CN115312792A - Carbon layer coated cobalt-zinc alloy composite material catalyst and preparation method thereof - Google Patents
Carbon layer coated cobalt-zinc alloy composite material catalyst and preparation method thereof Download PDFInfo
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- CN115312792A CN115312792A CN202210036781.4A CN202210036781A CN115312792A CN 115312792 A CN115312792 A CN 115312792A CN 202210036781 A CN202210036781 A CN 202210036781A CN 115312792 A CN115312792 A CN 115312792A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 62
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 57
- 239000003054 catalyst Substances 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 41
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 23
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 22
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000004202 carbamide Substances 0.000 claims abstract description 12
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 25
- CPOXHKWVHTWUGL-UHFFFAOYSA-J zinc;cobalt(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Zn+2] CPOXHKWVHTWUGL-UHFFFAOYSA-J 0.000 claims description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 14
- 230000003197 catalytic effect Effects 0.000 claims description 13
- 239000011701 zinc Substances 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 238000012360 testing method Methods 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 238000004140 cleaning Methods 0.000 claims description 8
- 239000002244 precipitate Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 238000003763 carbonization Methods 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 2
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004917 carbon fiber Substances 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 claims description 2
- 238000002484 cyclic voltammetry Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 2
- 230000002209 hydrophobic effect Effects 0.000 claims description 2
- 238000004502 linear sweep voltammetry Methods 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims description 2
- 239000010405 anode material Substances 0.000 claims 1
- 238000000970 chrono-amperometry Methods 0.000 claims 1
- 239000011258 core-shell material Substances 0.000 abstract description 10
- 239000002114 nanocomposite Substances 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 239000002184 metal Substances 0.000 abstract description 7
- 239000011148 porous material Substances 0.000 abstract description 5
- 150000003624 transition metals Chemical class 0.000 abstract description 5
- 229910000000 metal hydroxide Inorganic materials 0.000 abstract description 4
- 150000004692 metal hydroxides Chemical class 0.000 abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 3
- 239000001301 oxygen Substances 0.000 abstract description 3
- 229910052723 transition metal Inorganic materials 0.000 abstract description 3
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 abstract description 3
- 230000001276 controlling effect Effects 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract 2
- 230000002349 favourable effect Effects 0.000 abstract 1
- 229910052757 nitrogen Inorganic materials 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 45
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 4
- 239000012467 final product Substances 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 239000012300 argon atmosphere Substances 0.000 description 3
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- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 238000007885 magnetic separation Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
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- 229910000510 noble metal Inorganic materials 0.000 description 2
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- 239000010970 precious metal Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
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- 238000005406 washing Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000002159 adsorption--desorption isotherm Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
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- 230000005294 ferromagnetic effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
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- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000005291 magnetic effect Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
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- 239000002245 particle Substances 0.000 description 1
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- 239000007774 positive electrode material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inert Electrodes (AREA)
- Hybrid Cells (AREA)
Abstract
The invention discloses a carbon layer coated cobalt-zinc alloy composite catalyst and a preparation method thereof, and particularly relates to a carbon layer coated cobalt-zinc alloy composite material serving as a zinc-air battery cathode catalyst and a preparation method thereof, belonging to the technical field of electrochemical energy storage batteries. The catalyst adopts cobalt nitrate, zinc nitrate, melamine and urea as raw materials, and successfully prepares the carbon layer coated cobalt-zinc alloy nanocomposite material for the metal zinc-air battery by regulating and controlling the proportion of metal hydroxide and a carbon source, the nanocomposite material comprises a carrier and a core-shell structure loaded on the carrier, the shell layer of the core-shell structure is a graphitized carbon layer containing nitrogen and oxygen, the core of the core-shell structure is transition metal nanoparticles, the core-shell structure is constructed by taking transition metal as the core, and the core-shell structure is loaded on the carrier to form the nanocomposite material, so that the mass transfer efficiency and the strength of the nanocomposite material are improved, and the nanocomposite material has a better form and can be better applied to the zinc-air battery. In addition, the nano composite material can also be a multi-level pore structure material with abundant mesopores or micropores and mesopores, and is favorable for better playing a role in more applications, particularly the applications in the field of catalysis.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage batteries, particularly relates to a carbon layer coated cobalt-zinc alloy composite catalyst and a preparation method thereof, and more particularly relates to a carbon layer coated cobalt-zinc alloy composite material as a zinc-air battery cathode catalyst and a preparation method thereof.
Background
The metal-air battery is a novel energy conversion device with high energy density, zero emission and no pollution, and has wide application prospect. Since their overall performance is limited by the reaction rate of the oxygen reduction (ORR) reaction that occurs at the cathode, high ORR catalytically active catalysts are needed to accelerate the cathode reaction. At present, the commercialized catalyst with excellent performance is a precious metal Pt-based catalyst, but the commercialization progress of the metal-air battery is severely limited by the problems of high price, resource scarcity and the like, and the development of an ORR catalyst with wide source, low price and high activity instead of precious metal Pt is urgently needed.
The carbon-coated non-noble metal material with good conductivity, low price, good electrochemical stability and wide source is an important subject for improving the ORR catalytic performance and applying the material to a metal-air battery. Recent studies have found that coating metal nanoparticles with a carbon layer can greatly increase the ORR catalytic activity of the material, with the potential to replace commercial Pt/C under alkaline conditions. For example, encapsulation of metal nanoparticles into a carbon shell to form an armor catalyst, zinc-made porous structure during pyrolysis to promote the activity of the carbon layer greatly improved the ORR catalytic activity, and this result was confirmed by theoretical calculations. Currently, the ORR catalytic performance can be improved by adjusting the type and amount of metal nanoparticles and the activity of the carbon layer.
The double metal hydroxide is a metal hydroxide composed of two or more metal elements, and the structure is formed by mutually overlapping main layer plates, interlayer anions and water molecules. Due to the specific composition, such as the type and proportion of metal ions on the laminate, the type of anions and the like, the structure is easy to modulate, the layer number, the layer spacing and the like are easy to cut, and the LDHs are easy to be compounded with other materials to realize functionalization and the like, and the LDHs have good application prospects in energy conversion and electrochemical energy storage of super capacitors, secondary batteries, electrocatalysis and the like.
Patent application CN113410475A discloses a high-loading graphitized carbon layer coated transition metal nanoparticle catalyst and a preparation method thereof. The transition metal nanoparticle catalyst coated by the graphite carbon layer is formed by distributing nanoparticles with a core-shell structure anchored by a porous carbon network on a carbon substrate. Compared with the patent application, the precursor is not required to be loaded on a graphene substrate in the preparation process, other alkaline aqueous solution is not required to be added as a precipitating agent, in addition, when the graphitized carbon layer is prepared, any high molecular polymer is not required to be added, melamine is directly utilized as a carbon source, carbon-containing gas generated in the pyrolysis process of the melamine can form a carbon structure under the action of metal catalysis, and the cobalt-zinc alloy composite material coated by the carbon layer can be obtained through primary heat treatment.
In addition, the cathode ORR catalyst currently commercialized for metal-air batteries is a noble metal Pt-based catalyst (Pt/C, pt/transition metal alloy), which limits the large-scale popularization and application of such devices due to its high price. Therefore, the development of the cheap and high-performance ORR catalyst has important significance for large-scale popularization and application of the metal-air battery. The preparation method is simple, the raw materials are cobalt nitrate, zinc nitrate, melamine and urea, and the prepared carbon-coated cobalt-zinc catalyst has excellent performance, can be comparable with commercial Pt/C catalyst, and is a metal-air battery cathode catalyst with great prospect.
Disclosure of Invention
In order to solve the problems in the prior art, the invention firstly discloses a method for preparing a carbon-layer-coated cobalt-zinc alloy composite material with high ORR catalytic activity as a zinc-air battery cathode catalyst by using cobalt nitrate, zinc nitrate, urea and melamine as raw materials, wherein the mass ratio of cobalt-zinc hydroxide powder prepared from the zinc nitrate and the cobalt nitrate to the melamine is 1;
preferably, the mass ratio of cobalt zinc hydroxide powder to melamine is 1.
Secondly, the invention also discloses a manufacturing process of the composite material, which comprises the following steps: 1) Adding Zn (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water, stirring at room temperature for 10-60 min, and slowly adding zinc nitrate solution into cobalt nitrate solution, wherein Zn (NO) is added 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 1:1-3; 2) Dissolving urea in a mixture of deionized water and ethanol, stirring uniformly, adding the mixture into a mixture of zinc nitrate and cobalt nitrate, and magnetically stirring again for 30 minutes at room temperature, wherein Zn (NO) is added 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O to urea is 1:1-3:1-2; 3) Adding the mixed solution prepared in the step 2) into the mixed solution of zinc nitrate and cobalt nitrate, and magnetically stirring the mixed solution at room temperature again to be uniform; 4) Adding the mixed solution prepared in the step 3) into a high-pressure reaction kettle, and performing hydrothermal reaction to form cobalt-zinc hydroxide precipitate; 5) Centrifugally cleaning and drying the cobalt-zinc hydroxide precipitate obtained in the step 4) by using deionized water and absolute ethyl alcohol to obtain cobalt-zinc hydroxide powder; 6) Mixing the cobalt-zinc hydroxide powder obtained in the step 5) with melamine, putting the mixture into a tube furnace for carbonization, wherein the mass ratio of the cobalt-zinc hydroxide powder to the melamine is 1; 7) Testing the ORR catalytic performance of the carbon layer coated cobalt-zinc alloy composite material and the electrochemical performance of the cathode serving as a zinc-air electrode by using an electrochemical workstation, a rotating disc electrode and a blue battery testing system;
preferably, zn (NO) described in step 2) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 1:2:1;
wherein the hydrothermal reaction temperature of the mixed solution in the step 3) is kept at 120 ℃, and the reaction time is 16 hours;
wherein, the centrifugation step in the step 5) is operated for 5min at the rotating speed of 4000r/min, after the centrifugation is finished, supernatant is removed, distilled water and absolute ethyl alcohol are added to repeat the centrifugation step for cleaning for 2 to 4 times, the drying temperature is 60 ℃, and the time is 8 hours;
wherein, in the carbonization process in the step 6), the mass ratio of the cobalt zinc hydroxide to the melamine is 1.5, 1, 5, 1;
wherein, in the step 7), the ORR performance of the material is tested by mainly using methods such as cyclic voltammetry, linear sweep voltammetry, timing current and the like, the voltage range is-1.0-0V, specifically, a three-electrode testing device is used, ag/AgCl is used as a reference electrode, pt wire is used as an auxiliary electrode, and a glassy carbon electrode (GCE; diameter 3 mm), respectively coating a catalyst as a working electrode, wherein the electrolyte is 0.1M KOH aqueous solution, a catalyst prepared by taking hydrophobic carbon fiber paper as a current collector load is used as a positive electrode material in a zinc-air battery test, a commercial zinc sheet with the thickness of about 0.2mm is adopted as a negative electrode material, the catalyst is polished to be smooth before use to ensure full contact, and the electrolyte is 6.0M KOH aqueous solution;
finally, the invention also discloses the application of the composite material catalyst and the preparation method thereof in the preparation of metal-air batteries.
The preparation method disclosed by the invention is simple in preparation process, expensive equipment is not required, the obtained product is excellent in performance and good in electrochemical stability, and has a wide prospect in popularization and application of the metal-air battery, and compared with the patent application CN113410475A, the method disclosed by the invention reduces the using amount of metal salt by regulating and controlling the proportion of a carbon source, is lower in cost and is beneficial to environmental protection; in addition, the atom utilization rate of the precursor transition metal can reach 100%, no high molecular polymer is required to be added, melamine is directly used as a carbon source, carbon-containing gas generated in the pyrolysis process of the melamine can form a carbon structure under the action of metal catalysis, and the cobalt-zinc alloy composite material coated by the carbon layer can be obtained through one-time heat treatment.
The carbon layer coated cobalt-zinc alloy nano composite material prepared by the method disclosed by the invention is not spontaneous combustion in air, can be stored in air for a long time like common commodities, and does not influence the service performance of the carbon layer coated cobalt-zinc alloy nano composite material in reactions such as catalytic oxidation, catalytic hydrogenation and the like.
According to one embodiment of the present invention, the nanocomposite has one mesopore distribution peak. In the prior art, it is difficult to manufacture a nano-scale core-shell structure with a tightly coated graphitized carbon layer and a transition metal core, and particularly, the nano-scale core-shell structure containing the tightly coated graphitized carbon layer and the transition metal core can be manufactured into a rich mesoporous structure at the same time. In the composite material prepared by the invention, the tightness of the nano metal particles coated by the graphitized carbon layer is higher, and the electronic characteristics of the graphitized carbon layer can be adjusted, so that the composite material is suitable for different catalytic reactions.
The carbon layer coated cobalt-zinc alloy composite material prepared by the invention is beneficial to improving the efficiency of catalytic reaction, particularly has excellent catalytic effect and selectivity on ORR reaction, has performance comparable to that of Pt/C in current commercial application, and has good industrial application prospect.
The carbon layer coated cobalt-zinc alloy composite material prepared by the method, the graphitized carbon layer, the ferromagnetic metal core coated by the graphitized carbon layer and the abundant pore structure, can better combine the magnetic separation function with the adsorption function, and is particularly suitable for the field of adsorption separation.
Advantageous effects
1. According to the invention, the mass ratio of cobalt-zinc hydroxide powder to melamine is 1.5-1, and the carbon material has catalytic activity by high-temperature carbonization, and a mesoporous structure is manufactured on a carbon layer by high-temperature pyrolysis of Zn, so that the mass transfer efficiency of the nano composite material is improved, on one hand, the ORR performance of the zinc-air battery can be improved, and on the other hand, the circulation stability of the zinc-air battery can be further improved, thereby improving the circulation life of the zinc-air battery.
2. The invention is not based on the prior art, and can manufacture abundant multilevel mesoporous structures in the composite material while manufacturing the core-shell structure containing tight cladding.
3. In the composite material prepared by the invention, the tightness of the nano metal particles coated by the graphitized carbon layer is higher, and the electronic characteristics of the graphitized carbon layer can be adjusted, so that the composite material is suitable for different catalytic reactions.
4. The carbon layer coated cobalt-zinc alloy composite material prepared by the invention is beneficial to improving the efficiency of catalytic reaction, particularly has excellent catalytic effect and selectivity on ORR reaction, has performance comparable to that of Pt/C in current commercial application, and has good industrial application prospect.
5. The carbon layer coated cobalt-zinc alloy composite material prepared by the method disclosed by the invention has the advantages that the graphitized carbon layer, the strongly magnetic metal core coated by the graphitized carbon layer and rich pore structures are adopted, so that the magnetic separation function and the adsorption function are better combined, and the composite material is particularly suitable for the field of adsorption separation.
Drawings
FIG. 1 is a scanning electron microscope image of the carbon-layer-coated cobalt-zinc alloy composite material obtained in example 2 according to a ratio of 1:5, and the fiber morphology of the composite material is obviously visible.
FIG. 2A is a TEM image of a carbon-layer-coated cobalt-zinc alloy composite material obtained in example 2 at a ratio of 1:5. As can be seen from fig. 2A, a plurality of cobalt nanoparticles having a uniform particle size are distributed in a carbon material matrix; fig. 2B is a high-resolution TEM image (HRTEM), which shows that metal nanoparticles (lattice fringe spacing of 0.20 nm) are coated with a graphitized carbon layer (interlayer spacing of 0.34 nm) to form a complete core-shell structure;
fig. 3 is an XRD pattern of the cobalt-zinc alloy composite material coated with carbon layers obtained according to different ratios in examples 1, 2 and 3, and the crystalline phase and structure of the composite material are characterized, and it can be seen that the material has diffraction peaks corresponding to C (2 theta angle of 25.9 °) and Co (2 theta angles of 44.5 °, 51.7 ° and 76.2 °), indicating that the material contains carbon with a certain degree of graphitization, wherein Co exists in a face-centered cubic structure.
FIG. 4 is a Raman spectrum of the carbon-layer-coated cobalt-zinc alloy composite material obtained in examples 1, 2 and 3 at different proportions, and further studies the carbon structure;
FIG. 5 shows N in the carbon-layer-coated cobalt-zinc alloy composite materials obtained in examples 1, 2 and 3 at different ratios 2 Adsorption-desorption isotherms and BJH pore size distribution curves, fig. 5A showing typical type IV curve characteristics, at relatively low pressures (P/P0)<0.05 Showing obvious absorption in the range, and showing that an H3 type desorption loop line appears in the relative pressure range of 0.5-1.0, which indicates that the obtained material mainly consists of mesopores; fig. 5B also confirms the presence of a mesoporous structure with an average pore size of about 3.9nm.
FIG. 6 is an ORR linear scan curve of the carbon-layer coated cobalt-zinc alloy composite and commercial Pt/C measured using the electrochemical workstation and selected disk electrode in examples 1, 2 and 3, the initial potential (0.935V), half-wave potential (0.814V), and limiting current density (-4.712 mA cm/cm) -2 ) The performance is close to that of a commercial Pt/C catalyst.
FIG. 7 is a polarization curve and power density curve for the carbon layer coated cobalt zinc alloy composite of examples 1, 2, 3 and commercial Pt/C used as the cathode of a zinc-air battery, showing that the current density and power density of a zinc-air battery using a carbon coated cobalt zinc catalyst are higher than those of the Pt/C catalyst, indicating that the prepared product has great feasibility as an effective air cathode catalyst in ZABs.
FIG. 8 is a graph showing different current density discharge curves at 25-300mA cm for the carbon layer coated cobalt-zinc alloy composites and commercial Pt/C used as the cathode of a zinc-air battery in examples 1, 2, 3 -2 The discharge voltage drop is very small under different current densities, which shows that the material has excellent discharge rate performance.
Detailed Description
The present invention will be described in detail with reference to specific examples, but the present invention is not limited thereto. The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Zn (NO) 3 ) 2 ·6H 2 O (0.595 g) and Co (NO) 3 ) 2 ·6H 2 Dissolving O (1.164 g) in 30ml of deionized water respectively, stirring for 30 minutes at room temperature, slowly adding a zinc nitrate solution into a cobalt nitrate solution, dissolving urea (0.601 g) in a mixture of 20ml of deionized water and 20ml of ethanol, uniformly stirring, adding into a mixture of zinc nitrate and cobalt nitrate, magnetically stirring for 30 minutes again at room temperature, transferring the obtained solution into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into a 120 ℃ oven for hydrothermal reaction for 16 hours, naturally cooling the high-pressure reaction kettle to the ambient temperature after the hydrothermal reaction is finished, taking out pink precipitates from the high-pressure reaction kettle, centrifugally cleaning, collecting the obtained solid, and drying for 8 hours in the 60 ℃ oven to obtain cobalt-zinc hydroxide. Mixing cobalt zinc hydroxide powder and melamine according to a ratio of 1:2.5, carbonizing for 1 hour at 700 ℃ in an argon atmosphere, washing for 12 hours by using 1M hydrochloric acid solution, washing and drying to obtain a final product, and carrying out electrochemical test on the obtained final product, namely the metal catalyst zinc-air battery cathode catalyst by using an electrochemical workstation, a rotating disc electrode and a blue battery test system.
Example 2
Zn (NO) 3 ) 2 ·6H 2 O (0.595 g) and Co (NO) 3 ) 2 ·6H 2 Dissolving O (1.164 g) in 30ml of deionized water respectively, stirring and stirring at room temperature for 30 minutes, slowly adding a zinc nitrate solution into a cobalt nitrate solution, dissolving urea (0.601 g) in a mixture of 20ml of deionized water and 20ml of ethanol, stirring uniformly, adding into a mixture of zinc nitrate and cobalt nitrate, magnetically stirring again at room temperature for 30 minutes, transferring the obtained solution into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into a 120 ℃ oven for hydrothermal reaction for 16 hours, naturally cooling the high-pressure reaction kettle to the ambient temperature after the hydrothermal reaction is finished, taking out a pink precipitate from the high-pressure reaction kettle, centrifugally cleaning, collecting the obtained solid, and drying in the 60 ℃ oven for 8 hours to obtain the pink precipitateCobalt zinc hydroxide, cobalt zinc hydroxide powder and melamine are mixed according to the proportion of 1:5, the mixture is carbonized for 1 hour at 700 ℃ in the argon atmosphere, the mixture is washed by 1M hydrochloric acid solution for 12 hours and then is cleaned and dried to obtain a carbon layer coated cobalt zinc alloy composite material, and the obtained final product, namely the carbon layer coated cobalt zinc alloy composite material zinc-air battery cathode catalyst is subjected to electrochemical test by utilizing an electrochemical workstation, a rotating disc electrode and a blue battery test system.
This example shows that when the ratio of metal hydroxide to melamine is 1:5, the material has excellent oxygen reduction (ORR) catalytic performance at an initial potential (0.935V), half-wave potential (0.814V), and limiting current density (-4.712 mA cm) -2 ) The performance is close to that of a commercial Pt/C catalyst, and the excellent catalytic stability is shown. The material is used as a cathode material in a zinc-air battery, shows a voltage higher than Pt/C under the same discharge current density, and has a current density and a power density higher than those of a Pt/C catalyst, and the prepared product has great feasibility as an effective air cathode catalyst in ZABs.
Example 3
Adding Zn (NO) 3 ) 2 ·6H 2 O (0.595 g) and Co (NO) 3 ) 2 ·6H 2 Dissolving O (1.164 g) in 30ml of deionized water respectively, stirring for 30 minutes at room temperature, slowly adding a zinc nitrate solution into a cobalt nitrate solution, dissolving urea (0.601 g) in a mixture of 20ml of deionized water and 20ml of ethanol, stirring uniformly, adding into the mixture of zinc nitrate and cobalt nitrate, magnetically stirring for 30 minutes again at room temperature, transferring the obtained solution into a high-pressure reaction kettle, sealing the high-pressure reaction kettle, putting the high-pressure reaction kettle into a 120 ℃ oven for hydrothermal reaction for 16 hours, naturally cooling the high-pressure reaction kettle to the ambient temperature after the hydrothermal reaction is finished, taking a pink precipitate out of the high-pressure reaction kettle, centrifugally cleaning, collecting the obtained solid, drying for 8 hours in a 60 ℃ oven to obtain cobalt-zinc hydroxide, mixing the cobalt-zinc hydroxide powder and melamine according to the ratio of 1:10, carbonizing for 1 hour at 700 ℃ in an argon atmosphere, pickling for 12 hours by using a 1M hydrochloric acid solution, cleaning and drying to obtain the final productAnd (3) obtaining the product. And carrying out electrochemical test on the obtained final product, namely the cathode catalyst of the zinc-air battery with the cobalt-zinc alloy composite material coated by the carbon layer by using an electrochemical workstation, a rotating disc electrode and a blue battery test system.
Claims (9)
1. The carbon layer coated cobalt-zinc alloy composite material catalyst is characterized in that raw materials of the catalyst comprise cobalt nitrate, zinc nitrate, urea and melamine, wherein the mass ratio of cobalt-zinc hydroxide powder prepared from the zinc nitrate and the cobalt nitrate to the melamine is 1.5-1.
2. The composite catalyst of claim 1, wherein the ratio of cobalt zinc hydroxide powder to melamine is 1.
3. The method for preparing a composite catalyst according to claims 1-2, wherein the manufacturing process comprises the steps of: 1) Zn (NO) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 Dissolving O in deionized water, stirring at room temperature for 10-60 min, slowly adding zinc nitrate solution into cobalt nitrate solution, wherein Zn (NO) is added 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O is 1:1-3; 2) Dissolving urea in a mixture of deionized water and ethanol, stirring uniformly, adding into a mixture of zinc nitrate and cobalt nitrate, and magnetically stirring at room temperature for 10-60 min, wherein Zn (NO) is added 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O to urea is 1:1-3:1-2; 3) Adding the mixed solution prepared in the step 2) into the mixed solution of zinc nitrate and cobalt nitrate, and magnetically stirring the mixed solution uniformly again at room temperature; 4) Adding the mixed solution prepared in the step 3) into a high-pressure reaction kettle, and performing hydrothermal reaction to form cobalt-zinc hydroxide precipitate; 5) Centrifugally cleaning and drying the cobalt-zinc hydroxide precipitate obtained in the step 4) by using deionized water and absolute ethyl alcohol to obtain cobalt-zinc hydroxide powder; 6) Obtained in step 5)The cobalt-zinc hydroxide powder and melamine are mixed and put into a tube furnace for carbonization, wherein the mass ratio of the cobalt-zinc hydroxide powder to the melamine is (1) and (2.5-1); 7) And (3) testing the ORR catalytic performance of the carbon layer coated cobalt-zinc alloy composite material and the electrochemical performance of the carbon layer coated cobalt-zinc alloy composite material serving as a zinc-air electrode cathode by using an electrochemical workstation, a rotating disk electrode and a blue battery testing system.
4. The method according to claim 3, wherein Zn (NO) in the step 2) 3 ) 2 ·6H 2 O and Co (NO) 3 ) 2 ·6H 2 The mass ratio of O to urea is 1:2:1.
5. the method according to claim 3, wherein the hydrothermal reaction temperature of the mixed solution in the step 3) is maintained at 120 ℃ and the reaction time is 16 hours.
6. The preparation method according to claim 3, wherein the centrifugation step in the step 5) is performed for 5min at a rotation speed of 4000r/min, after the centrifugation is finished, supernatant is removed, distilled water and absolute ethyl alcohol are added to repeat the centrifugation step for cleaning for 2-4 times, and the drying temperature is 60 ℃ and the time is 8 hours.
7. The preparation method according to claim 1, wherein the mass ratio of the cobalt zinc hydroxide to the melamine added in the carbonization process in step 6) is 1.5, 1, 5, 1.
8. The method according to claim 3, wherein in step 7), the ORR performance of the material is tested by mainly using cyclic voltammetry, linear sweep voltammetry, chronoamperometry and the like, wherein the voltage is in the range of-1.0-0V, and specifically, a three-electrode testing device is used, ag/AgCl is used as a reference electrode, pt wire is used as an auxiliary electrode, and a glassy carbon electrode (GCE; diameter 3 mm) as a working electrode, electrolyte is 0.1M KOH aqueous solution, a catalyst prepared by taking hydrophobic carbon fiber paper as a current collector load is used as an anode material in a zinc-air battery test, a commercial zinc sheet with the thickness of about 0.2mm is used as a cathode material, the catalyst is polished to be smooth before use to ensure full contact, and the electrolyte is 6.0M KOH aqueous solution.
9. Use of the composite catalyst according to claims 1-2 and the method of preparation according to claim 3 for the preparation of a metal-air battery.
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| CN108565469A (en) * | 2017-12-28 | 2018-09-21 | 东华大学 | A kind of cobalt-nitrogen-doped carbon composite material and preparation method |
| CN109309212A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | Carbon coating cobalt nanocomposite and preparation method thereof |
| CN111682224A (en) * | 2020-06-19 | 2020-09-18 | 郑州大学 | Monoatomic cobalt-loaded nitrogen-doped graphite carbon cathode catalyst for rechargeable zinc-air battery and preparation method thereof |
| CN112090441A (en) * | 2020-09-28 | 2020-12-18 | 浙江师范大学 | Preparation method, product and application of cobalt-based carbon nano material |
| KR20210001130A (en) * | 2019-06-27 | 2021-01-06 | 중앙대학교 산학협력단 | Method for producing carbon-based catalyst material, carbon-based catalyst produced by the same, and metal-air battery including the same |
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| CN109309212A (en) * | 2017-07-28 | 2019-02-05 | 中国石油化工股份有限公司 | Carbon coating cobalt nanocomposite and preparation method thereof |
| CN108565469A (en) * | 2017-12-28 | 2018-09-21 | 东华大学 | A kind of cobalt-nitrogen-doped carbon composite material and preparation method |
| KR20210001130A (en) * | 2019-06-27 | 2021-01-06 | 중앙대학교 산학협력단 | Method for producing carbon-based catalyst material, carbon-based catalyst produced by the same, and metal-air battery including the same |
| CN111682224A (en) * | 2020-06-19 | 2020-09-18 | 郑州大学 | Monoatomic cobalt-loaded nitrogen-doped graphite carbon cathode catalyst for rechargeable zinc-air battery and preparation method thereof |
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