CN115064660A - Preparation method and application of magnesium metal battery negative electrode functional coating and negative electrode plate - Google Patents
Preparation method and application of magnesium metal battery negative electrode functional coating and negative electrode plate Download PDFInfo
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- CN115064660A CN115064660A CN202210781328.6A CN202210781328A CN115064660A CN 115064660 A CN115064660 A CN 115064660A CN 202210781328 A CN202210781328 A CN 202210781328A CN 115064660 A CN115064660 A CN 115064660A
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 110
- 239000011248 coating agent Substances 0.000 title claims abstract description 77
- 238000000576 coating method Methods 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 239000002923 metal particle Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 9
- 239000010954 inorganic particle Substances 0.000 claims abstract description 9
- 239000002033 PVDF binder Substances 0.000 claims description 15
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 13
- 238000005498 polishing Methods 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 6
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 5
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- UDKXBPLHYDCWIG-UHFFFAOYSA-M [S-2].[S-2].[SH-].S.[V+5] Chemical compound [S-2].[S-2].[SH-].S.[V+5] UDKXBPLHYDCWIG-UHFFFAOYSA-M 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- ROUIDRHELGULJS-UHFFFAOYSA-N bis(selanylidene)tungsten Chemical compound [Se]=[W]=[Se] ROUIDRHELGULJS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 claims description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 2
- 239000003792 electrolyte Substances 0.000 abstract description 6
- 230000008021 deposition Effects 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000012983 electrochemical energy storage Methods 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 230000000087 stabilizing effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 239000012300 argon atmosphere Substances 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- IWCVDCOJSPWGRW-UHFFFAOYSA-M magnesium;benzene;chloride Chemical compound [Mg+2].[Cl-].C1=CC=[C-]C=C1 IWCVDCOJSPWGRW-UHFFFAOYSA-M 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229910017267 Mo 6 S 8 Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
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Classifications
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0416—Methods of deposition of the material involving impregnation with a solution, dispersion, paste or dry powder
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/621—Binders
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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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
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
Abstract
The invention relates to the technical field of electrochemical energy storage, and relates to a preparation method of a negative functional coating and a negative pole piece of a magnesium metal battery and application of the negative functional coating and the negative pole piece in the magnesium metal battery. The functional coating is one or more of metal particles, carbon materials or inorganic particles, and is adhered to the surface of the magnesium metal sheet through an organic binder to form the magnesium metal battery negative electrode functional coating. The invention utilizes metal particles or carbon materials or inorganic particles to increase the surface energy of the magnesium metal cathode surface, thereby achieving the purposes of inhibiting the side reaction between the magnesium metal cathode and the electrolyte and stabilizing the uniform deposition of magnesium metal. The invention has the advantages of easily obtained raw materials, low cost and high production efficiency, and the preparation technology is compatible with the preparation equipment and process of the existing battery pole piece and is applicable to both magnesium metal primary batteries and secondary battery systems.
Description
Technical Field
The invention relates to the technical field of electrochemical energy storage, and relates to a preparation method of a negative functional coating and a negative pole piece of a magnesium metal battery and application of the negative functional coating and the negative pole piece in the magnesium metal battery.
Background
Magnesium metal negative electrode relies on its high volumetric specific capacity (3833 mAh/cm) 3 ) The raw materials are rich, the price is low, the safety is high, and the like, and the method is greatly concerned by the research and development circles. However, magnesium metal anodes face several challenges in commercial applications that need to be overcome, particularly in magnesium metal secondary battery systems. Firstly, magnesium metal, as a metal with high reducibility, can have a significant redox side reaction with an electrolyte system, so that the surface of magnesium metal is seriously corroded or passivated, and the normal operation of a magnesium metal cathode is influenced. Secondly, in the magnesium metal secondary battery system, along with the progress of the charging and discharging process, the electrochemical reaction rate on the surface of the magnesium metal is not uniform, so that the obvious phenomenon of uneven deposition or dissolution can occur, and if serious, a dendritic crystal structure or a convex structure penetrating through a battery diaphragm can be formed, thereby causing short circuit in the battery and bringing uncontrollable potential safety hazard. Luo et al tried to construct an artificial interface layer on the surface of magnesium metal cathode (National science review,2020,7(2):333-ials 2020,26:408 and 413), but the modification means generally have the problem of complex process, and the effectiveness of the interface protection layers is not examined under the condition of high surface capacity, so the commercial application prospect is still to be examined.
In order to solve the technical problems, the invention provides a preparation method of a negative electrode functional coating and a negative electrode plate of a magnesium metal battery and an application of the negative electrode functional coating and the negative electrode plate in the magnesium metal battery, which can effectively solve the problems of interface side reaction and uneven deposition of the magnesium metal negative electrode, have simple process and are suitable for large-scale production.
Disclosure of Invention
The invention aims to provide a negative electrode functional coating of a magnesium metal battery, a preparation method of a negative electrode pole piece and application of the negative electrode pole piece in the magnesium metal battery.
In order to achieve the purpose, the invention adopts the technical scheme that:
the functional coating is one or more of metal particles, carbon materials or inorganic particles, and is adhered to the surface of a magnesium metal sheet through an organic binder to form the magnesium metal battery cathode functional coating.
The metal particles are one or more of magnesium powder, tungsten powder, molybdenum powder, vanadium powder, bismuth powder and tin powder; the inorganic particles are one or more of molybdenum disulfide, titanium disulfide, vanadium tetrasulfide and tungsten diselenide; the carbon material is one or more of graphene, graphite, carbon nano tubes, conductive carbon black, vapor-grown carbon fibers and Ketjen black; the binder is one or more of polyvinylidene fluoride, polyacrylic acid, polytetrafluoroethylene and polyvinyl alcohol.
A preparation method of a magnesium metal battery negative electrode functional coating comprises the following steps: the method comprises the following steps:
1) in an inert atmosphere or dry air, polishing the surface oxide layer of the magnesium metal sheet completely by using sand paper;
2) dissolving a binder in an organic solvent, and then dispersing functional coating particles in the solution to obtain a uniform solution of the functional coating particles and the organic binder;
3) and (3) coating the functional coating solution obtained in the step (2) on the surface of the magnesium metal sheet obtained in the step (1), forming a uniform functional coating surface on the surface of the magnesium metal sheet, and drying to obtain the stable magnesium metal negative electrode functional coating.
The mesh number of the sand paper used for polishing in the step 1) is 400-2000 meshes, and the polishing time is 2-30 min.
The final concentration of the binder in the uniform solution of the functional coating particles and the organic binder in the step 2) is 5 mg/ml -1 ～300mg·ml -1 (ii) a The organic solvent for dissolving the binder is one or more of acetone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide; the mass ratio of the metal particles or the carbon material or the inorganic particles to the binder is 20: 1-1: 2.
The organic solvent is used for dispersing the binder.
The binder provides adhesion between the functional coating and the magnesium metal negative electrode, and prevents the functional coating from falling off.
The thickness of the functional coating solution coated in the step 3) is between 10 and 500 micrometers, and the thickness of the dried coating is between 1 and 100 micrometers.
The application of the magnesium metal battery negative electrode functional coating is an application of the magnesium metal battery negative electrode functional coating in preparation of a magnesium metal negative electrode sheet.
The magnesium metal negative plate comprises the negative functional coating.
A magnesium metal battery comprises a magnesium metal primary battery and a magnesium metal secondary battery, and comprises the magnesium metal negative plate.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention utilizes metal particles or carbon materials or inorganic particles to increase the surface energy of the magnesium metal cathode surface, and isolates the direct contact between magnesium metal and electrolyte, thereby effectively inhibiting the side reaction between the magnesium metal cathode and electrolyte and simultaneously realizing the uniformity and stability of the deposition and dissolution process of the magnesium metal cathode.
(2) The organic binder used in the invention can provide adhesion between the coating material and the magnesium metal negative electrode, and prevent the coating material from falling off in the charging and discharging processes.
(3) The invention has the advantages of easily obtained raw materials, low cost and high production efficiency, and the preparation technology is compatible with the preparation equipment and process of the existing battery pole piece and is applicable to both magnesium metal primary batteries and secondary battery systems.
Drawings
FIG. 1 is a surface photograph of a scanning electron microscope of a magnesium metal negative electrode protected in example 1 of the present invention.
FIG. 2 is a scanning electron micrograph of a magnesium metal negative electrode protected in example 1 of the present invention.
Fig. 3 is a curve of the charge-discharge capacity and the coulombic efficiency of the magnesium metal battery after protection according to the embodiment 1 of the present invention, as a function of the number of cycles.
Fig. 4 is a curve of the charge-discharge capacity and the coulombic efficiency of the magnesium metal battery after protection in example 2 of the present invention according to the number of cycles.
Fig. 5 is a curve showing the charge-discharge capacity and coulombic efficiency of the magnesium metal battery after protection in example 3 of the present invention as a function of the number of cycles.
Fig. 6 is a curve of the charge-discharge capacity and the coulombic efficiency of the magnesium metal battery after protection in the embodiment 4 of the present invention according to the number of cycles.
Fig. 7 is a graph showing the charge and discharge capacity and coulombic efficiency according to the number of cycles of the magnesium metal battery of comparative example 1 of the present invention.
Detailed Description
The invention is described below by means of specific embodiments. Unless otherwise specified, all technical means used in the present invention are well known to those skilled in the art. In addition, the embodiments should be considered illustrative, and not restrictive, of the scope of the invention, which is defined solely by the claims. It will be apparent to those skilled in the art that various changes or modifications in the components and amounts of the materials used in these embodiments can be made without departing from the spirit and scope of the invention.
The following examples are all operated in the dry environment with dew point of-35 ℃ or in the oxygen-free and water-free argon environment to prepare the magnesium metal negative plate with the functional coating.
Example 1
A functional coating of a magnesium metal battery cathode is characterized in that the functional coating is molybdenum metal particles and is adhered to the surface of a magnesium metal sheet through a polyvinylidene fluoride adhesive.
The specific operation is as follows:
1) in argon atmosphere or dry air (dew point is below-30 ℃), polishing the surface oxide layer of the magnesium metal sheet by 600-mesh abrasive paper;
2) dissolving 0.2g polyvinylidene fluoride (number average molecular weight is larger than 100000) binder in 10mL N-methyl pyrrolidone organic solvent, and stirring uniformly to obtain 20mg mL -1 Then 2g of molybdenum metal powder (average particle size is 500 nm) is dispersed in the solution to obtain a uniform solution of the molybdenum metal powder and the polyvinylidene fluoride;
3) and (3) coating the functional coating solution obtained in the step 2) on the surface of the magnesium metal sheet obtained in the step 1) by using a scraper with the thickness of 200 micrometers, forming a uniform functional coating surface on the surface of the magnesium metal sheet, and drying to obtain the magnesium metal negative plate protected by molybdenum metal particles.
Scanning electron microscope (abbreviated as SEM) tests are performed on the magnesium metal negative electrode functional coating prepared in example 1 according to fig. 1 and fig. 2, the SEM image of the surface is shown in fig. 1, the SEM image of the cross section is shown in fig. 2, and it can be seen that the magnesium metal negative electrode surface functional coating is uniform and dense, and the thickness is 15-30 μm.
Example 2
A functional coating of a magnesium metal battery cathode is characterized in that the functional coating is tungsten metal particles and is adhered to the surface of a magnesium metal sheet through a polyvinylidene fluoride adhesive.
The specific operation is as follows:
1) in argon atmosphere or dry air (dew point is below-30 ℃), polishing the surface oxide layer of the magnesium metal sheet by 600-mesh abrasive paper;
2) dissolving 0.2g polyvinylidene fluoride (number average molecular weight greater than 100000) binder in 10mL N-methyl pyrrolidoneStirring the mixture evenly in an organic solvent to obtain the solution with the concentration of 20mg ml -1 Then 2g of tungsten metal powder (with an average particle size of 500 nm) is dispersed in the solution to obtain a uniform solution of the tungsten metal powder and polyvinylidene fluoride;
3) and (3) coating the functional coating solution obtained in the step (2) on the surface of the magnesium metal sheet obtained in the step (1) by using a scraper with the thickness of 200 microns, forming a uniform functional coating surface on the surface of the magnesium metal sheet, and drying to obtain the magnesium metal negative plate protected by tungsten metal particles, wherein the functional coating is uniform and compact and has the thickness of 15-30 microns.
Example 3
A functional coating of a magnesium metal battery cathode is molybdenum disulfide and is adhered to the surface of a magnesium metal sheet through a polyvinylidene fluoride binder.
The specific operation is as follows:
1) in argon atmosphere or dry air (dew point is below-30 ℃), polishing the surface oxide layer of the magnesium metal sheet by 600-mesh abrasive paper;
2) dissolving 0.2g polyvinylidene fluoride (number average molecular weight is larger than 100000) binder in 10mL N-methyl pyrrolidone organic solvent, and stirring uniformly to obtain 20mg mL -1 Then dispersing 1g of molybdenum disulfide powder into the solution to obtain a uniform solution of molybdenum disulfide and polyvinylidene fluoride;
3) and (3) coating the functional coating solution obtained in the step (2) on the surface of the magnesium metal sheet obtained in the step (1) by using a scraper with the thickness of 200 micrometers, forming a uniform functional coating surface on the surface of the magnesium metal sheet, and drying to obtain the molybdenum disulfide-protected magnesium metal negative electrode sheet, wherein the functional coating is uniform and compact and has the thickness of 15-30 micrometers.
Example 4
A functional coating of a magnesium metal battery cathode is conductive carbon black and is adhered to the surface of a magnesium metal sheet through a polyvinylidene fluoride binder.
The specific operation is as follows:
1) in argon atmosphere or dry air (dew point is below-30 ℃), polishing the surface oxide layer of the magnesium metal sheet by 600-mesh abrasive paper;
2) dissolving 0.2g polyvinylidene fluoride (number average molecular weight is larger than 100000) binder in 10mL N-methyl pyrrolidone organic solvent, and stirring uniformly to obtain 20mg mL -1 Then 0.5g of conductive carbon black powder is dispersed in the polyvinylidene fluoride solution to obtain a uniform solution of the conductive carbon black and the polyvinylidene fluoride;
3) and (3) coating the functional coating solution obtained in the step (2) on the surface of the magnesium metal sheet obtained in the step (1) by using a scraper with the thickness of 200 microns, forming a uniform functional coating surface on the surface of the magnesium metal sheet, and drying to obtain the conductive carbon black protected magnesium metal negative plate, wherein the functional coating is uniform and compact and has the thickness of 15-30 microns.
Comparative example 1:
the comparative example only performed polishing and grinding treatment on the magnesium metal sheet. And polishing the magnesium metal sheet by using 600-mesh sand paper to remove a surface oxide layer.
The magnesium metal sheets coated with the functional coating obtained in examples 1 to 4 and the magnesium metal sheets polished in comparative example 1 were cut into small pieces of 14mm, and used as cathodes of magnesium metal batteries, and then scherrel phase Mo was used 6 S 8 The material is used as an anode, and the button cell is assembled by a cathode shell, a magnesium sheet, a diaphragm, electrolyte, an anode sheet and an anode shell in sequence, wherein the diaphragm is a common polypropylene (PP) diaphragm, and the anode is Mo 6 S 8 The loading of the material was 15mg cm -2 The electrolyte is commonly used phenylmagnesium chloride + AlCl 3 Tetrahydrofuran solution (phenylmagnesium chloride concentration 0.8M, AlCl) 3 Is 0.4M). These Mg// Mo compounds 6 S 8 The battery is subjected to a multiplying power charge and discharge performance test on LAND equipment, the charge and discharge multiplying power is 0.5C, and the theoretical specific capacity is set to be 128mAh g -1 The respective charge and discharge curves are shown in fig. 3 to 7. The technical effect achieved by the functional coating was evaluated here using the specific charge-discharge capacity of the battery positive electrode and the number of final cycles before short-circuiting. A sudden overcharge phenomenon during charge and discharge is generally understood as a short circuit of the battery. The specific experimental data are summarized in table 1 below.
TABLE 1 Mg// Mo in examples and comparative examples 6 S 8 Comparison of cell Performance
As can be seen from fig. 7, the battery assembled from the unprotected magnesium metal sheets in comparative example 1 suffered from a serious internal short circuit failure after 78 cycles of charging and discharging. As can be seen by comparing the specific charge/discharge capacities (FIGS. 3 to 6) of the batteries of examples 1 to 4, the functional coating of the present invention can improve Mg// Mo well 6 S 8 The battery has heavy short circuit risk in the charging and discharging process, the capacity retention rate and the long cycle stability of the battery are greatly improved, and the experimental data fully prove the beneficial effects of the protection technology.
Claims (9)
1. The magnesium metal battery negative electrode functional coating is characterized in that: the functional coating is one or more of metal particles, carbon materials or inorganic particles, and is adhered to the surface of the magnesium metal sheet through an organic binder to form the magnesium metal battery negative electrode functional coating.
2. The magnesium metal battery negative electrode functional coating of claim 1, wherein: the metal particles are one or more of magnesium powder, tungsten powder, molybdenum powder, vanadium powder, bismuth powder and tin powder; the inorganic particles are one or more of molybdenum disulfide, titanium disulfide, vanadium tetrasulfide and tungsten diselenide; the carbon material is one or more of graphene, graphite, carbon nano tubes, conductive carbon black, vapor-grown carbon fibers and Ketjen black; the binder is one or more of polyvinylidene fluoride, polyacrylic acid, polytetrafluoroethylene and polyvinyl alcohol.
3. A method for preparing the magnesium metal battery negative electrode functional coating according to claim 1, which is characterized in that: the method comprises the following steps:
1) in an inert atmosphere or dry air, polishing the surface oxide layer of the magnesium metal sheet completely by using sand paper;
2) dissolving a binder in an organic solvent, and then dispersing the functional coating particles in the solution to obtain a uniform solution of the functional coating particles and the organic binder;
3) and (3) coating the functional coating solution obtained in the step (2) on the surface of the magnesium metal sheet obtained in the step (1), forming a uniform functional coating surface on the surface of the magnesium metal sheet, and drying to obtain the stable magnesium metal negative electrode functional coating.
4. The preparation method of the magnesium metal battery cathode functional coating according to claim 3, characterized in that: the mesh number of the sand paper used for polishing in the step 1) is 400-2000 meshes, and the polishing time is 2-30 min.
5. The preparation method of the magnesium metal battery negative electrode functional coating according to claim 3, characterized in that: the final concentration of the binder in the uniform solution of the functional coating particles and the organic binder in the step 2) is 5 mg/ml -1 ～300mg·ml -1 (ii) a The organic solvent for dissolving the binder is one or more of acetone, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and dimethyl sulfoxide; the mass ratio of the metal particles or the carbon material or the inorganic particles to the binder is 20: 1-1: 2.
6. The preparation method of the magnesium metal battery negative electrode functional coating according to claim 3, characterized in that: the thickness of the functional coating solution coated in the step 3) is between 10 and 500 micrometers, and the thickness of the dried coating is between 1 and 100 micrometers.
7. The application of the magnesium metal battery negative electrode functional coating of claim 1, which is characterized in that: the magnesium metal battery negative electrode functional coating is applied to preparation of a magnesium metal negative electrode sheet.
8. A magnesium metal negative electrode sheet, characterized by comprising the negative electrode functional coating according to claim 1.
9. A magnesium metal battery comprises a magnesium metal primary battery and a magnesium metal secondary battery, and is characterized in that: comprising the magnesium metal negative electrode sheet according to claim 7.
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Citations (5)
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| CN102439761A (en) * | 2009-02-27 | 2012-05-02 | 丰田自动车工程及制造北美公司 | Electrode compositions and processes |
| CN110783551A (en) * | 2019-11-13 | 2020-02-11 | 华南师范大学 | Lithium electrode material, preparation method thereof and battery containing lithium electrode material |
| CN111463403A (en) * | 2020-04-13 | 2020-07-28 | 武汉大学 | Negative electrode material modified by composite artificial solid electrolyte interface film and battery application thereof |
| WO2022012715A1 (en) * | 2020-07-15 | 2022-01-20 | Schaeffler Technologies AG & Co. KG | Anode for a magnesium battery and method for the production thereof |
| CN114792773A (en) * | 2021-01-26 | 2022-07-26 | 杨曦 | Battery cathode protected by hydrophobic insulating layer, preparation method and battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102439761A (en) * | 2009-02-27 | 2012-05-02 | 丰田自动车工程及制造北美公司 | Electrode compositions and processes |
| CN110783551A (en) * | 2019-11-13 | 2020-02-11 | 华南师范大学 | Lithium electrode material, preparation method thereof and battery containing lithium electrode material |
| CN111463403A (en) * | 2020-04-13 | 2020-07-28 | 武汉大学 | Negative electrode material modified by composite artificial solid electrolyte interface film and battery application thereof |
| WO2022012715A1 (en) * | 2020-07-15 | 2022-01-20 | Schaeffler Technologies AG & Co. KG | Anode for a magnesium battery and method for the production thereof |
| CN114792773A (en) * | 2021-01-26 | 2022-07-26 | 杨曦 | Battery cathode protected by hydrophobic insulating layer, preparation method and battery |
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