CN117219927A - Zinc-air battery, composite electrode for zinc-air battery and preparation method of composite electrode - Google Patents
Zinc-air battery, composite electrode for zinc-air battery and preparation method of composite electrode Download PDFInfo
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- CN117219927A CN117219927A CN202311217013.XA CN202311217013A CN117219927A CN 117219927 A CN117219927 A CN 117219927A CN 202311217013 A CN202311217013 A CN 202311217013A CN 117219927 A CN117219927 A CN 117219927A
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- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 30
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 16
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 229920000642 polymer Polymers 0.000 claims abstract description 11
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 9
- 239000010941 cobalt Substances 0.000 claims abstract description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 9
- 239000006260 foam Substances 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 13
- 238000005245 sintering Methods 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 9
- 239000011574 phosphorus Substances 0.000 claims description 9
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 9
- 239000012498 ultrapure water Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 8
- 239000002184 metal Substances 0.000 claims description 8
- 239000007853 buffer solution Substances 0.000 claims description 7
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 229910052759 nickel Inorganic materials 0.000 claims description 7
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 6
- 239000000956 alloy Substances 0.000 claims description 6
- 229960001149 dopamine hydrochloride Drugs 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 229910052697 platinum Inorganic materials 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910001092 metal group alloy Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000004321 preservation Methods 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 8
- 238000012546 transfer Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 8
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 7
- 235000019441 ethanol Nutrition 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000004382 potting Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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Abstract
The invention provides a zinc-air battery and a preparation method of a composite electrode for the zinc-air battery, comprising the following steps: (1) Dispersing a first catalyst in a mixed solution of a perfluorinated sulfonic acid polymer and ethanol to obtain a precursor solution A; (2) Preparing a mixed solution containing a cobalt source, ammonium fluoride and urea, and placing the mixed solution and a carrier in a reaction kettle to prepare a precursor B; (3) Placing the precursor B in a tube furnace for heating to obtain a precursor C; (4) The precursor A is dripped on the surface of the precursor C, and the finished product is obtained by drying, so that the composite electrode prepared by the invention can solve the problems of poor mass transfer and large electrochemical impedance in the reaction process, and the performance of the zinc-air battery is improved.
Description
Technical Field
The invention relates to the technical field of zinc-air batteries, in particular to a zinc-air battery, a composite electrode for the zinc-air battery and a preparation method of the composite electrode.
Background
Rechargeable zinc-air cell (ZAB) due to its high energy density (1086 Wh kg -1 ) The advantages of low cost, safety, environmental protection and the like are considered as an electrochemical energy storage technology with great potential. However, the slow reaction kinetics of oxygen reduction (ORR) and Oxygen Evolution (OER) reactions of zinc-rechargeable air cells at the air anode limit the activity of these electrochemical devices, which is a major obstacle to their large scale practical application.
Platinum (Pt) and platinum-based materials have heretofore been considered the most effective ORR catalysts, but have exhibited poor catalytic activity for OER. While Ru/Ir based catalysts exhibit excellent electrochemical activity in OER, the catalytic activity for ORR is not ideal. These conditions severely limit the commercialization of rechargeable ZABs, how to obtain a simultaneous enhancement of the electrode reactivity in oxygen reduction (ORR) and Oxygen Evolution (OER) is critical to the development of zinc air cells (ZABs).
Disclosure of Invention
In view of the above, the present invention provides a zinc-air battery and a method for preparing a composite electrode for a zinc-air battery, which solve the above problems.
The technical scheme of the invention is realized as follows:
a preparation method of a zinc-air battery and a composite electrode for the zinc-air battery comprises the following steps:
(1) Dispersing a first catalyst in a mixed solution of a perfluorinated sulfonic acid polymer and ethanol to obtain a precursor solution A;
(2) Preparing a mixed solution containing a cobalt source, ammonium fluoride and urea, and placing the mixed solution and a carrier in a reaction kettle to prepare a precursor B;
(3) Placing the precursor B in a tube furnace for heating to obtain a precursor C;
(4) And (3) dropwise adding the precursor A on the surface of the precursor C, and drying to obtain a finished product.
Further, in the step (1), the preparation method of the first catalyst includes the following steps:
s1: mixing monoatomic powder, hydrochloric acid solution and melamine, and heating to obtain a precursor 1;
s2: and placing the precursor 1 in a muffle furnace, sintering at 400-600 ℃, mixing the sintered precursor 1 with a buffer solution, adding dopamine hydrochloride, drying, and sintering in a tube furnace to obtain the first catalyst.
Further, in step S1, the monoatomic powder is one of a monoatomic cobalt catalyst, a monoatomic iron catalyst, and a platinum-based powder catalyst; the feed liquid ratio of the monoatomic powder, the melamine and the hydrochloric acid solution is 75-85mg:8-9g:110-130mL.
Further, the cobalt source is one of cobalt nitrate, cobalt acetylacetonate and cobalt chloride.
In step S1, the monoatomic cobalt catalyst is cobalt chloride, the monoatomic iron catalyst is ferric chloride, and the platinum-based powder catalyst is Pt/C powder.
Further, in step S2, the ratio of the precursor 1 to the buffer solution to the dopamine hydrochloride solution is 1.8-2.2g:70-80mL:0.8-1g, wherein the drying is carried out for 20-28h at 70-90 ℃, the sintering temperature of the tube furnace is 750-850 ℃, and the heat preservation is carried out for 100-140min.
Further, in step S2, the buffer solution is 1.5M Tris-HCl with a pH value of 8.8.
Further, in the step (1), the mass ratio of the first catalyst to the perfluorinated sulfonic acid type polymer solution to the ethanol is 1:0.15-0.25:0.7-0.9.
Further, in the step (2), the mass ratio of the cobalt source, the ammonium fluoride and the urea is 1:0.17-0.19:0.8-0.9; the reaction kettle is used for reacting for 7-9 hours at 135-145 ℃, the carrier after the reaction is washed by ultrapure water and ethanol, and the carrier after the washing is dried for 20-28 hours at 70-90 ℃.
Further, in the step (2), the carrier is a foam metal simple substance carrier or a foam metal alloy carrier, and the foam metal simple substance carrier is one of foam nickel, foam copper and foam iron; the foam metal alloy carrier is one of foam nickel-containing alloy, foam copper-containing alloy and foam iron-containing alloy.
Further, the preparation method of the carrier comprises the steps of respectively ultrasonically cleaning the carrier for half an hour by using acetone, hydrochloric acid and ultrapure water, transferring the carrier to a vacuum oven, and drying the carrier at 80 ℃ for 24 hours.
Further, in the step (3), the precursor B is placed in the downstream of a tube furnace, a phosphorus source is placed in the upstream of the tube furnace, and the temperature is raised to 330-370 ℃ by 1.5-2.5 ℃/min, and the temperature is kept for 100-140min.
Further, in the step (4), the number of dropping times is 3-4 times, and 45-55 mu L each time.
Compared with the prior art, the invention has the beneficial effects that:
according to the preparation method of the zinc-air battery, the zinc-air battery with more excellent performance can be prepared, the problems of poor mass transfer caused by adopting two metal carriers in the traditional zinc-air battery can be avoided by optimizing the preparation steps of depositing a phosphorus source on the carrier and adopting one metal carrier, and the like.
Drawings
FIG. 1 comparative graphs of example 1 and comparative example 1
Detailed Description
In order to better understand the technical content of the present invention, the following provides specific examples to further illustrate the present invention.
The experimental methods used in the embodiment of the invention are conventional methods unless otherwise specified.
Materials, reagents, and the like used in the examples of the present invention are commercially available unless otherwise specified.
In the embodiment of the invention, foam nickel is adopted as a carrier, the carrier is cut into 3 x 4 cm, the thickness of a foam nickel sheet can be 0.1-1.5 cm, the preferred thickness of the embodiment of the invention is 1cm, acetone, hydrochloric acid and ultrapure water are respectively used for ultrasonic cleaning for half an hour, and the foam nickel is transferred to a vacuum oven and dried for 24 hours at 80 ℃.
The buffer was 1.5M Tris-HCl at pH 8.8.
Example 1
The preparation method of the first catalyst comprises the following steps:
s1: adding 20 mL hydrochloric acid into 100 mL ultrapure water, adding 80 mg cobalt chloride into a beaker, adding 8.5 g melamine, stirring, transferring into an oil bath pot, and evaporating at 120 ℃ to obtain a precursor 1;
s2: placing the precursor 1 in a muffle furnace, sintering at 500 ℃, adding 75 mL buffer solution into the precursor 1 after 2g sintering, carrying out ultrasonic treatment to make the precursor uniform, adding 0.9 g dopamine hydrochloride, carrying out suction filtration after full reaction, taking filter residues, drying the filter residues through a vacuum oven, wherein the temperature of the vacuum oven is 80 ℃, the heat preservation time is 24 hours, placing the dried precursor in a tube furnace, sintering, heating to 800 ℃ at 5 ℃/min, and preserving heat for 120 minutes.
Zinc-air battery and preparation method of composite electrode for zinc-air battery
(1) Dispersing a first catalyst in a mixed solution of a perfluorinated sulfonic acid polymer solution and absolute ethyl alcohol, wherein the mass ratio of the first catalyst to the perfluorinated sulfonic acid polymer solution to the absolute ethyl alcohol is 1:0.2:0.8, so as to obtain a precursor solution A;
(2) Preparing a mixed solution of cobalt nitrate, ammonium fluoride and urea, wherein the mass ratio of the cobalt nitrate to the ammonium fluoride to the urea is 1:0.18:0.85, placing the mixed solution and the carrier in a reaction kettle, reacting at 140 ℃ for 8 hours, respectively cleaning the reacted carrier with ultrapure water and ethanol for 10 minutes, and drying the cleaned carrier at 80 ℃ for 24 hours to prepare a precursor B;
(3) Placing the precursor B in the downstream of a tube furnace, placing 1g of phosphorus source in the upstream of the tube furnace, and heating to 350 ℃ at 2 ℃/min for 120min to prepare a precursor C;
(4) And (3) dropwise adding the precursor A on the surface of the precursor C for 5 times, wherein 50 mu L of the precursor A is added each time, baking is carried out by an infrared lamp in the dropwise adding process, and the precursor A is transferred to a vacuum oven for drying after the dropwise adding is finished, so that the composite electrode (SAC-Co/NC, coPx) is obtained.
Example 2
The preparation method of the first catalyst comprises the following steps:
s1: adding 20 mL hydrochloric acid into 100 mL ultrapure water, adding 80 mg ferric chloride into a beaker, adding 8.5 g melamine, stirring, transferring into an oil bath pot, and evaporating at 120 ℃ to obtain a precursor 1;
s2: placing the precursor 1 in a muffle furnace, sintering at 500 ℃, adding 75 mL buffer solution into the precursor 1 after 2g sintering, carrying out ultrasonic treatment to make the precursor uniform, adding 0.9 g dopamine hydrochloride, carrying out suction filtration after full reaction, taking filter residues, drying the filter residues through a vacuum oven, wherein the temperature of the vacuum oven is 80 ℃, the heat preservation time is 24 hours, placing the dried precursor in a tube furnace, sintering, heating to 800 ℃ at 5 ℃/min, and preserving heat for 120 minutes.
Zinc-air battery and preparation method of composite electrode for zinc-air battery
(1) Dispersing a first catalyst in a mixed solution of a perfluorinated sulfonic acid polymer solution and absolute ethyl alcohol, wherein the mass ratio of the first catalyst to the perfluorinated sulfonic acid polymer solution to the absolute ethyl alcohol is 1:0.2:0.8, so as to obtain a precursor solution A;
(2) Preparing a mixed solution of cobalt nitrate, ammonium fluoride and urea, wherein the mass ratio of the cobalt nitrate to the ammonium fluoride to the urea is 1:0.18:0.85, placing the mixed solution and the carrier in a reaction kettle, reacting at 140 ℃ for 8 hours, respectively cleaning the reacted carrier with ultrapure water and ethanol for 10 minutes, and drying the cleaned carrier at 80 ℃ for 24 hours to prepare a precursor B;
(3) Placing the precursor B in the downstream of a tube furnace, placing 1g of phosphorus source in the upstream of the tube furnace, and heating to 350 ℃ at 2 ℃/min for 120min to prepare a precursor C;
(4) And (3) dropwise adding the precursor A on the surface of the precursor C for 5 times, wherein 50 mu L of the precursor A is added each time, baking is carried out by an infrared lamp in the dropwise adding process, and the precursor A is transferred to a vacuum oven for drying after the dropwise adding is finished, so that the composite electrode (SAC-Fe/NC, niPx) is obtained.
Example 3
Zinc-air battery and preparation method of composite electrode for zinc-air battery
(1) Weighing 10 mg of Pt/C powder catalyst, then adding a mixed solution of perfluorosulfonic acid polymer solution and absolute ethyl alcohol, wherein the mass ratio of the Pt/C powder catalyst to the perfluorosulfonic acid polymer solution to the absolute ethyl alcohol is 1:0.2:0.8, and carrying out ultrasonic treatment to uniformly disperse the Pt/C powder catalyst to obtain a precursor A;
(2) Preparing a mixed solution of cobalt nitrate, ammonium fluoride and urea, wherein the mass ratio of the cobalt nitrate to the ammonium fluoride to the urea is 1:0.18:0.85, placing the mixed solution and the carrier in a reaction kettle, reacting at 140 ℃ for 8 hours, respectively cleaning the reacted carrier with ultrapure water and ethanol for 10 minutes, and drying the cleaned carrier at 80 ℃ for 24 hours to prepare a precursor B;
(3) Placing the precursor B in the downstream of a tube furnace, placing 1g of phosphorus source in the upstream of the tube furnace, and heating to 350 ℃ at 2 ℃/min for 120min to prepare a precursor C;
(4) Dripping the precursor A on the surface of the precursor C for 5 times (50 mu L each time), baking by an infrared lamp in the dripping process, and transferring to a vacuum oven for drying after the dripping is finished to obtain the composite electrode (Pt/C, fe) 2 P）。
Comparative example 1
The composite electrode for zinc-air cell was prepared by a method for preparing composite electrode for zinc-air cell with reference to CN 115719816A. (SAC-Co/NC, coPx)
Test example 1
The composite electrodes prepared in example 1 and comparative example 1 were tested using a three electrode system with zinc sheets as the reference and counter electrodes and the composite electrode as the operating electricity.
Referring to fig. 1, the composite electrode prepared by the present invention exhibits high power density and current density in a zinc-air battery. Compared with comparative example 1, the invention only adopts one metal carrier, can effectively avoid the problem of poor mass transfer between two metal carriers, and can effectively reduce electrochemical impedance in the reaction process, thereby exhibiting more excellent performance. |
Comparative example 2
On the basis of the embodiment 1, the preparation method of the zinc-air battery and the preparation method of the composite electrode for the zinc-air battery in the step (3) is specifically: and placing the precursor B in the downstream of a tube furnace, placing 500mg of phosphorus source in the upstream of the tube furnace, and heating to 300 ℃ at 2 ℃/min for 120min to prepare the precursor C.
Through tests, the performance of the composite electrode prepared in the comparative example 2 is reduced, the consumption and the reaction temperature of the phosphorus source are adjusted in the comparative example 2, so that the phosphorus source cannot fully react with the precursor, the phosphide is single, the OER performance of the catalyst is further reduced, and the charge and discharge of the zinc-air battery are not facilitated.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (9)
1. A preparation method of a zinc-air battery and a composite electrode for the zinc-air battery is characterized in that: the method comprises the following steps:
(1) Dispersing a first catalyst in a mixed solution of a perfluorinated sulfonic acid polymer and ethanol to obtain a precursor solution A;
(2) Preparing a mixed solution containing a cobalt source, ammonium fluoride and urea, and placing the mixed solution and a carrier in a reaction kettle to prepare a precursor B;
(3) Placing the precursor B in a tube furnace for heating to obtain a precursor C;
(4) And (3) dropwise adding the precursor A on the surface of the precursor C, and drying to obtain a finished product.
2. The zinc-air cell, the method for producing the composite electrode for zinc-air cell, according to claim 1, characterized in that: in the step (1), the preparation method of the first catalyst comprises the following steps:
s1: mixing monoatomic powder, hydrochloric acid solution and melamine, and heating to obtain a precursor 1;
s2: and placing the precursor 1 in a muffle furnace, sintering at 400-600 ℃, mixing the sintered precursor 1 with a buffer solution, adding dopamine hydrochloride, drying, and sintering in a tube furnace to obtain the first catalyst.
3. The zinc-air cell, the method for producing the composite electrode for zinc-air cell, according to claim 2, characterized in that: in the step S1, the monoatomic powder is one of a monoatomic cobalt catalyst, a monoatomic iron catalyst and a platinum-based powder catalyst; the feed liquid ratio of the monoatomic powder, the melamine and the hydrochloric acid solution is 75-85mg:8-9g:110-130mL.
4. The zinc-air cell, the method for producing the composite electrode for zinc-air cell, according to claim 2, characterized in that: in the step S2, the feed liquid ratio of the precursor 1 to the buffer solution to the dopamine hydrochloride is 1.8-2.2g:70-80mL:0.8-1g, wherein the drying is carried out for 20-28h at 70-90 ℃, the sintering temperature of the tube furnace is 750-850 ℃, and the heat preservation is carried out for 100-140min.
5. The zinc-air cell, the method for producing the composite electrode for zinc-air cell, according to claim 1, characterized in that: in the step (1), the mass ratio of the first catalyst to the perfluorinated sulfonic acid polymer to the ethanol is 1:0.15-0.25:0.7-0.9.
6. The zinc-air cell, the method for producing the composite electrode for zinc-air cell, according to claim 1, characterized in that: in the step (2), the mass ratio of the cobalt source, the ammonium fluoride and the urea is 1:0.17-0.19:0.8-0.9; the reaction kettle is used for reacting for 7-9 hours at 135-145 ℃, the carrier after the reaction is washed by ultrapure water and ethanol, and the carrier after the washing is dried for 20-28 hours at 70-90 ℃.
7. The zinc-air cell, the method for producing the composite electrode for zinc-air cell, according to claim 1, characterized in that: in the step (2), the carrier is a foam metal simple substance carrier or a foam metal alloy carrier, and the foam metal simple substance carrier is one of foam nickel, foam copper and foam iron; the foam metal alloy carrier is one of foam nickel-containing alloy, foam copper-containing alloy and foam iron-containing alloy.
8. The zinc-air cell, the method for producing the composite electrode for zinc-air cell, according to claim 1, characterized in that: in the step (3), the precursor B is placed in the downstream of a tube furnace, a phosphorus source is placed in the upstream of the tube furnace, and the temperature is raised to 330-370 ℃ by 1.5-2.5 ℃/min, and the temperature is kept for 100-140min.
9. The zinc-air cell, the method for producing the composite electrode for zinc-air cell, according to claim 1, characterized in that: in the step (4), the dripping time is 3-4 times, and each time is 45-55 mu L.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941674A (en) * | 2015-06-18 | 2015-09-30 | 西南大学 | Catalyst for loading cobalt phosphide on activated carbon as well as preparation and application of catalyst |
| CN111545241A (en) * | 2020-06-23 | 2020-08-18 | 东华大学 | Cobalt phosphide-loaded heteroatom-doped porous carbon material, and preparation method and application thereof |
| CN113249739A (en) * | 2021-06-04 | 2021-08-13 | 中国科学技术大学 | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst |
| CN114433085A (en) * | 2022-02-24 | 2022-05-06 | 海南大学 | Monoatomic catalyst and its preparing process |
| KR20220058260A (en) * | 2020-10-30 | 2022-05-09 | 한국과학기술원 | Precious metal single atom-nanoparticle catalysts derived from single atom sites using hydrothermal method and Manufacturing method of the Same |
| CN114807996A (en) * | 2022-04-13 | 2022-07-29 | 北京工业大学 | Preparation method of monatomic platinum-loaded transition metal phosphide hydrogen evolution catalyst |
| CN115692746A (en) * | 2022-10-24 | 2023-02-03 | 河南农业大学 | Method for preparing ORR and OER dual-function catalyst by one-step deposition |
| CN115719816A (en) * | 2022-11-23 | 2023-02-28 | 海南大学 | Preparation method of composite electrode for zinc-air battery |
| CN116180128A (en) * | 2023-04-25 | 2023-05-30 | 北京建工环境修复股份有限公司 | Self-supporting non-noble metal electrocatalyst material, and preparation method and application thereof |
-
2023
- 2023-09-20 CN CN202311217013.XA patent/CN117219927B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104941674A (en) * | 2015-06-18 | 2015-09-30 | 西南大学 | Catalyst for loading cobalt phosphide on activated carbon as well as preparation and application of catalyst |
| CN111545241A (en) * | 2020-06-23 | 2020-08-18 | 东华大学 | Cobalt phosphide-loaded heteroatom-doped porous carbon material, and preparation method and application thereof |
| KR20220058260A (en) * | 2020-10-30 | 2022-05-09 | 한국과학기술원 | Precious metal single atom-nanoparticle catalysts derived from single atom sites using hydrothermal method and Manufacturing method of the Same |
| CN113249739A (en) * | 2021-06-04 | 2021-08-13 | 中国科学技术大学 | Metal phosphide-loaded monatomic catalyst, preparation method thereof and application of metal phosphide-loaded monatomic catalyst as hydrogen evolution reaction electrocatalyst |
| CN114433085A (en) * | 2022-02-24 | 2022-05-06 | 海南大学 | Monoatomic catalyst and its preparing process |
| CN114807996A (en) * | 2022-04-13 | 2022-07-29 | 北京工业大学 | Preparation method of monatomic platinum-loaded transition metal phosphide hydrogen evolution catalyst |
| CN115692746A (en) * | 2022-10-24 | 2023-02-03 | 河南农业大学 | Method for preparing ORR and OER dual-function catalyst by one-step deposition |
| CN115719816A (en) * | 2022-11-23 | 2023-02-28 | 海南大学 | Preparation method of composite electrode for zinc-air battery |
| CN116180128A (en) * | 2023-04-25 | 2023-05-30 | 北京建工环境修复股份有限公司 | Self-supporting non-noble metal electrocatalyst material, and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| PENG RAO 等: "Isolated Co Atoms Anchored on Defective Nitrogen-doped Carbon Graphene as Efficient Oxygen Reduction Reaction Electrocatalysts", 24 February 2022, pages: 12371 * |
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