CN113224329A - Co3O4/MXene composite catalyst and preparation method and application thereof - Google Patents
Co3O4/MXene composite catalyst and preparation method and application thereof Download PDFInfo
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- CN113224329A CN113224329A CN202110479555.9A CN202110479555A CN113224329A CN 113224329 A CN113224329 A CN 113224329A CN 202110479555 A CN202110479555 A CN 202110479555A CN 113224329 A CN113224329 A CN 113224329A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 84
- 239000002131 composite material Substances 0.000 title claims abstract description 65
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 21
- 150000001868 cobalt Chemical class 0.000 claims abstract description 12
- 239000012716 precipitator Substances 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 30
- 239000006185 dispersion Substances 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 16
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 16
- 239000011230 binding agent Substances 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 11
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 9
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 9
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 9
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 9
- 239000007774 positive electrode material Substances 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 235000013877 carbamide Nutrition 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 229940044175 cobalt sulfate Drugs 0.000 claims description 2
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 11
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 5
- 238000009792 diffusion process Methods 0.000 abstract description 5
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 5
- HPGPEWYJWRWDTP-UHFFFAOYSA-N lithium peroxide Chemical compound [Li+].[Li+].[O-][O-] HPGPEWYJWRWDTP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000010405 anode material Substances 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 description 20
- 238000003756 stirring Methods 0.000 description 17
- 239000000843 powder Substances 0.000 description 15
- 239000000243 solution Substances 0.000 description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 13
- 238000002156 mixing Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001291 vacuum drying Methods 0.000 description 11
- 238000005406 washing Methods 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- 229910001323 Li2O2 Inorganic materials 0.000 description 7
- 239000007795 chemical reaction product Substances 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000002356 single layer Substances 0.000 description 7
- 239000010410 layer Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 6
- PPVRVNPHTDGECD-UHFFFAOYSA-M F.[Cl-].[Li+] Chemical compound F.[Cl-].[Li+] PPVRVNPHTDGECD-UHFFFAOYSA-M 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 238000005530 etching Methods 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 229910001220 stainless steel Inorganic materials 0.000 description 5
- 239000010935 stainless steel Substances 0.000 description 5
- 239000006228 supernatant Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 238000003917 TEM image Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000000703 high-speed centrifugation Methods 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000006183 anode active material Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000012983 electrochemical energy storage Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 208000032953 Device battery issue Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 238000001453 impedance spectrum Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
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- 239000002994 raw material Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M12/00—Hybrid cells; Manufacture thereof
- H01M12/04—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type
- H01M12/06—Hybrid cells; Manufacture thereof composed of a half-cell of the fuel-cell type and of a half-cell of the primary-cell type with one metallic and one gaseous electrode
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- 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
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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)
- Hybrid Cells (AREA)
- Inert Electrodes (AREA)
Abstract
The invention provides a Co3O4a/MXene composite catalyst, a preparation method and application thereof. Co3O4The preparation method of the/MXene composite catalyst comprises the following steps: co preparation method of MXene, cobalt salt and precipitator through in-situ hydrothermal method3O4the/MXene composite catalytic material. The catalyst of the invention has simple preparation method and low cost, MXene provides good conductivity for the catalyst, and improves the diffusion rate of lithium ions, and Co3O4Provides abundant catalytic active sites. The catalyst is used for preparing the anode material of the lithium-air battery, and effectively promotes the lithium peroxide (Li) product of the lithium-air battery2O2) Avoids the problem of anode blockage, and greatly improves the cycle performance of the lithium-air battery。
Description
Technical Field
The invention belongs to the technical field of battery electrode materials, and particularly relates to Co3O4a/MXene composite catalyst, a preparation method and application thereof.
Background
In order to cope with the increasingly serious energy crisis and environmental problems, a new energy system is one of the important directions of future research while maintaining human survival and socioeconomic development. The current lithium ion battery technology is difficult to meet the requirement of a rapidly-developed long-endurance electric automobile because the relatively low energy density limits the driving mileage of the automobile. In order to make the electric vehicle develop healthily and stably and be widely used, a battery energy storage technology with higher energy density is needed, and the development of a secondary battery system with energy density higher than that of the current lithium ion battery is a necessary way for the development of the future electric vehicle.
Among the numerous electrochemical energy storage systems, lithium air batteries are due to their extremely high theoretical energy density (3500Wh/kg, based on the product Li on the positive electrode)2O2Calculated from the production amount of (b) and is receiving wide attention. Theoretically, the lithium air battery has an ultra-high energy density and a low cost, and is a novel environmental-friendly battery technology, and thus is considered to be a very promising electrochemical energy storage technology.
Although lithium air batteries have many advantages, improvements are still needed in some important areas. Among them, the discharge product of lithium-air batteries is lithium peroxide (Li)2O2) The material is a wide-band-gap insulating material, has strong insulativity and is difficult to decompose in the charging process, so the material can be continuously accumulated on a positive electrode in the battery circulating process to block the positive electrode, hinder the diffusion of oxygen of a positive electrode active material, reduce reactive active sites, reduce the energy efficiency of the battery, cause overhigh charging potential and finally shorten the battery circulating life.
Therefore, how to promote Li effectively2O2Decomposition during charging has been a focus of great concern to researchers. Among them, an important research direction is to solve Li by developing a highly efficient catalyst2O2The decomposition problem of (1).
Disclosure of Invention
In order to solve the problem of Li caused by discharge product in the lithium-air battery2O2The invention provides a Co catalyst, which has the problems of low energy efficiency and poor cycle performance caused by difficult decomposition3O4The catalyst is/MXene composite catalyst.
The invention also provides the above Co3O4A preparation method of a/MXene composite catalyst and application of the catalyst in a lithium air battery.
Co3O4The preparation method of the/MXene composite catalyst comprises the following steps:
MXene, cobalt salt and a precipitator are subjected to hydrothermal reaction, and after the reaction is finished, the Co is obtained through post-treatment3O4The catalyst is/MXene composite catalyst.
The preparation method utilizes hydrothermal reaction to generate Co3O4And particles are coated on the MXene surface. By utilizing the excellent conductivity of MXene, Co is improved3O4The conductivity of (2) contributes to the migration of lithium ions.
Co prepared by the preparation method3O4In the/MXene composite catalyst, Co3O4Has excellent catalytic activity and moderate cost; the MXene has good conductivity, large specific surface area and stable electrochemical performance, and the two-dimensional layered structure of the MXene can provide an ideal diffusion channel for the anode active material (oxygen). Mixing Co3O4the/MXene composite catalyst is applied to the anode of the lithium-air battery and can reduce Li2O2The charging voltage required for decomposition is effectively promoted to Li2O2The cycle performance of the lithium-air battery is decomposed and optimized, and the cycle life of the battery is greatly prolonged.
Preferably, MXene is Ti3C2TxWherein, TxRepresents a surface termination group.
Preferably, the mass ratio of MXene to cobalt salt to the precipitant is (1-6): 1: (1-6). In a further preferable scheme, the mass ratio of MXene to cobalt salt to the precipitant is (1-3): 1: (1-3).
Preferably, the cobalt salt is one or more of cobalt chloride, cobalt sulfate, cobalt acetate and cobalt nitrate. Cobalt nitrate is more preferable.
Preferably, the precipitant is one or more of hexamethylenetetramine, ammonium carbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide and urea. More preferably hexamethylenetetramine.
Preferably, the reaction temperature of the hydrothermal reaction is 150-200 ℃, and the reaction time is 12-24 h. More preferably, the reaction temperature of the hydrothermal reaction is 160 ℃ and the reaction time is 12 hours.
Preferably, the pH value of the system of the hydrothermal reaction is 7-9. Further preferably, the pH value is 7.5 to 8.5.
Preferably, the MXene is a single-few layer and is prepared by stripping MAX phase by etching, and the operation steps are as follows:
and 3, re-dispersing the multiple layers of MXene by using deionized water, shaking and stripping, carrying out high-speed centrifugation and layering, collecting supernatant, and carrying out freeze drying to obtain the single-few-layer MXene.
In the technical scheme, MXene adopts a single few layers with larger specific surface area, and is more suitable for preparing the catalyst.
More preferably, the mass ratio of the MAX phase to lithium fluoride in the lithium fluoride-hydrochloric acid solution is 1: 1.
more preferably, in the lithium fluoride-hydrochloric acid solution, the mass ratio of lithium fluoride to hydrogen chloride (HCl) is 1: (1-4), the concentration of the hydrochloric acid is 1-8M.
More preferably, in step 1, the MAX phase is etched in a lithium fluoride-hydrochloric acid solution under oil bath heating and stirring conditions; wherein the oil bath temperature is 30-55 ℃; the stirring speed is 300-500 rpm; the stirring time is 48-100 h. Further preferably, the oil bath temperature is 30-40 ℃; the stirring speed is 400-500 rpm; the stirring time is 90-100 h.
Preferably, in the step 2, after the etching is finished, the rotating speed of centrifugal washing of the reaction precipitate is 10000-15000 rpm; the centrifugation time is 10-30 min.
Preferably, in the step 3, the shaking and stripping time is 30-90 min; the rotating speed of the high-speed centrifugation is 3500-10000 rpm; the high-speed centrifugation time is 0.5-1 h.
Preferably, the method comprises the following steps:
(1) adding MXene into deionized water, and adjusting the pH value to obtain MXene dispersion liquid;
(2) cobalt salt and a precipitator are put into the MXene dispersion liquid for hydrothermal reaction, and after the reaction is finished, the Co is obtained by post-treatment3O4The catalyst is/MXene composite catalyst.
Preferably, in the step (1), MXene is added into deionized water, stirred by ultrasonic waves and adjusted in pH value to obtain MXene dispersion liquid; wherein the ultrasonic time is 0.5-1 h; the stirring time is 5-20 min.
More preferably, in the step (2), the hydrothermal reaction is performed in an argon atmosphere, the cobalt salt and the precipitant are added into the MXene dispersion liquid, the mixture is stirred for 0.5-1 h in the argon atmosphere, and then the dispersion liquid is transferred to a reaction kettle for hydrothermal reaction.
More preferably, in the step (2), after completion of the hydrothermal reaction, the following post-treatment is performed: washing the reaction product, and then drying for 6-12 h at 60-100 ℃ in vacuum to obtain the Co3O4The catalyst is/MXene composite catalyst.
As a further preferable mode, the vacuum drying temperature is 60 ℃ and the vacuum drying time is 12 hours.
Co of the invention3O4The preparation method of the/MXene composite catalyst comprises the step of etching the MAX phase material by using lithium fluoride-hydrochloric acid mixed solutionHeating and stirring in an oil bath, washing with ionized water, shaking by hand, and centrifuging at a high speed to obtain single-few-layer MXene; adding cobalt salt and precipitator into the MXene dispersion liquid to prepare Co by an in-situ hydrothermal method3O4the/MXene composite catalytic material.
The catalyst of the invention has simple preparation process and low cost, MXene provides good conductivity for the catalyst, and improves the diffusion rate of lithium ions, and Co3O4Provides abundant catalytic active sites. The catalyst is used in the lithium-air battery, and effectively promotes the lithium peroxide (Li) product of the lithium-air battery2O2) The problem of anode blockage is avoided, and the cycle performance of the lithium-air battery is greatly improved.
The invention also provides Co prepared by the preparation method of any one of the technical schemes3O4The catalyst is/MXene composite catalyst.
The invention also provides Co prepared by any one of the technical schemes3O4The positive electrode material of the lithium-air battery is prepared from the/MXene composite catalyst.
Preferably, the positive electrode material is made of Super P and Co3O4the/MXene composite catalyst and PTFE binder;
wherein, Super P and Co3O4The mass ratio of the/MXene composite catalyst to the PTFE in the PTFE binder is as follows: (7-9): (0.5-1.5): (0.5 to 1.5).
More preferably, Super P and Co in the positive electrode material3O4The mass ratio of the/MXene composite catalyst to the PTFE in the PTFE binder is as follows: 8: 1: 1.
preferably, the method for preparing the lithium air battery positive electrode by using the positive electrode material comprises the following steps:
mixing the Co3O4the/MXene composite catalyst, Super P and PTFE binder are fully mixed and coated on a current collector, and then vacuum drying is carried out to obtain the catalyst containing Co3O4The positive electrode of the lithium-air battery of the/MXene composite catalyst.
Preferably, the current collector is made of stainless steel mesh.
Preferably, the vacuum drying temperature is 110-130 ℃, and the vacuum drying time is 10-15 h. More preferably, the vacuum drying temperature is 120 ℃ and the vacuum drying time is 12 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) co of the invention3O4the/MXene composite catalyst has excellent catalytic activity, large MXene specific surface area, favorable oxygen diffusion of the anode active material, capability of providing rich surface catalytic reaction sites, good conductivity and capability of improving Co3O4Increase the ionic and electronic conductivity of Co3O4The catalytic ability of (a).
(2) The preparation process is simple, the preparation method is safe and feasible, and the cost of raw materials is low.
(3) The invention mixes Co3O4the/MXene composite catalyst is introduced into the anode of the lithium-air battery, so that the discharge product Li of the lithium-air battery is effectively promoted2O2Avoid the battery from Li2O2The problem of rapid battery failure caused by continuous accumulation on the positive electrode greatly prolongs the cycle life of the lithium-air battery.
Drawings
FIG. 1 is a TEM and SEM images of MXene powder prepared in example 1 of the present invention;
FIG. 2 shows Co obtained in example 1 of the present invention3O4TEM image of/MXene composite catalyst;
FIG. 3 is a graph comparing the cycle performance curves of lithium-air batteries manufactured in examples 1 to 3 of the present invention and comparative example;
FIG. 4 is a comparative image of a scanning electron microscope showing the positive electrodes of the lithium-air batteries of examples 1 to 3 of the present invention after 40 cycles of cycling;
FIG. 5 is a graph showing a comparison of electrochemical impedances of 40 cycles of lithium-air batteries manufactured in examples 1 to 3 of the present invention and comparative examples.
Detailed Description
The technical solution of the present invention is further described with reference to the following specific examples, but the scope of the present invention is not limited thereto.
Example 1
Co3O4The preparation method of the/MXene composite catalyst comprises the following steps:
adding 0.55g of lithium fluoride powder into 15mL of 1M hydrochloric acid solution, and magnetically stirring until the solution is clear to obtain a mixed solution of lithium fluoride and hydrochloric acid; 0.55g of MAX phase material (Ti) was taken3AlC2) The powder was slowly added to the prepared mixed solution of lithium fluoride and hydrochloric acid with magnetic stirring, and heated and stirred at 35 ℃ in an oil bath at 450rpm for 96 hours. And after stirring, centrifugally washing the reaction precipitate for 3 times by using deionized water (the centrifugal rotation speed is 10000rpm, and the washing time is 20min) until the pH of the centrifuged supernatant is about 6-7 to obtain a multilayer MXene, and taking out and sealing for later use. And re-dispersing the prepared multi-layer MXene by using deionized water, shaking and stripping for 60min, centrifuging at the rotating speed of 3500rpm for 0.5h, taking the upper suspension, and drying at 60 ℃ for 8h to obtain single-layer and small-layer MXene powder.
Fig. 1 is a TEM image and an SEM image of the resulting MXene powder, and it can be seen from fig. 1 that the resulting MXene powder is a single layer.
0.3g of single-layer MXene powder is added into 40mL of deionized water, magnetically stirred for 5 minutes and then ultrasonically dispersed for 0.5 hour to obtain MXene dispersion liquid. The appropriate amount of tetrabutylammonium hydroxide solution was added to the dispersion until the pH of the dispersion was about 8. Respectively weighing 0.1g of cobalt nitrate and 0.3g of hexamethylenetetramine, placing the cobalt nitrate and the hexamethylenetetramine into the dispersion, stirring the mixture for 0.5h in an argon atmosphere, transferring the mixture into a 50mL hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an electrothermal blowing dry box, reacting the mixture for 12h at 160 ℃, cleaning the obtained reaction product for 2-3 times by using deionized water after the reaction is finished, drying the reaction product for 12h in a vacuum oven at 60 ℃, and finally obtaining Co3O4The catalyst is/MXene composite catalyst.
Mixing the obtained Co3O4The preparation method comprises the following steps of doping the/MXene composite catalyst into the positive electrode of the lithium-air battery:
16mg of Super P was weighed into a glass sample bottleIn (1), a small amount of ethanol was added to the mixture by a dropper, and 2mg of Co was weighed3O4the/MXene composite catalyst was mixed with Super P, and 20mg of 10 wt% PTFE binder (prepared by diluting the binder sold under the trademark D30LX with water) was added to the bottle using a pipette to obtain a positive electrode mixture. Super P and Co are maintained in the positive electrode mixture3O4The mass ratio of the/MXene composite catalyst to the PTFE is 8: 1: 1. and pouring the positive electrode mixture on a clean glass plate, fully mixing uniformly, evenly dividing into 20 parts, respectively coating the 20 parts on a stainless steel net with the diameter of 12mm to prepare positive electrode pieces, and keeping the amount of the positive electrode mixture on each positive electrode piece to be about 1 mg. After the manufacture is finished, the positive pole piece is placed in a vacuum drying furnace and dried for 12 hours under the vacuum condition of 120 ℃, and finally the Co-containing material is prepared3O4The positive electrode of the lithium-air battery of the/MXene composite catalyst.
Mixing the obtained mixture containing Co3O4The positive electrode of the/MXene composite catalyst is assembled in a lithium air battery and subjected to electrochemical performance test.
Example 2
Co3O4The preparation method of the/MXene composite catalyst comprises the following steps:
adding 1.09g of lithium fluoride powder into 20mL of 3M hydrochloric acid solution, and magnetically stirring until the solution is clear to obtain a mixed solution of lithium fluoride and hydrochloric acid; 1.09g of MAX phase material (Ti) was taken3AlC2) The powder was slowly added to the prepared mixed solution of lithium fluoride and hydrochloric acid with magnetic stirring, and heated and stirred at 35 ℃ in an oil bath at 450rpm for 96 hours. And after stirring, centrifugally washing the reaction precipitate for 3 times by using deionized water (the centrifugal rotation speed is 10000rpm, and the washing time is 20min) until the pH of the centrifuged supernatant is about 6-7 to obtain a multilayer MXene, and taking out and sealing for later use. And re-dispersing the prepared multilayer MXene by using deionized water, shaking and stripping for 60min, centrifuging at the rotating speed of 3500rpm for 0.5h, taking the upper suspension, and drying at the temperature of 60 ℃ for 8h to obtain single-layer MXene powder.
0.8g of single-layer MXene powder is added into 40mL of deionized water, magnetically stirred for 5 minutes and then super-stirredAnd performing sound dispersion for 0.5h to obtain MXene dispersion liquid. The appropriate amount of tetrabutylammonium hydroxide solution was added to the dispersion until the pH of the dispersion was about 8. Respectively weighing 0.4g of cobalt nitrate and 1.2g of hexamethylenetetramine, placing the cobalt nitrate and the hexamethylenetetramine into the dispersion, stirring the mixture for 0.5h in an argon atmosphere, transferring the mixture into a 50mL hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an electrothermal blowing dry box, reacting the mixture for 12h at 160 ℃, cleaning the obtained reaction product for 2-3 times by using deionized water after the reaction is finished, drying the reaction product for 12h in a vacuum oven at 60 ℃, and finally obtaining Co3O4The catalyst is/MXene composite catalyst.
Mixing the obtained Co3O4The preparation method comprises the following steps of doping the/MXene composite catalyst into the positive electrode of the lithium-air battery:
16mg of Super P was weighed into a glass sample bottle and dipped with a small amount of ethanol using a dropper, and 2mg of Co was weighed3O4the/MXene composite catalyst was mixed with Super P, and 20mg of 10 wt% PTFE binder (prepared by diluting the binder sold under the trademark D30LX with water) was added to the bottle using a pipette to obtain a positive electrode mixture. Super P, Co is maintained in the positive electrode mixture3O4The mass ratio of the/MXene composite catalyst to the PTFE is 8: 1: 1. and pouring the positive electrode mixture on a clean glass plate, fully mixing uniformly, evenly dividing into 20 parts, respectively coating the 20 parts on a stainless steel net with the diameter of 12mm to prepare positive electrode pieces, and keeping the amount of the positive electrode mixture on each positive electrode piece to be about 1 mg. After the manufacture is finished, the positive pole piece is placed in a vacuum drying furnace and dried for 12 hours under the vacuum condition of 120 ℃, and finally the Co-containing material is prepared3O4The positive electrode of the lithium-air battery of the/MXene composite catalyst.
Mixing the obtained mixture containing Co3O4The positive electrode of the/MXene composite catalyst is assembled in a lithium air battery and subjected to electrochemical performance test.
Example 3
Co3O4The preparation method of the/MXene composite catalyst comprises the following steps:
2.56g of lithium fluoride powder was added to 35mL of 8M hydrochloric acid solution and magnetically stirred until the solution was clear to give fluorideA mixed solution of lithium and hydrochloric acid; 2.56g of MAX phase material (Ti) was again taken3AlC2) The powder was slowly added to the prepared mixed solution of lithium fluoride and hydrochloric acid with magnetic stirring, and heated and stirred at 35 ℃ in an oil bath at 450rpm for 96 hours. And after stirring, centrifugally washing the reaction precipitate for 3 times by using deionized water (the centrifugal rotation speed is 10000rpm, and the washing time is 20min) until the pH of the centrifuged supernatant is about 6-7 to obtain a multilayer MXene, and taking out and sealing for later use. And re-dispersing the prepared multilayer MXene by using deionized water, shaking and stripping for 60min, centrifuging at the rotating speed of 3500rpm for 0.5h, taking the upper suspension, and drying at the temperature of 60 ℃ for 8h to obtain single-layer MXene powder.
Adding 1.53g of single-layer MXene powder into 40mL of deionized water, magnetically stirring for 5 minutes, and then ultrasonically dispersing for 0.5 hour to obtain MXene dispersion liquid. The appropriate amount of tetrabutylammonium hydroxide solution was added to the dispersion until the pH of the dispersion was about 8. Respectively weighing 1.53g of cobalt nitrate and 2g of hexamethylenetetramine, placing the cobalt nitrate and the hexamethylenetetramine into the dispersion, stirring the mixture for 0.5h in an argon atmosphere, transferring the mixture into a 50mL hydrothermal reaction kettle, placing the hydrothermal reaction kettle into an electrothermal blowing dry box, reacting the mixture for 12h at 160 ℃, cleaning the obtained reaction product for 2-3 times by using deionized water after the reaction is finished, drying the reaction product for 12h in a vacuum oven at 60 ℃, and finally obtaining Co3O4The catalyst is/MXene composite catalyst.
Mixing the obtained Co3O4The preparation method comprises the following steps of doping the/MXene composite catalyst into the positive electrode of the lithium-air battery:
16mg of Super P was weighed into a glass sample bottle and dipped with a small amount of ethanol using a dropper, and 2mg of Co was weighed3O4the/MXene composite catalyst was mixed with Super P, and 20mg of 10 wt% PTFE binder (prepared by diluting the binder sold under the trademark D30LX with water) was added to the bottle using a pipette to obtain a positive electrode mixture. Super P, Co is maintained in the positive electrode mixture3O4The mass ratio of the/MXene composite catalyst to the PTFE is 8: 1: 1. pouring the positive mixture on a clean glass plate, fully and uniformly mixing, evenly dividing into 20 parts, respectively coating on a stainless steel net with the diameter of 12mm to prepare a positive pole piece,about 1mg of the positive electrode mix was maintained on each positive electrode sheet. After the manufacture is finished, the positive pole piece is placed in a vacuum drying furnace and dried for 12 hours under the vacuum condition of 120 ℃, and finally the Co-containing material is prepared3O4The positive electrode of the lithium-air battery of the/MXene composite catalyst.
Mixing the obtained mixture containing Co3O4The positive electrode of the/MXene composite catalyst is assembled in a lithium air battery and subjected to electrochemical performance test.
Comparative example
In comparison with example 3, in this comparative example, Co was not added to the positive electrode material for lithium-air battery3O4The catalyst is/MXene composite catalyst.
16mg of Super P was weighed into a glass sample bottle, and a small amount of ethanol was dropped using a dropper, and 20mg of 10% (wt) PTFE binder (prepared by diluting the binder of brand D30LX with water) was added to the bottle using a pipette, to obtain a positive electrode mixture. And pouring the positive electrode mixture on a clean glass plate, fully mixing uniformly, evenly dividing into 20 parts, respectively coating the 20 parts on a stainless steel net with the diameter of 12mm to prepare positive electrode pieces, and keeping the amount of the positive electrode mixture on each positive electrode piece to be about 1 mg. After the manufacturing is finished, the positive pole piece is placed in a vacuum drying furnace and dried for 12 hours under the vacuum condition of 120 ℃, and finally the Super positive pole of the lithium-air battery is manufactured.
The Super-containing anode prepared in the way is applied and assembled in a lithium air battery, and an electrochemical performance test is carried out.
Case evaluation
FIG. 2 shows Co obtained in example 1 of the present invention3O4Transmission electron microscopy of the/MXene composite catalyst. As can be seen in FIG. 2, Co3O4The particles are uniformly coated on the MXene surface, which shows that the preparation of the composite catalyst is very successful and can effectively exert Co3O4Excellent catalytic activity and high conductivity of MXene.
Fig. 3 is a graph comparing the cycle performance curves of the lithium-air batteries provided in examples 1, 2, 3 and comparative examples. Wherein the charge-discharge current density is 0.2mA cm-2BatteriesCapacity set to 500mAh g-1The charge and discharge cutoff voltages were set to 4.5V and 2.2V, respectively. As shown in FIG. 3, the positive electrodes were doped with Co respectively3O4Examples 1, 2 and 3 of the/MXene composite catalyst provided lithium air batteries capable of cycling 116, 112 and 118 cycles, respectively; in contrast, the positive electrode was not Co-doped3O4The comparative example of/MXene composite catalyst provided a lithium air cell that could only cycle 47 cycles. Thus, Co is doped3O4The lithium air battery cycle performance of the/MXene composite catalyst is obviously improved.
Fig. 4 is a scanning electron microscope comparison graph of the positive electrode after 40 cycles of the lithium-air battery provided in example 1, example 2, example 3 and the comparative example. As shown in FIG. 4, the positive electrode is not doped with Co3O4Comparative example of/MXene composite catalyst the lithium-air cell provided in the comparative example was cycled 40 cycles before the surface of the positive electrode had been discharged with the product Li2O2Coverage, indicating Li during battery cycling2O2The electrolyte is difficult to decompose and is continuously accumulated on the positive electrode, the performance of the battery is deteriorated, and the battery can only circulate 47 circles (figure 3); in contrast, the positive electrodes were doped with Co, respectively3O4The lithium-air batteries provided in examples 1, 2 and 3 of the/MXene composite catalyst still maintain the porous structure on the surface of the positive electrode after 40 cycles of circulation, which shows that Li is deposited on the positive electrode2O2In small amounts, Li during cycling2O2Can be effectively decomposed, which shows that Co3O4the/MXene composite catalyst can effectively promote Li2O2Improves the cycle performance of the battery (fig. 3).
Fig. 5 is a graph comparing electrochemical impedance spectra of lithium-air batteries according to examples 1, 2, 3 and comparative examples after 40 cycles. Positive electrode undoped Co3O4Comparative example of/MXene composite catalyst provides a lithium-air battery with a higher impedance after 40 cycles due to the insulating Li that is difficult to decompose2O2The result of the constant accumulation on the positive electrode; the positive electrodes are respectively doped with Co3O4Implementation of the/ MXene Complex catalystExamples 1, 2 and 3 provided lithium-air batteries with still low impedance after 40 cycles, which is mainly insulating Li2O2The accumulation amount on the positive electrode was less than that in the comparative example, so that the battery resistance was lowered, further embodying Co3O4the/MXene composite catalyst can effectively promote Li2O2Decomposition and excellent catalytic performance.
Exemplary embodiments of the present invention are described above in detail. It should be understood that the scope of the present invention is not limited to the above-described embodiments. Modifications and variations of the present invention based on the prior art, which are considered to be within the basic concept of the invention as defined in the appended claims, are also within the scope of protection of the person skilled in the art, as determined by the doctrine of equivalents.
Claims (10)
1. Co3O4The preparation method of the/MXene composite catalyst is characterized by comprising the following steps:
MXene, cobalt salt and a precipitator are subjected to hydrothermal reaction, and after the reaction is finished, the Co is obtained through post-treatment3O4The catalyst is/MXene composite catalyst.
2. The method according to claim 1, wherein MXene is Ti3C2TxWherein, TxRepresents a surface termination group.
3. The preparation method according to claim 1, wherein the mass ratio of MXene, cobalt salt and precipitant is (1-6): 1: (1-6).
4. The preparation method according to claim 1, wherein the cobalt salt is a mixture of one or more of cobalt chloride, cobalt sulfate, cobalt acetate and cobalt nitrate.
5. The preparation method according to claim 1, wherein the precipitant is one or more of hexamethylenetetramine, ammonium carbonate, ammonium bicarbonate, sodium hydroxide, potassium hydroxide and urea.
6. The preparation method according to claim 1, wherein the reaction temperature of the hydrothermal reaction is 150-200 ℃ and the reaction time is 12-24 h;
the pH value of the system of the hydrothermal reaction is 7-9.
7. The method of claim 1, comprising the steps of:
(1) adding MXene into deionized water, and adjusting the pH value to obtain MXene dispersion liquid;
(2) cobalt salt and a precipitator are put into the MXene dispersion liquid for hydrothermal reaction, and after the reaction is finished, the Co is obtained by post-treatment3O4The catalyst is/MXene composite catalyst.
8. Co3O4the/MXene composite catalyst is characterized by being prepared by the preparation method of any one of claims 1 to 7.
9. A positive electrode material for a lithium-air battery, which comprises the Co of claim 83O4the/MXene composite catalyst is prepared.
10. The positive electrode material for a lithium-air battery according to claim 9, wherein the positive electrode material is made of Super P, Co3O4the/MXene composite catalyst and PTFE binder;
wherein, Super P and Co3O4The mass ratio of the/MXene composite catalyst to the PTFE in the PTFE binder is as follows: (7-9): (0.5-1.5): (0.5 to 1.5).
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