CN113972355A - ZnNi/C composite material modified lithium/carbon fluoride battery positive plate and preparation method thereof - Google Patents
ZnNi/C composite material modified lithium/carbon fluoride battery positive plate and preparation method thereof Download PDFInfo
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- CN113972355A CN113972355A CN202111231404.8A CN202111231404A CN113972355A CN 113972355 A CN113972355 A CN 113972355A CN 202111231404 A CN202111231404 A CN 202111231404A CN 113972355 A CN113972355 A CN 113972355A
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- 239000002131 composite material Substances 0.000 title claims abstract description 55
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 37
- 150000002641 lithium Chemical class 0.000 title claims abstract description 33
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 41
- 238000010438 heat treatment Methods 0.000 claims abstract description 32
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000000227 grinding Methods 0.000 claims abstract description 21
- 239000011267 electrode slurry Substances 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 16
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 15
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 15
- 239000011701 zinc Substances 0.000 claims abstract description 15
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 13
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011888 foil Substances 0.000 claims abstract description 13
- 239000011230 binding agent Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 230000005674 electromagnetic induction Effects 0.000 claims abstract description 9
- 238000004806 packaging method and process Methods 0.000 claims abstract description 9
- 239000011261 inert gas Substances 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 11
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 11
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 239000004584 polyacrylic acid Substances 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- 239000007888 film coating Substances 0.000 claims description 9
- 238000009501 film coating Methods 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002033 PVDF binder Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 claims description 3
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- OSOVKCSKTAIGGF-UHFFFAOYSA-N [Ni].OOO Chemical compound [Ni].OOO OSOVKCSKTAIGGF-UHFFFAOYSA-N 0.000 claims 1
- 229910000483 nickel oxide hydroxide Inorganic materials 0.000 claims 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 229910052744 lithium Inorganic materials 0.000 description 9
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/06—Electrodes for primary cells
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
Abstract
The invention discloses a ZnNi/C composite material modified lithium/carbon fluoride battery positive plate and a preparation method thereof, and the preparation method comprises the following steps: firstly, mixing a zinc source, a nickel source and a carbon source according to the mass ratio of zinc, nickel and carbon atoms of 1 (5-20) to (20-50), grinding to obtain a mixture A, putting the mixture A into a high-temperature tubular furnace, introducing inert gas, heating from room temperature to 150 ℃ at the speed of 10-30 ℃/min, preserving heat for 0.5-2h to obtain a product B; grinding the product B, then packaging the product B in a test tube filled with inert gas through a sealed glove box, putting the test tube into an electromagnetic induction heater, heating the test tube to 400-700 ℃, and cooling the test tube to obtain a ZnNi/C composite material; and then according to the mass ratio (7-9): (0.5-2): (0.5-1) mixing the carbon fluoride, the ZnNi/C composite material and a binder, dripping a solvent and stirring to obtain positive electrode slurry with fluidity, coating the positive electrode slurry on an aluminum foil, and drying to obtain the ZnNi/C composite material modified lithium/carbon fluoride battery positive electrode plate. The conductivity of the positive plate is improved, and the specific capacity, the storage performance and the rate capability of the battery are improved.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to an electrode material and a preparation method thereof, and particularly relates to a ZnNi/C composite material modified lithium/carbon fluoride battery positive plate and a preparation method thereof.
Background
Carbon fluoride (CFx) is one of the highest capacity positive electrodes in primary lithium batteries. Therefore, the Li/CFx primary battery is obviously superior to other competitive primary lithium batteries, and has an ultra-long shelf life, a wide working temperature range and a flat discharge voltage. However, the rate performance of Li/CFx cells is poor because the electron conductivity of CFx decreases with increasing fluorine content. These inherent disadvantages severely hamper their use in high power devices.
Based on the problems, the method has important practical significance for improving the specific capacity and the storage performance of the lithium/carbon fluoride battery and improving the conductivity and the rate performance of the positive plate.
Disclosure of Invention
The invention aims to provide a ZnNi/C composite material modified lithium/carbon fluoride battery positive plate and a preparation method thereof, which improve the conductivity of the positive plate and improve the specific capacity, storage performance and rate capability of the battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a ZnNi/C composite material modified lithium/carbon fluoride battery positive plate comprises the following steps:
(1) mixing a zinc source, a nickel source and a carbon source according to the mass ratio of zinc, nickel and carbon atoms of 1 (5-20) to (20-50), and fully grinding and dispersing to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing inert gas, heating from room temperature to 150-;
(3) grinding the product B, then packaging the product B in a test tube filled with inert gas through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating the test tube to the temperature of 400-700 ℃, stopping heating, and collecting the test tube after natural cooling to obtain the ZnNi/C composite material;
(4) according to the mass ratio (7-9): (0.5-2): (0.5-1) uniformly mixing carbon fluoride powder, ZnNi/C composite material powder and a binder to obtain a mixture, dropwise adding a solvent into the mixture, stirring until positive electrode slurry with fluidity is obtained, uniformly coating the positive electrode slurry on an aluminum foil by using a film coating device, and drying in vacuum to obtain the ZnNi/C composite material modified lithium/carbon fluoride battery positive electrode sheet.
Further, the zinc source in the step (1) is zinc acetate or zinc sulfate.
Further, the nickel source in the step (1) is analytically pure nickel sulfate, nickel nitrate, nickel chloride, nickel sulfamate, nickel bromide or nickel hydroxide.
Further, the carbon source in the step (1) is urea, melamine or glucose.
Further, the grinding and dispersion in the step (1) adopts a high-speed centrifugal dispersion tank with the rotation speed of 1000-.
Further, the inert gas in the step (2) and the step (3) is argon or nitrogen.
Further, the binder in the step (4) is any one of polyvinylidene fluoride, hydroxymethyl cellulose or polyacrylic acid, or a mixture of hydroxymethyl cellulose and polyacrylic acid in any mass ratio.
Further, when the binder in the step (4) is polyvinylidene fluoride, the solvent is N-methylpyrrolidone or N, N-dimethylformamide; when the binder is hydroxymethyl cellulose, polyacrylic acid or a mixture prepared by hydroxymethyl cellulose and polyacrylic acid according to any mass ratio, the solvent is deionized water.
Further, the vacuum drying in the step (4) is drying for 6-12 hours in a vacuum drying oven at the temperature of 60-80 ℃.
A ZnNi/C composite material modified lithium/carbon fluoride battery positive plate is prepared by coating positive slurry on an aluminum foil and then performing vacuum drying, wherein the positive slurry is prepared by the following steps: (0.5-2): (0.5-1) mixing carbon fluoride powder, ZnNi/C composite material powder and a binder, and dropwise adding a solvent and stirring to obtain a slurry with fluidity.
The invention has the following beneficial effects:
the preparation method comprises the steps of mixing a ZnNi/C composite material with a binder and carbon fluoride powder, then dropwise adding a solvent and stirring until a positive electrode slurry with slight fluidity is prepared, then uniformly coating the positive electrode slurry on an aluminum foil by using a film coating device, and carrying out vacuum drying to prepare a ZnNi/C composite material modified lithium/carbon fluoride battery positive electrode plate; the zinc-nickel alloy/carbon nano tube can provide good conductivity and a plurality of active sites, so that the catalytic effect is achieved, the electrochemical reaction activity of the electrode material is improved, the dynamic problem of the battery is improved, the electrochemical performance of the electrode plate of the battery is improved, the conductivity of the positive plate of the battery is obviously improved, and the specific capacity, the storage performance and the rate capability of the battery are improved.
The preparation method of the ZnNi/C composite material modified lithium/carbon fluoride battery positive plate has the advantages of simple process and low cost, and has important practical significance for improving the performance of the lithium/carbon fluoride battery.
Drawings
FIG. 1: XRD pattern of ZnNi/C composite material prepared in example 1;
FIG. 2: TEM image of ZnNi/C composite prepared in example 1;
FIG. 3: the invention utilizes the performance diagram of the carbon fluoride primary battery assembled by the modified lithium/carbon fluoride battery positive plate under the 0.1C test condition.
Detailed Description
The present invention will be explained in further detail with reference to examples, but the present invention is not limited thereto.
Example 1
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 5: 20, putting zinc acetate, nickel nitrate and melamine into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 1000r/min for 20min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing argon of 200sccm, heating from room temperature to 150 ℃ at the heating rate of 10 ℃/min, preserving the heat for 2 hours, and taking out the mixture after the temperature is reduced to the room temperature to obtain a product B;
(3) and grinding the product B, then packaging the product B in a test tube filled with argon through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating the test tube to 700 ℃, stopping heating, and collecting the test tube after natural cooling to obtain the ZnNi/C composite material.
(4) According to the mass ratio of 7: 2: 1, uniformly mixing carbon fluoride powder, ZnNi/C composite material powder and polyvinylidene fluoride to obtain a mixture, dropwise adding N-methyl pyrrolidone into the mixture, stirring until positive electrode slurry with slight fluidity is obtained, uniformly coating the positive electrode slurry on an aluminum foil by using a film coating device, and drying for 12 hours in a vacuum drying oven at the temperature of 80 ℃ to obtain the ZnNi/C composite material modified lithium/carbon fluoride battery positive electrode sheet.
FIG. 1 is an XRD pattern of the ZnNi/C composite material prepared in example 1, in which the diffraction peak at 26 ℃ is a carbon peak and the diffraction peaks at 44 ℃ and 52 ℃ are zinc and nickel peaks.
FIG. 2 is a TEM image of the ZnNi/C composite material prepared in example 1, and it can be seen from the image that the carbon nanotubes have complete morphology and about 200nm in size, and a large number of folds exist on the surface of the carbon nanotubes, so that the specific surface area is increased, the reaction is facilitated to be fully performed, and more active sites are provided.
Example 2
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 6: 25 putting zinc acetate, nickel sulfate and urea into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 1500r/min for 15min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing argon of 200sccm, heating from room temperature to 200 ℃ at the heating rate of 20 ℃/min, preserving the heat for 1h, and taking out the mixture after the temperature is reduced to the room temperature to obtain a product B;
(3) grinding the product B, then packaging the product B in a test tube filled with argon through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating to 500 ℃, stopping heating, and collecting after natural cooling to obtain a ZnNi/C composite material;
(4) according to the mass ratio of 8: 1: 1, uniformly mixing carbon fluoride powder, ZnNi/C composite material powder and polyvinylidene fluoride to obtain a mixture, dropwise adding N, N-dimethylformamide into the mixture, stirring until positive slurry with slight fluidity is obtained, uniformly coating the positive slurry on an aluminum foil by using a film coating device, and drying for 8 hours in a vacuum drying oven at 60 ℃ to obtain the ZnNi/C composite material modified lithium/carbon fluoride battery positive plate.
Example 3
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 20: 50, putting zinc sulfate, nickel chloride and glucose into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 2000r/min for 5min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing nitrogen of 200sccm, heating from room temperature to 250 ℃ at the heating rate of 25 ℃/min, preserving heat for 0.5h, and taking out after the temperature is reduced to room temperature to obtain a product B;
(3) grinding the product B, then packaging the product B in a test tube filled with nitrogen through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating to 600 ℃, stopping heating, and collecting after natural cooling to obtain a ZnNi/C composite material;
(4) according to the mass ratio of 9: 0.5: 0.5, uniformly mixing carbon fluoride powder, ZnNi/C composite material powder and hydroxymethyl cellulose to obtain a mixture, dropwise adding deionized water into the mixture, stirring until positive electrode slurry with fluidity is obtained, uniformly coating the positive electrode slurry on an aluminum foil by using a film coating device, and drying in a vacuum drying oven at 70 ℃ for 8 hours to obtain the ZnNi/C composite material modified lithium/carbon fluoride battery positive plate.
Example 4
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 10: 30 putting zinc sulfate, nickel sulfamate and urea into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 1800r/min for 10min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing argon of 200sccm, heating from room temperature to 150 ℃ at the heating rate of 15 ℃/min, preserving the heat for 2 hours, and taking out the mixture after the temperature is reduced to the room temperature to obtain a product B;
(3) grinding the product B, then packaging the product B in a test tube filled with argon through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating to 400 ℃, stopping heating, and collecting after natural cooling to obtain a ZnNi/C composite material;
(4) according to the mass ratio of 8: 1.5: 0.5, uniformly mixing carbon fluoride powder, ZnNi/C composite material powder and polyacrylic acid to obtain a mixture, dropwise adding deionized water into the mixture until positive electrode slurry with slight fluidity is obtained, uniformly coating the positive electrode slurry on aluminum foil by using a film coating device, and drying in a vacuum drying oven at the temperature of 80 ℃ for 6 hours to obtain the ZnNi/C composite material modified lithium/carbon fluoride battery positive electrode sheet.
Example 5
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 9: 27 putting zinc acetate, nickel bromide and melamine into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 2000r/min for 10min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing nitrogen of 200sccm, heating from room temperature to 200 ℃ at the heating rate of 20 ℃/min, preserving heat for 1.5h, and taking out after the temperature is reduced to room temperature to obtain a product B;
(3) grinding the product B, then packaging the product B in a test tube filled with nitrogen through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating to 400 ℃, stopping heating, and collecting after natural cooling to obtain a ZnNi/C composite material;
(4) according to the mass ratio of 7: 0.5: 0.5 mixing carbon fluoride powder, ZnNi/C composite material powder and a mixture of hydroxymethyl cellulose and polyacrylic acid according to a mass ratio of 1: 1, uniformly mixing the above substances, then dropwise adding deionized water, stirring until positive electrode slurry with slight fluidity is obtained, uniformly coating the positive electrode slurry on an aluminum foil by using a film coating device, and drying in a vacuum drying oven at 70 ℃ for 10 hours to obtain the ZnNi/C composite material modified lithium/carbon fluoride battery positive plate.
Example 6
(1) According to the mass ratio of zinc, nickel and carbon atoms of 1: 15: 40 putting zinc sulfate, nickel hydroxide and glucose into a high-speed centrifugal dispersion tank, and grinding and dispersing at the rotating speed of 1000r/min for 20min to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing flowing nitrogen of 200sccm, heating from room temperature to 150 ℃ at the heating rate of 30 ℃/min, preserving the heat for 2 hours, and taking out the mixture after the temperature is reduced to the room temperature to obtain a product B;
(3) grinding the product B, then packaging the product B in a test tube filled with nitrogen through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating the test tube to 550 ℃, stopping heating, and collecting the test tube after natural cooling to obtain the ZnNi/C composite material;
(4) according to the mass ratio of 9: 2: 0.5, uniformly mixing carbon fluoride powder, ZnNi/C composite material powder and hydroxymethyl cellulose to obtain a mixture, dropwise adding deionized water into the mixture, stirring until positive slurry with slight fluidity is obtained, uniformly coating the positive slurry on an aluminum foil by using a film coating device, and drying for 12 hours in a vacuum drying oven at 60 ℃ to obtain the ZnNi/C composite material modified lithium/carbon fluoride battery positive plate.
The modified lithium/carbon fluoride battery positive plate is assembled into a lithium/carbon fluoride primary battery for electrochemical performance test:
and (3) winding or laminating the modified lithium/carbon fluoride battery positive plate, the lithium diaphragm and the negative metal lithium, injecting liquid and sealing to assemble the lithium/carbon fluoride primary battery. Wherein: an electrolyte solution is adopted, wherein the electrolyte is at least one of lithium salt LiTFSI, LiClO4 and LiPF6, and the solvent is at least one of PC, EC, DEC, DMC and EMC
And finally, performing constant-current discharge test on the battery by adopting a Xinwei electrochemical workstation, wherein the test voltage is 1.5V-3.0V:
fig. 3 is a performance graph of the modified fluorocarbon primary battery under 0.1C test conditions, from which it can be seen that the lithium/fluorocarbon battery has a high voltage plateau around 2.45V and a specific capacity of 859.5mAh/g over a voltage range of 1.5V-3V. Therefore, when the ZnNi/C composite material modified lithium/carbon fluoride positive plate is applied to a battery, the battery has high capacity, a high-voltage platform is more stable, and the electrochemical reaction is stable.
Claims (10)
1. A preparation method of a ZnNi/C composite material modified lithium/carbon fluoride battery positive plate is characterized by comprising the following steps:
(1) mixing a zinc source, a nickel source and a carbon source according to the mass ratio of zinc, nickel and carbon atoms of 1 (5-20) to (20-50), and fully grinding and dispersing to obtain a mixture A;
(2) putting the mixture A into a high-temperature tube furnace, introducing inert gas, heating from room temperature to 150-;
(3) grinding the product B, then packaging the product B in a test tube filled with inert gas through a sealed glove box, putting the test tube packaged with the product B into an electromagnetic induction heater, heating the test tube to the temperature of 400-700 ℃, stopping heating, and collecting the test tube after natural cooling to obtain the ZnNi/C composite material;
(4) according to the mass ratio (7-9): (0.5-2): (0.5-1) uniformly mixing carbon fluoride powder, ZnNi/C composite material powder and a binder to obtain a mixture, dropwise adding a solvent into the mixture, stirring until positive electrode slurry with fluidity is obtained, uniformly coating the positive electrode slurry on an aluminum foil by using a film coating device, and drying in vacuum to obtain the ZnNi/C composite material modified lithium/carbon fluoride battery positive electrode sheet.
2. The method for preparing a ZnNi/C composite modified lithium/fluorocarbon battery positive electrode sheet according to claim 1, wherein the zinc source of the step (1) is zinc acetate or zinc sulfate.
3. The method for preparing the ZnNi/C composite modified lithium/fluorocarbon battery positive electrode sheet according to claim 1, wherein the nickel source in the step (1) is analytically pure nickel sulfate, nickel nitrate, nickel chloride, nickel sulfamate, nickel bromide or nickel oxyhydroxide.
4. The method for preparing the ZnNi/C composite modified lithium/fluorocarbon battery positive electrode sheet according to claim 1, wherein the carbon source in the step (1) is urea, melamine or glucose.
5. The preparation method of the ZnNi/C composite modified lithium/carbon fluoride battery positive plate as claimed in claim 1, wherein the grinding dispersion in the step (1) adopts a high-speed centrifugal dispersion tank with the rotation speed of 1000-2000r/min, and the grinding dispersion is carried out for 5-20 min.
6. The method for preparing a ZnNi/C composite modified lithium/fluorocarbon battery positive electrode sheet according to claim 1, wherein the inert gas of the steps (2) and (3) is argon or nitrogen.
7. The preparation method of the ZnNi/C composite modified lithium/fluorocarbon battery positive plate according to claim 1, wherein the binder in the step (4) is any one of polyvinylidene fluoride, hydroxymethyl cellulose or polyacrylic acid, or a mixture of hydroxymethyl cellulose and polyacrylic acid in any mass ratio.
8. The method for preparing a ZnNi/C composite modified lithium/fluorocarbon battery positive electrode sheet according to claim 7, wherein, when the binder in the step (4) is polyvinylidene fluoride, the solvent is N-methylpyrrolidone or N, N-dimethylformamide; when the binder is hydroxymethyl cellulose, polyacrylic acid or a mixture prepared by hydroxymethyl cellulose and polyacrylic acid according to any mass ratio, the solvent is deionized water.
9. The preparation method of the ZnNi/C composite modified lithium/carbon fluoride battery positive plate as claimed in claim 1, wherein the vacuum drying in the step (4) is drying for 6-12 h at 60-80 ℃ in a vacuum drying oven.
10. The ZnNi/C composite material modified lithium/carbon fluoride battery positive plate prepared by the method of claim 1, which is characterized in that the ZnNi/C composite material modified lithium/carbon fluoride battery positive plate is prepared by coating positive slurry on an aluminum foil and then drying the aluminum foil in vacuum, wherein the positive slurry is prepared from the following components in percentage by mass (7-9): (0.5-2): (0.5-1) mixing carbon fluoride powder, ZnNi/C composite material powder and a binder, and dropwise adding a solvent and stirring to obtain a slurry with fluidity.
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