In order to more clearly illustrate the technical solutions of embodiments of the present application, the following description will briefly explain the embodiments or the drawings required to be used in the description of the prior art, where the drawings are intended to provide a further description of the present application and form a part thereof, and the exemplary embodiments of the present application and the description thereof are intended to explain the present application and not to limit the present application unduly.
Fig. 1 is a Scanning Transmission Electron Microscope (STEM) photograph of a carbon aerogel supported cobalt monoatomic catalyst for a metal-air battery of example 1.
Fig. 2 is an XRD characterization of the carbon aerogel supported cobalt monoatomic catalyst for a metal-air battery of example 1.
Fig. 3 is a BET characterization of a carbon aerogel supported cobalt single-atom catalyst for a metal-air battery of example 1.
Fig. 4 is a Cyclic Voltammetry (CV) curve of electrocatalytic oxygen reduction with a carbon aerogel supported cobalt monoatomic catalyst for a metal air battery of example 1.
Fig. 5 is a Linear Scan (LSV) curve of electrocatalytic oxygen reduction with a carbon aerogel supported cobalt monoatomic catalyst for a metal air battery of example 1.
FIG. 6 is a methanol resistance test of example 1 carbon aerogel supported cobalt single atom catalyst for metal air batteries and commercial Pt/C electrocatalytic oxygen reduction.
Fig. 7 is a stability test of electrocatalytic oxygen reduction with carbon aerogel supported cobalt single atom catalyst for metal air battery of example 1.
Fig. 8 is an open circuit potential test of example 1 carbon aerogel supported cobalt single atom catalyst for metal air cells and commercial Pt/C application to zinc air cells.
Fig. 9 is a specific capacity test of example 1 carbon aerogel supported cobalt single-atom catalyst for metal-air batteries applied to zinc-air batteries.
Fig. 10 is a charge-discharge curve of example 1 carbon aerogel supported cobalt single-atom catalyst for metal-air batteries applied to zinc-air batteries.
Detailed Description
For a better understanding of the present application, reference will be made to the following description of the application taken in conjunction with the accompanying drawings and examples. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
Example 1
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) 78 mg chitosan (viscosity 100-200 mpa.s, deacetylation degree more than or equal to 95%) is weighed and dissolved in 7.7 ml of 2 wt% acetic acid aqueous solution, stirring is carried out at room temperature to obtain chitosan aqueous solution, then 78 mg silicon dioxide pore-forming agent is added into the chitosan aqueous solution, after stirring is carried out uniformly, 41 ml aqueous solution with 7.41 g urea dissolved therein is added, stirring is carried out uniformly, then 5.6 ml aqueous solution with 234 mg sulfonated cobalt phthalocyanine dissolved therein is continuously added dropwise, stirring is carried out continuously for 1h, and ultrasonic 2h defoaming is carried out until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 5 ℃, the ultrasonic treatment temperature is 15 ℃, and the ultrasonic treatment frequency is 800W; (2) Placing the chitosan hybrid hydrogel obtained in the step (1) into a freeze dryer at the temperature of minus 45 ℃ to cool 12 h, and drying 24-h in a vacuum environment of 10-Mpa to obtain chitosan hybrid aerogel; (3) Placing the chitosan hybrid aerogel obtained in the step (2) in a tube furnace, under the protection of high-purity argon (gas flow rate is 5 ml/min), performing high-temperature carbonization treatment on the chitosan hybrid aerogel, heating to 800 ℃ at a speed of 4 ℃/min, roasting 2h, and then cooling to room temperature at a speed of 5 ℃/min; (4) And (3) putting the sample obtained in the step (3) into 0.5 mol/L hydrofluoric acid solution at 80 ℃ to remove silicon dioxide nano particles, then washing to be neutral by deionized and suction filtration, and vacuum drying at-0.5 Mpa and 100 ℃ for 12 h to obtain the carbon aerogel loaded Co single-atom electrocatalyst which is named as Co SA-N-S/C-800.
The carbon aerogel loaded with Co monoatoms is characterized by adopting a Scanning Transmission Electron Microscope (STEM), and as can be seen from the attached figure 1, co is uniformly dispersed on the surface of the porous carbon aerogel in a monodisperse atom form. The catalyst was examined by XRD, and as can be seen from the XRD results of fig. 2, the obtained catalyst did not find diffraction peaks of Co-based nanoparticles, indicating that Co was dispersed in the form of single atoms on the porous carbon aerogel. The catalyst is characterized by BET, and the BET result of the attached figure 3 shows that the specific surface area of the obtained catalyst is 145 m 2g-1, and the pore size structure is 2-100 nm.
Example 2
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) Weighing 390 mg chitosan (viscosity 100-200 mpa.s, deacetylation degree not less than 95%) and dissolving in 19.11 ml of 2wt% acetic acid aqueous solution, stirring uniformly at room temperature to obtain chitosan aqueous solution, then adding 390 mg sodium chloride pore-forming agent, adding 18.1 ml aqueous solution with 6.006 g urea dissolved therein after stirring uniformly, continuously and slowly dropwise adding 12 ml aqueous solution with 1.014 g sulfonated cobalt phthalocyanine dissolved therein after stirring uniformly, continuously stirring 1 h, and removing bubbles by ultrasonic 5 h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 15 ℃, the ultrasonic treatment temperature is 20 ℃, and the ultrasonic treatment frequency is 100W; (2) Putting the chitosan hybrid hydrogel obtained in the step (1) into a freeze dryer at the temperature of minus 55 ℃ to be frozen for 10 h, and drying 36 h in a vacuum environment of 8 Mpa to obtain chitosan hybrid aerogel; (3) Placing the chitosan hybrid aerogel obtained in the step (2) in a tube furnace, under the protection of high-purity argon (gas flow rate is 5 ml/min), performing high-temperature carbonization treatment on the chitosan hybrid aerogel, heating to 1000 ℃ at a speed of 4 ℃/min, roasting 2 h, and then cooling to room temperature at a speed of 5 ℃/min; (4) And (3) placing the sample obtained in the step (3) into 2 mol/L sulfuric acid solution at 60 ℃ to remove Co-based nano particles possibly generated, then washing to neutrality by deionized and suction filtration, and vacuum drying 8 h at-1 Mpa and 120 ℃ to obtain the carbon aerogel loaded Co single-atom electrocatalyst which is denoted as Co SA-N-S/C-1000.
Example 3
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) 78 mg chitosan (viscosity 100-200 mpa.s, deacetylation degree more than or equal to 95%) is weighed and dissolved in 7.7 ml of 2 wt% acetic acid aqueous solution, stirring is carried out at room temperature to obtain chitosan aqueous solution, then 234 mg sodium carbonate pore-forming agent is added into the chitosan aqueous solution, after stirring is carried out uniformly, 27. 27 ml aqueous solution with 6.708g thiourea dissolved therein is added, stirring is carried out uniformly, then 7 ml aqueous solution with 780 mg sulfonated cobalt phthalocyanine dissolved therein is slowly added dropwise, stirring is carried out continuously for 1 h, ultrasonic 3h foam removal is carried out until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 25 ℃, the ultrasonic treatment temperature is 35 ℃, and the ultrasonic treatment frequency is 1200W; (2) Placing the chitosan hybrid hydrogel obtained in the step (1) into a freeze dryer at the temperature of minus 45 ℃ to be frozen by 8 h, and drying 48 and h in a vacuum environment of 5 and Mpa to obtain chitosan hybrid aerogel; (3) Placing the chitosan hybrid aerogel obtained in the step (2) in a tube furnace, under the protection of high-purity argon (gas flow rate is 5 ml/min), performing high-temperature carbonization treatment on the chitosan hybrid aerogel, heating to 800 ℃ at a speed of 4 ℃/min, roasting 2h, and then cooling to room temperature at a speed of 5 ℃/min; (4) And (3) placing the sample obtained in the step (3) into 0.5 mol/L sulfuric acid solution at 100 ℃ to remove Co-based nano particles possibly generated, then washing to be neutral by deionized and suction filtration, and drying in vacuum at-1 Mpa and 60 ℃ for 10 h to obtain the carbon aerogel loaded Co single-atom electrocatalyst.
Example 4
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) 78 mg chitosan (viscosity 100-200 mpa.s, deacetylation degree more than or equal to 95%) is weighed and dissolved in 7.7 ml of 3 wt% acetic acid aqueous solution, stirring is carried out at room temperature to obtain chitosan aqueous solution, then 390 mg calcium carbonate pore-forming agent is added into the chitosan aqueous solution, after stirring is carried out uniformly, 27. 27 ml aqueous solution with 6.708 g dicyandiamide dissolved therein is added into the chitosan aqueous solution, stirring is carried out uniformly, then 3.85 ml aqueous solution with 624 mg sulfonated cobalt phthalocyanine dissolved therein is continuously dropwise added into the chitosan aqueous solution, stirring is carried out continuously for 1 h, and ultrasonic 2 h defoaming is carried out until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 8 ℃, the ultrasonic treatment temperature is 5 ℃, and the ultrasonic treatment frequency is 1000W; (2) Placing the chitosan hybrid hydrogel obtained in the step (1) into a freeze dryer at the temperature of minus 50 ℃ to be frozen for 12 h, and drying 24. 24 h in a vacuum environment of 0.0 Mpa to obtain chitosan hybrid aerogel; (3) Placing the chitosan hybrid aerogel obtained in the step (2) in a tube furnace, under the protection of high-purity argon (gas flow rate is 5 ml/min), performing high-temperature carbonization treatment on the chitosan hybrid aerogel, heating to 800 ℃ at a speed of 4 ℃/min, roasting 2 h, and then cooling to room temperature at a speed of 5 ℃/min; (4) And (3) placing the sample obtained in the step (3) into a sulfuric acid solution with the temperature of 0.5 mol/L and the temperature of 80 ℃ to remove Co-based nano particles possibly generated, then washing to be neutral by deionized and suction filtration, and drying in vacuum at the temperature of minus 0.5 Mpa and the temperature of 100 ℃ for 12 h to obtain the carbon aerogel loaded Co single-atom electrocatalyst.
Example 5
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) Weighing 234 mg chitosan (viscosity 100-200 mpa.s, deacetylation degree not less than 95%) and dissolving in 7.6 ml of 3 wt% acetic acid aqueous solution, stirring uniformly at room temperature to obtain chitosan aqueous solution, then adding 234 mg zinc chloride pore-forming agent, adding 27 ml aqueous solution dissolved with 6.708 g urea after stirring uniformly, continuously and slowly dropwise adding 3.85 ml aqueous solution dissolved with 624 mg sulfonated cobalt phthalocyanine after stirring uniformly, continuously stirring 1 h, and removing bubbles by ultrasonic 3 h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 30 ℃, the ultrasonic treatment temperature is 10 ℃, and the ultrasonic treatment frequency is 300W; (2) Placing the chitosan hybrid hydrogel obtained in the step (1) into a freeze dryer at the temperature of minus 30 ℃ to be frozen for 5h hours, and drying for 24 hours in a vacuum environment of 2Mpa to obtain chitosan hybrid aerogel; (3) Placing the chitosan hybrid aerogel obtained in the step (2) in a tubular furnace, under the protection of high-purity argon (gas flow rate is 5 ml/min), performing high-temperature carbonization treatment on the chitosan hybrid aerogel, heating to 700 ℃ at a speed of 8 ℃/min, roasting 3 h, and then cooling to room temperature at a speed of 4 ℃/min; (4) And (3) placing the sample obtained in the step (3) into a sulfuric acid solution with the temperature of 0.5 mol/L and the temperature of 80 ℃ to remove Co-based nano particles possibly generated, then washing to be neutral by deionized and suction filtration, and drying in vacuum at the temperature of minus 0.5 Mpa and the temperature of 100 ℃ for 12 h to obtain the carbon aerogel loaded Co single-atom electrocatalyst.
Example 6
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) Weighing 234 mg chitosan (viscosity 100-200 mpa.s, deacetylation degree not less than 95%) and dissolving in 7.6 ml of 3 wt% acetic acid aqueous solution, stirring uniformly at room temperature to obtain chitosan aqueous solution, then adding 78 mg calcium carbonate pore-forming agent, adding 27 ml aqueous solution dissolved with 6.708 g ethylenediamine after stirring uniformly, continuously and slowly dropwise adding 7 ml aqueous solution dissolved with 780 mg sulfonated cobalt phthalocyanine after stirring uniformly, continuously stirring 1 h, and removing bubbles by ultrasonic 4h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 20 ℃, the ultrasonic treatment temperature is 40 ℃, and the ultrasonic treatment frequency is 500W; (2) Putting the chitosan hybrid hydrogel obtained in the step (1) into a freeze dryer at the temperature of minus 25 ℃ to cool 12 h, and drying 24-h in a vacuum environment of 5-Mpa to obtain chitosan hybrid aerogel; (3) Placing the chitosan hybrid aerogel obtained in the step (2) in a tube furnace, under the protection of high-purity argon (gas flow rate is 5 ml/min), performing high-temperature carbonization treatment on the chitosan hybrid aerogel, heating to 800 ℃ at a speed of 4 ℃/min, roasting 2 h, and then cooling to room temperature at a speed of 5 ℃/min; (4) And (3) placing the sample obtained in the step (3) into a sulfuric acid solution with the temperature of 0.5 mol/L and the temperature of 80 ℃ to remove Co-based nano particles possibly generated, then washing to be neutral by deionized and suction filtration, and freeze-drying at the temperature of 0.0 Mpa and minus 55 ℃ for 24h to obtain the carbon aerogel loaded Co single-atom electrocatalyst.
Example 7
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) Weighing 390 mg chitosan (viscosity 100-200 mpa.s, deacetylation degree not less than 95%) and dissolving in 19.11 ml of 5wt% acetic acid aqueous solution, stirring uniformly at room temperature to obtain chitosan aqueous solution, then adding 78 mg silicon dioxide pore-forming agent, adding 19 ml aqueous solution with 6.318 g cysteine dissolved therein after stirring uniformly, continuously and slowly dropwise adding 12 ml aqueous solution with 1.014 g sulfonated cobalt phthalocyanine dissolved therein after stirring uniformly, continuously stirring 1h, and removing bubbles by ultrasonic 5 h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 18 ℃, the ultrasonic treatment temperature is 25 ℃, and the ultrasonic treatment frequency is 700W; (2) Placing the chitosan hybrid hydrogel obtained in the step (1) into a freeze dryer at the temperature of minus 45 ℃ to be frozen for 10 h, and drying 48 and h in a vacuum environment of 3 and Mpa to obtain the chitosan hybrid aerogel; (3) Placing the chitosan hybrid aerogel obtained in the step (2) in a tube furnace, under the protection of high-purity argon (gas flow rate is 5 ml/min), performing high-temperature carbonization treatment on the chitosan hybrid aerogel, heating to 700 ℃ at a speed of 6 ℃/min, roasting 1: 1h, and then cooling to room temperature at a speed of 10 ℃/min; (4) And (3) placing the sample obtained in the step (3) into 0.5 mol/L hydrofluoric acid solution at 80 ℃ to remove silicon dioxide nano particles and Co-based nano particles possibly generated, then washing to be neutral by deionized suction filtration, and freeze-drying at 10 Mpa-25 ℃ for 48 h to obtain the carbon aerogel loaded Co single-atom electrocatalyst.
Example 8
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) Weighing 390 mg chitosan (viscosity 100-200 mpa.s, deacetylation degree not less than 95%) and dissolving in 19.11 ml 5 wt% acetic acid aqueous solution, stirring uniformly at room temperature to obtain chitosan aqueous solution, then adding 234 mg calcium carbonate pore-forming agent, adding 39 ml aqueous solution with 6.942 g lysine dissolved therein after stirring uniformly, continuously and slowly dropwise adding 5.6 ml aqueous solution with 234 mg sulfonated cobalt phthalocyanine dissolved therein after stirring uniformly, continuously stirring 1h, and removing bubbles by ultrasonic 5h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 10 ℃, the ultrasonic treatment temperature is 30 ℃, and the ultrasonic treatment frequency is 900W; (2) Putting the chitosan hybrid hydrogel obtained in the step (1) into a freeze dryer at the temperature of minus 35 ℃ to cool 12 h, and drying 36 h in a vacuum environment of 8 Mpa to obtain chitosan hybrid aerogel; (3) Placing the chitosan hybrid aerogel obtained in the step (2) in a tube furnace, under the protection of high-purity argon (gas flow rate is 5 ml/min), performing high-temperature carbonization treatment on the chitosan hybrid aerogel, heating to 900 ℃ at a speed of 4 ℃/min, roasting 2 h, and then cooling to room temperature at a speed of 5 ℃/min; (4) And (3) placing the sample obtained in the step (3) into a sulfuric acid solution with the temperature of 0.5 mol/L and the temperature of 80 ℃ to remove Co-based nano particles possibly generated, then washing to be neutral by deionized and suction filtration, and freeze-drying at the temperature of 50 Mpa and 35 ℃ to 36 h to obtain the carbon aerogel loaded Co single-atom electrocatalyst.
Example 9
The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery comprises the following steps:
(1) Weighing 234 mg chitosan (viscosity 100-200 mpa.s, deacetylation degree not less than 95%) and dissolving in 7.6 ml of 5 wt% acetic acid aqueous solution, stirring uniformly at room temperature to obtain chitosan aqueous solution, then adding 390 mg sodium chloride pore-forming agent, adding 19 ml aqueous solution with 6.552 g glutamic acid dissolved therein after stirring uniformly, continuously and slowly dropwise adding 3.85 ml aqueous solution with 624 mg sulfonated cobalt phthalocyanine dissolved therein after stirring uniformly, continuously stirring 1 h, and removing bubbles by ultrasonic 4 h until chitosan hybrid hydrogel is obtained; wherein the stirring temperature is 22 ℃, the ultrasonic treatment temperature is 12 ℃, and the ultrasonic treatment frequency is 600W; (2) Placing the chitosan hybrid hydrogel obtained in the step (1) into a freeze dryer at the temperature of minus 55 ℃ to cool 12 h, and drying 24-h in a vacuum environment of 10-Mpa to obtain chitosan hybrid aerogel; (3) Placing the chitosan hybrid aerogel obtained in the step (2) in a tube furnace, under the protection of high-purity argon (gas flow rate is 5 ml/min), performing high-temperature carbonization treatment on the chitosan hybrid aerogel, heating to 1000 ℃ at a speed of 4 ℃/min, roasting 2 h, and then cooling to room temperature at a speed of 5 ℃/min; (4) And (3) placing the sample obtained in the step (3) into a sulfuric acid solution with the temperature of 0.5 mol/L and the temperature of 80 ℃ to remove Co-based nano particles possibly generated, then washing to be neutral by deionized and suction filtration, and freeze-drying at the temperature of 50 Mpa and 35 ℃ to 36 h to obtain the carbon aerogel loaded Co single-atom electrocatalyst.
The electrocatalytic oxygen reduction performance test is carried out on the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery:
three electrode system testing was performed using an Shanghai Chenhua electrochemical workstation (CHI 760E). The carbon aerogel loaded Co single-atom electrocatalyst mixed slurry prepared in the examples 1-9 is dripped on a rotary disc glassy carbon electrode to be naturally dried to be used as a working electrode, a Pt wire is used as a counter electrode, a reference electrode is an Ag/AgCl electrode, and an electrolyte is 0.1 mol/L KOH aqueous solution. Mixing the slurry: 4 mg catalyst, 800 ml isopropanol, 200 ml water and 10 uL Nafion.
The test results are shown in figures 4-7. The catalyst prepared by the invention has excellent electrocatalytic oxygen reduction performance. As can be seen from fig. 4, the O 2 -saturated electrolyte has a distinct cathodic oxygen reduction peak, whereas the curve in the N 2 -saturated electrolyte is approximately rectangular in shape, with no distinct oxygen reduction peak being found. This indicates that O 2 is catalytically reduced, and the carbon aerogel supported Co single-atom catalyst has catalytic oxygen reduction performance. Fig. 5 is a LSV curve of the prepared catalyst electrocatalytic oxygen reduction at different rotational speeds. It can be seen from the graph that as the rotational speed increases, the limiting current density increases, mainly due to the increase in the diffusion rate of oxygen in the electrolyte as the rotational speed increases. As can be seen from fig. 6, the catalyst has very good methanol resistance. As can be seen from fig. 7, the catalyst has very good cycle stability, catalyzes the reduction of O 2 by 24: 24 h, and the current density remains substantially unchanged.
The carbon aerogel loaded cobalt monoatomic catalyst for the metal-air battery is subjected to zinc-air battery performance test:
the performance test of the zinc-air battery adopts a gas diffusion layer added with a carbon aerogel loaded Co monoatomic catalyst as an air anode, adopts a polished zinc sheet as a cathode, and adopts a mixed aqueous solution of 6 mol/L KOH+0.2 mol/L zinc acetate or gel electrolyte thereof. The preparation of the air positive electrode adopts a conventional method in the field to load a 4mg catalyst on carbon paper in an electrode composite matrix of 2 x 2 cm 2, wherein the composition of the electrode composite matrix is foamed nickel, a waterproof diaphragm and conductive carbon paper.
The catalyst prepared by the invention can be used as a cathode catalyst of a zinc-air battery. FIG. 8 shows the open circuit potential of a catalyst prepared according to the present invention applied to a zinc air cell. The open circuit potential of the catalyst of the present invention is higher than commercial Pt/C catalysts. The specific capacity of the catalyst of the present invention was 771 mAhg -1, which is higher than 751 mAhg -1 of the commercial catalyst (see figure 9). Fig. 10 shows the charge-discharge curve of the catalyst of the present invention as a cathode catalyst, from which it can be seen: the catalyst of the invention has good cyclic charge and discharge performance at a current density of 10 mAcm -2, which is superior to commercial catalysts.
The foregoing has been a clear and complete description of the technical solutions of embodiments of the present invention, and the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Claims (3)
1. The preparation method of the carbon aerogel supported cobalt monoatomic catalyst for the metal-air battery is characterized by comprising the following steps of:
(1) Synthesis of chitosan hybrid hydrogel: dissolving chitosan in an acetic acid aqueous solution, uniformly stirring to obtain a chitosan aqueous solution, then adding a pore-forming agent into the chitosan aqueous solution, uniformly stirring and mixing, sequentially slowly dropwise adding a heteroatom-containing precursor solution and a cobalt precursor solution into a uniformly mixed system under stirring, uniformly stirring, and performing ultrasonic treatment until chitosan hybrid hydrogel is obtained;
Wherein the acetic acid aqueous solution is 2% -5% acetic acid aqueous solution by mass percent concentration; the mass fraction of the chitosan aqueous solution is 1% -3%; the pore-forming agent is one or more of silicon dioxide, calcium carbonate, sodium carbonate, zinc chloride and sodium chloride, and the mass fraction of the pore-forming agent is 1% -5%; the heteroatom-containing precursor solution is an aqueous solution or an organic solution with the mass percentage concentration of 15% -25%; the cobalt precursor is one or more of cobalt-based ionic liquid, vitamin B12, cobalt porphyrin, cobalt phthalocyanine, porphyrin-cobalt acetate complex, cobalt-phenanthroline complex and sulfonated cobalt phthalocyanine, and the cobalt precursor solution is an aqueous solution or an organic solution with the mass percentage concentration of 4% -14%; the stirring mode is mechanical stirring or magnetic stirring, and the stirring temperature is 5-30 ℃; the ultrasonic treatment temperature is 5-40 ℃, the ultrasonic treatment time is 2-5 h, and the ultrasonic treatment frequency is 100-1200W;
(2) Performing vacuum freeze drying on the chitosan hybrid hydrogel prepared in the step (1) to obtain chitosan hybrid aerogel;
the vacuum freeze drying step comprises the steps of freezing 5-12 h at the temperature of minus 2 to minus 55 ℃ and then drying 24-48 h in a vacuum environment of 0.0-10 Mpa;
The chitosan hybrid aerogel consists of the following precursors in percentage by mass:
chitosan: 1 wt to 5 wt percent,
Pore-forming agent: 1 wt to 5 wt percent,
Heteroatom-containing precursors: 77 weight percent to 95 wt percent,
Cobalt precursor: 3 wt% -13% wt%;
(3) Carbonizing the chitosan hybrid aerogel obtained in the step (2) at a high temperature under the protection of inert atmosphere to enable cobalt atoms and nitrogen atoms to carry out coordination reaction in a high-temperature environment; wherein the inert atmosphere is high-purity nitrogen or high-purity argon; the high-temperature carbonization comprises the following steps: the first step: heating from room temperature to T, wherein T is 700-1000 ℃, the heating rate is 4-8 ℃/min, and the second step is that: keeping the temperature T constant at 1-3 h, and performing a third step: cooling from T to room temperature at a cooling rate of 4-10 ℃/min;
(4) Soaking in acid solution to remove pore-forming agent, repeatedly filtering with deionized water, washing to neutrality, and finally drying to obtain carbon aerogel-loaded cobalt monoatomic catalyst for metal air batteries;
The acid solution is at least one of hydrofluoric acid aqueous solution, hydrochloric acid aqueous solution, nitric acid aqueous solution and sulfuric acid aqueous solution, the acid solution is 0.5-2 mol/L acid solution, the acid soaking time is 12-24 h, and the acid soaking temperature is 60-100 ℃; the drying mode is freeze drying or vacuum drying, wherein the pressure is 0.0-10 Mpa, the drying temperature is-25-55 ℃ and the drying time is 24-48 h in freeze drying, the pressure is-0.5-1 Mpa, the drying temperature is 60-120 ℃ and the drying time is 8-12 h in vacuum drying;
The carbon aerogel supported cobalt monoatomic catalyst carrier for the metal air battery is porous carbon aerogel, the specific surface area of the porous carbon aerogel is 100-800 m 2g-1, the pore diameter is 2-100 nm, the pore volume is 0.05-1.0 cm 3g-1, and the active component is cobalt monoatoms which are uniformly distributed on the surface of the porous carbon aerogel and coordinate with hetero atoms; the composition of the catalyst is as follows: the content of the porous carbon aerogel is 67-wt% -95.95 wt%, the content of cobalt single atoms is 0.05-wt% -8.0 wt%, and the content of hetero atoms is 4-wt% -25 wt%.
2. The method of claim 1, wherein the carbon aerogel supported cobalt single-atom catalyst for metal-air batteries is used in electrocatalytic oxygen reduction.
3. A metal-air battery, includes air positive pole, diaphragm, electrolyte and metal negative pole, and air positive pole includes gas diffusion layer, current collector layer and catalyst layer, its characterized in that: the carbon aerogel supported cobalt monoatomic catalyst for the metal air battery, which is prepared by the method of claim 1.
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| CN113584514B (en) * | 2021-08-27 | 2022-08-19 | 中国人民解放军国防科技大学 | Preparation method of monoatomic metal-nitrogen doped carbon aerogel electrocatalyst |
| CN113937307B (en) * | 2021-09-10 | 2023-03-14 | 华中科技大学 | Silicon-doped non-noble metal fuel cell cathode catalyst and preparation method thereof |
| CN114284512B (en) * | 2021-12-29 | 2023-09-19 | 吉林大学 | Preparation method of carbon molecular sieve-cobalt monoatomic catalyst for zinc-air battery |
| CN114887639B (en) * | 2022-04-19 | 2023-09-19 | 东莞理工学院 | CO (carbon monoxide) 2 Reduction catalyst, application and preparation method thereof |
| CN115036517B (en) * | 2022-05-11 | 2023-12-01 | 山东能源集团有限公司 | Graphene aerogel adsorption metalloporphyrin-based oxygen reduction catalyst, preparation method thereof, air electrode and fuel cell |
| CN114990567B (en) * | 2022-05-13 | 2023-12-19 | 北京理工大学 | Preparation method and application of carbon-based carrier-supported sulfur coordination cobalt monoatomic catalyst |
| CN115282999A (en) * | 2022-08-05 | 2022-11-04 | 兰州大学 | Preparation method of heteroatom-doped porous carbon-supported monatomic catalyst |
| CN115318210B (en) * | 2022-08-11 | 2024-04-02 | 宿辉 | Preparation method and application of cobalt disulfide/porous carbon/silicon carbide aerogel composite material for electromagnetic shielding |
| CN115395026B (en) * | 2022-08-12 | 2024-03-15 | 天津市顺红洋科技有限公司 | Fe single-atom-supported N-doped carbon aerogel electrocatalyst and preparation method and application thereof |
| CN116764636B (en) * | 2023-05-17 | 2024-04-26 | 浙江大学 | Low-cost metal aerogel catalyst with selective half-hydrogenation capability and preparation and application thereof |
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