CN113972438A - Cobalt-nickel alloy/carbon nano tube modified diaphragm and preparation method and application thereof - Google Patents
Cobalt-nickel alloy/carbon nano tube modified diaphragm and preparation method and application thereof Download PDFInfo
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- CN113972438A CN113972438A CN202111231453.1A CN202111231453A CN113972438A CN 113972438 A CN113972438 A CN 113972438A CN 202111231453 A CN202111231453 A CN 202111231453A CN 113972438 A CN113972438 A CN 113972438A
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- nickel alloy
- carbon nanotube
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 51
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 51
- 229910000990 Ni alloy Inorganic materials 0.000 title claims abstract description 47
- ZGDWHDKHJKZZIQ-UHFFFAOYSA-N cobalt nickel Chemical compound [Co].[Ni].[Ni].[Ni] ZGDWHDKHJKZZIQ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000011248 coating agent Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 14
- -1 polypropylene Polymers 0.000 claims abstract description 10
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- 239000004743 Polypropylene Substances 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- 229920001155 polypropylene Polymers 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims description 30
- 238000000227 grinding Methods 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 239000002904 solvent Substances 0.000 claims description 17
- 239000002002 slurry Substances 0.000 claims description 16
- 239000012528 membrane Substances 0.000 claims description 15
- 239000011230 binding agent Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 14
- 238000001816 cooling Methods 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 11
- 229920002125 Sokalan® Polymers 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 10
- 239000010941 cobalt Substances 0.000 claims description 10
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 10
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 10
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 10
- 239000004570 mortar (masonry) Substances 0.000 claims description 10
- 229910052759 nickel Inorganic materials 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
- 239000004584 polyacrylic acid Substances 0.000 claims description 9
- 239000002033 PVDF binder Substances 0.000 claims description 8
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 8
- 239000012300 argon atmosphere Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 239000012298 atmosphere Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 4
- 229940044175 cobalt sulfate Drugs 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000011261 inert gas 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
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 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 3
- 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 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 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims description 3
- 239000008103 glucose Substances 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
- 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
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- 239000003792 electrolyte Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 4
- 230000004048 modification Effects 0.000 abstract description 4
- 238000007086 side reaction Methods 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 description 5
- 150000001721 carbon Chemical group 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000007888 film coating Substances 0.000 description 2
- 238000009501 film coating Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000003860 storage 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
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/431—Inorganic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a cobalt-nickel alloy/carbon nanotube modified diaphragm, which comprises a diaphragm base film and a cobalt-nickel alloy/carbon nanotube composite material coating coated on the diaphragm base film; the diaphragm base film is any one of a polypropylene diaphragm, a polyethylene diaphragm or a multilayer composite diaphragm; the thickness of the cobalt-nickel alloy/carbon nano tube composite material coating is 2-15 mu m, and the invention also provides a preparation method and application of the cobalt-nickel alloy/carbon nano tube modified diaphragm; the method has the advantages of simple process and low modification cost, the mechanical strength of the prepared modified diaphragm is improved, the battery is safe and has good self-discharge performance, the conductivity of the electrode material can be improved, the battery expansion is relieved, the electrolyte loss caused by the side reaction of the material and the electrolyte is inhibited, the capacity loss is avoided, and the method has important practical significance for preparing the high-performance lithium fluorocarbon battery.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to a battery diaphragm, and particularly relates to a cobalt-nickel alloy/carbon nano tube modified diaphragm and a preparation method and application thereof.
Background
The lithium fluorocarbon battery is a high-energy-density primary battery, the practical specific energy can reach 250-700 Wh/kg, and is multiple times of that of a dry battery, and the lithium fluorocarbon battery is easy to miniaturize and lighten. Among the structures of lithium fluorocarbon batteries, the separator is one of the key inner layer components. The separator has a main function of separating the positive electrode and the negative electrode of the battery to prevent short circuit due to contact between the two electrodes, and also has a function of allowing electrolyte ions to pass therethrough. The separator material is non-conductive, and the physical and chemical properties of the separator have a great influence on the performance of the battery. The battery is different in kind and the separator used is different. The performance of the separator directly affects the capacity, rate, life and safety of the battery, and is referred to as the "third electrode" of the battery. However, because the diaphragm in the current market is small in quantity and high in price, the diaphragm is mainly used in the field of power lithium battery manufacturing, and therefore, how to fully utilize each diaphragm and improve the performances of the diaphragm such as thickness uniformity, mechanical property and the like is very important.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a cobalt-nickel alloy/carbon nanotube modified diaphragm and a preparation method and application thereof, which are used for improving the conductivity of a positive electrode, relieving the expansion of a battery, inhibiting the side reaction of the positive electrode and an electrolyte, improving the mechanical strength and puncture strength of the diaphragm, effectively improving the safety and self-discharge performance of the battery and preparing a high-performance lithium fluorocarbon battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a cobalt-nickel alloy/carbon nanotube modified diaphragm comprises the following steps:
the method comprises the following steps: weighing a cobalt source, a nickel source and a carbon source according to the atomic mass ratio of 1 (5-20) to (20-50), grinding and fully mixing to obtain a mixture A;
step two: placing the mixture A in a high-temperature tube furnace, rapidly heating the mixture A to 150-200 ℃ from room temperature at a heating rate of 15-30 ℃/min in an inert gas atmosphere, preserving heat for 0.5-1 h, naturally cooling to room temperature after heat preservation is finished, and taking out to obtain a product B;
step three: grinding the product B, then placing the product B into a freeze drying box, and standing for 3-6 h at the low temperature of-10 to-30 ℃;
step four: taking out the product, putting the product into a high-temperature tube furnace, rapidly heating the product to 500-600 ℃ from room temperature at a heating rate of 10-30 ℃/min in an inert gas atmosphere, naturally cooling the product to room temperature after heating, and taking out the product C, namely the cobalt-nickel alloy/carbon nanotube composite material;
step five: weighing 80-90 wt% of cobalt-nickel alloy/carbon nanotube composite material powder and 10-20 wt% of binder according to the mass percentage, uniformly grinding, dripping solvent to prepare slurry, coating the slurry on a diaphragm base film by using a coating machine, drying to remove the solvent, cutting the dried diaphragm with the cobalt-nickel alloy/carbon nanotube composite material coating, and die-cutting to prepare the modified diaphragm.
Preferably, the cobalt source is any one of analytically pure cobalt nitrate, cobalt sulfate or cobalt carbonate;
the nickel source is any one of analytically pure nickel sulfate, nickel nitrate, nickel chloride, nickel bromide or nickel hydroxide;
the carbon source is any one of urea, melamine or glucose.
Preferably, the grinding method in the first step and the third step is grinding for 20-30 min by adopting a mortar.
Preferably, the reactions of step two and step four are carried out in a flowing argon or nitrogen atmosphere of 100 sccm.
Preferably, the binder is any one of polyvinylidene fluoride, hydroxymethyl cellulose or polyacrylic acid or a mixture of the hydroxymethyl cellulose and the polyacrylic acid in any proportion.
Further, when the binder is polyvinylidene fluoride, the solvent is N-methyl pyrrolidone or N, N-dimethylformamide;
when the binder is hydroxymethyl cellulose, polyacrylic acid or a mixture of hydroxymethyl cellulose and polyacrylic acid, the solvent is deionized water.
Preferably, the membrane-based membrane is any one of a polypropylene membrane, a polyethylene membrane or a multilayer composite membrane.
Preferably, in the fifth step, a vacuum drying oven is adopted for drying for 6-12 hours at the temperature of 60-80 ℃, and the solvent is removed by drying.
The invention also discloses the cobalt-nickel alloy/carbon nano tube modified diaphragm prepared by the preparation method, and the thickness of the cobalt-nickel alloy/carbon nano tube material coating is 5-15 mu m.
The invention also discloses application of the cobalt-nickel alloy/carbon nanotube modified diaphragm in a lithium-carbon fluoride battery.
Compared with the prior art, the invention has the following technical effects:
the cobalt-nickel alloy/carbon nanotube composite material is prepared from raw materials containing a cobalt source, a nickel source and a carbon source, the mixed binder is coated on the diaphragm, the conductivity of the positive electrode is improved, the expansion of the battery is relieved, the electrolyte loss and the capacity loss caused by the side reaction of the material and the electrolyte are inhibited, so that the electrochemical performance of the battery is improved, the voltage platform and the platform stability of the carbon fluoride material are improved after the battery is assembled, the specific energy and the storage performance of the battery are improved, and the high-performance lithium carbon fluoride battery is prepared;
the invention adopts the self-synthesized cobalt-nickel alloy/carbon nano tube to modify the diaphragm, the method has simple process and low modification cost, the mechanical strength of the modified diaphragm is improved, and the battery has good safety and self-discharge performance.
Drawings
FIG. 1 is an XRD pattern of a cobalt-nickel alloy/carbon nanotube composite material;
FIG. 2 is an SEM image of a cobalt-nickel alloy/carbon nanotube composite material;
FIG. 3 is a performance diagram of a fluorinated carbon primary battery under 0.1C test conditions after modification of a diaphragm with the addition of a cobalt-nickel alloy/carbon nanotube composite material.
Detailed Description
The present invention will be explained in further detail with reference to examples.
Example 1:
the method comprises the following steps: weighing cobalt nitrate, nickel sulfate and urea according to the weight ratio of cobalt to nickel to carbon atom substances of 1:9:38, grinding for 20min by using a mortar, and fully mixing to obtain a mixture A;
step two: placing the mixture A in a high-temperature tubular furnace, rapidly heating to 150 ℃ from room temperature at a heating rate of 15 ℃/min in a flowing argon atmosphere of 100sccm, preserving heat for 0.5h, naturally cooling to room temperature after heat preservation, and taking out to obtain a product B;
step three: grinding the product B by using a mortar for 20min, then putting the product B into a freeze drying box, and standing the product B for 6h at the low temperature of minus 10 ℃;
step four: taking out the product, putting the product into a high-temperature tubular furnace, rapidly heating the product to 500 ℃ from room temperature at a heating rate of 10 ℃/min in a flowing argon atmosphere of 100sccm, naturally cooling the product to room temperature after heating is finished, and taking out the product C, namely the cobalt-nickel alloy/carbon nanotube composite material;
step five: weighing the cobalt-nickel alloy/carbon nanotube composite material and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 8:2, uniformly grinding, dropwise adding a proper amount of solvent N-methyl pyrrolidone to prepare slightly flowing slurry, uniformly coating the slurry on one side of a polypropylene diaphragm by using a film coating device, drying for 6 hours in a vacuum drying oven at 80 ℃, and drying the solvent to prepare a diaphragm sheet with the thickness of the slurry layer of 2-15 microns.
Example 2:
the method comprises the following steps: weighing cobalt sulfate, nickel nitrate and melamine according to the weight ratio of cobalt to nickel to carbon atom substances of 1:10:30, grinding for 25min by using a mortar, and fully mixing to obtain a mixture A;
step two: placing the mixture A in a high-temperature tubular furnace, rapidly heating to 200 ℃ from room temperature at a heating rate of 30 ℃/min in a flowing nitrogen atmosphere of 100sccm, preserving heat for 1h, naturally cooling to room temperature after heat preservation, and taking out to obtain a product B;
step three: grinding the product B by using a mortar for 25min, then putting the product B into a freeze drying box, and standing for 4h at the low temperature of-20 ℃;
step four: taking out the product, putting the product into a high-temperature tubular furnace, rapidly heating the product to 550 ℃ from room temperature at the heating rate of 20 ℃/min in the flowing nitrogen atmosphere of 100sccm, naturally cooling the product to room temperature after heating, and taking out the product C, namely the cobalt-nickel alloy/carbon nanotube composite material;
step five: weighing the cobalt-nickel alloy/carbon nanotube composite material and a binder hydroxymethyl cellulose (CMC) according to a mass ratio of 9:1, uniformly grinding, then dropwise adding a proper amount of deionized water to prepare slightly flowing slurry, uniformly coating the slurry on one side of a polyethylene diaphragm by using a film coater, drying for 10 hours at 70 ℃ in a vacuum drying oven, and drying to remove a solvent in the polyethylene diaphragm to prepare a diaphragm sheet with the thickness of the slurry layer of 2-15 microns.
Example 3:
the method comprises the following steps: weighing cobalt sulfate, nickel bromide and glucose according to the weight ratio of cobalt to nickel to carbon atom substances of 1:20:20, grinding for 30min by using a mortar, and fully mixing to obtain a mixture A;
step two: placing the mixture A in a high-temperature tubular furnace, rapidly heating to 180 ℃ from room temperature at a heating rate of 20 ℃/min in a flowing argon atmosphere of 100sccm, preserving heat for 0.8h, naturally cooling to room temperature after heat preservation, and taking out to obtain a product B;
step three: grinding the product B by using a mortar for 30min, then putting the product B into a freeze drying box, and standing the product B for 3h at the low temperature of minus 30 ℃;
step four: taking out the product, putting the product into a high-temperature tubular furnace, rapidly heating the product to 600 ℃ from room temperature at the heating rate of 30 ℃/min in the flowing hydrogen atmosphere of 100sccm, naturally cooling the product to room temperature after heating, and taking out the product C, namely the cobalt-nickel alloy/carbon nanotube composite material;
step five: according to the mass ratio of 85: 15, weighing the cobalt-nickel alloy/carbon nanotube composite material and a binder polyacrylic acid (PAA), uniformly grinding, then dropwise adding a proper amount of deionized water to prepare a slightly flowing slurry, uniformly coating the slurry on one side of the multilayer composite diaphragm by using a film coater, then drying for 12 hours in a vacuum drying oven at 60 ℃, and drying out the solvent to prepare the diaphragm sheet with the thickness of the slurry layer of 2-15 microns.
Example 4:
the method comprises the following steps: weighing cobalt carbonate, nickel chloride and melamine according to the weight ratio of cobalt to nickel to carbon atom substances of 1:5:50, grinding in a mortar for 30min, and fully mixing to obtain a mixture A;
step two: placing the mixture A in a high-temperature tubular furnace, rapidly heating to 200 ℃ from room temperature at a heating rate of 20 ℃/min in a flowing argon atmosphere of 100sccm, preserving heat for 1h, naturally cooling to room temperature after heat preservation, and taking out to obtain a product B;
step three: grinding the product B by using a mortar for 30min, then putting the product B into a freeze drying box, and standing the product B for 5h at the low temperature of minus 30 ℃;
step four: taking out the product, putting the product into a high-temperature tubular furnace, rapidly heating the product to 600 ℃ from room temperature at the heating rate of 30 ℃/min in the flowing argon atmosphere of 100sccm, naturally cooling the product to room temperature after heating, and taking out the product C, namely the cobalt-nickel alloy/carbon nano tube composite material;
step five: weighing the cobalt-nickel alloy/carbon nanotube composite material and a binder polyvinylidene fluoride (PVDF) according to a mass ratio of 88:12, uniformly grinding, then dropwise adding a proper amount of N, N-dimethylformamide to prepare a slightly flowing slurry, uniformly coating the slurry on one side of a polypropylene diaphragm by using a film coating device, drying for 12 hours in a vacuum drying oven at 80 ℃, and drying out a solvent in the vacuum drying oven to prepare a diaphragm sheet with the thickness of the slurry layer of 2-15 microns.
The product cobalt-nickel alloy/carbon nanotube composite material synthesized in example 1 was subjected to X-ray diffraction analysis, and the result is shown in fig. 1, in which a carbon peak exists at 26 ° 2 θ, and peaks exist at 44.4 ° and 51.8 ° 2 θ, which correspond to standard card Ni-PDF #70-1849, and the peak intensity at a high angle is high and sharp, which proves that the synthesized sample has good crystallinity.
The cobalt-nickel alloy/carbon nano tube modified diaphragm obtained in the example 1 and the positive and negative electrodes of the lithium-carbon fluoride battery are wound or laminated, injected and sealed, and the solute of the electrolyte is LiClO4And the solvent adopts EC to assemble the lithium fluorocarbon primary battery, and finally a Xinwei electrochemical workstation is adopted to carry out constant-current charge-discharge test on the battery, wherein the test voltage is 1.5V-3.0V.
FIG. 2 is an SEM image of a cobalt-nickel alloy/carbon nanotube composite material; the diameter of the carbon nano tube is 50nm-200nm, the carbon nano tube is in a hollow tubular structure, the alloy is distributed on the carbon nano tube, a large number of defect sites exist, the conductivity of the material is improved due to the defect sites, meanwhile, the carbon nano tube wall is not smooth, a large number of folds exist, the specific surface area is increased, and the ion transmission and the electron transfer are further improved.
FIG. 3 is a performance diagram of a lithium fluorocarbon primary battery with a cobalt-nickel alloy/carbon nanotube composite material modified diaphragm added under a 0.1C test condition, wherein the theoretical capacity of the fluorocarbon battery is 865mAh g-1The specific capacity of 782.7mAh/g is within the voltage range of 3V-1.5V, and the high voltage platform is stable, thereby reducing the generation of other side reactions.
Meanwhile, the cobalt-nickel alloy/carbon nanotube composite material prepared by the invention can be widely used and plays a role, not only can be used in a carbon fluoride primary battery, but also can be used in a secondary battery after modification, and the performance is obviously improved.
The foregoing is a further detailed description of the present invention, and it should not be understood that the embodiments of the present invention are not limited thereto, the cobalt source, the nickel source and the carbon source can be combined with other materials provided by the technical solution or in other ratios within the technical solution, the binder can be a mixture of hydroxymethylcellulose and polyacrylic acid with a proper amount of deionized water as a solvent, and those skilled in the art can make several simple deductions or substitutions without departing from the spirit of the present invention, and all such alterations and substitutions should be considered as falling within the scope of the present invention as defined by the claims.
Claims (10)
1. A preparation method of a cobalt-nickel alloy/carbon nanotube modified diaphragm is characterized by comprising the following steps:
the method comprises the following steps: weighing a cobalt source, a nickel source and a carbon source according to the atomic mass ratio of 1 (5-20) to (20-50), grinding and fully mixing to obtain a mixture A;
step two: placing the mixture A in a high-temperature tube furnace, rapidly heating the mixture A to 150-200 ℃ from room temperature at a heating rate of 15-30 ℃/min in an inert gas atmosphere, preserving heat for 0.5-1 h, naturally cooling to room temperature after heat preservation is finished, and taking out to obtain a product B;
step three: grinding the product B, then placing the product B into a freeze drying box, and standing for 3-6 h at the low temperature of-10 to-30 ℃;
step four: taking out the product, putting the product into a high-temperature tube furnace, rapidly heating the product to 500-600 ℃ from room temperature at a heating rate of 10-30 ℃/min in an inert gas atmosphere, naturally cooling the product to room temperature after heating, and taking out the product C, namely the cobalt-nickel alloy/carbon nanotube composite material;
step five: weighing 80-90 wt% of cobalt-nickel alloy/carbon nanotube composite material powder and 10-20 wt% of binder according to the mass percentage, uniformly grinding, dripping solvent to prepare slurry, coating the slurry on a diaphragm base film by using a coating machine, drying to remove the solvent, cutting the dried diaphragm with the cobalt-nickel alloy/carbon nanotube composite material coating, and die-cutting to prepare the modified diaphragm.
2. The method for preparing the cobalt-nickel alloy/carbon nanotube modified membrane according to claim 1, wherein the cobalt source is any one of analytically pure cobalt nitrate, cobalt sulfate or cobalt carbonate;
the nickel source is any one of analytically pure nickel sulfate, nickel nitrate, nickel chloride, nickel bromide or nickel hydroxide;
the carbon source is any one of urea, melamine or glucose.
3. The method for preparing the cobalt-nickel alloy/carbon nanotube modified membrane according to claim 1, wherein the grinding method in the first step and the third step is grinding for 20-30 min by using a mortar.
4. The method for preparing a cobalt-nickel alloy/carbon nanotube modified membrane according to claim 1, wherein the reaction in the second step and the reaction in the fourth step are performed in a flowing argon or nitrogen atmosphere of 100 seem.
5. The method for preparing the cobalt-nickel alloy/carbon nanotube modified diaphragm of claim 1, wherein the binder is any one of polyvinylidene fluoride, hydroxymethyl cellulose or polyacrylic acid or a mixture of hydroxymethyl cellulose and polyacrylic acid in any proportion.
6. The method for preparing the cobalt-nickel alloy/carbon nanotube modified diaphragm as claimed in claim 1 or 5, wherein when the binder is polyvinylidene fluoride, the solvent is N-methylpyrrolidone or N, N-dimethylformamide;
when the binder is hydroxymethyl cellulose, polyacrylic acid or a mixture of hydroxymethyl cellulose and polyacrylic acid, the solvent is deionized water.
7. The method for preparing the cobalt-nickel alloy/carbon nanotube modified membrane as claimed in claim 1, wherein the membrane-based membrane is any one of a polypropylene membrane, a polyethylene membrane or a multi-layer composite membrane.
8. The method for preparing the cobalt-nickel alloy/carbon nanotube modified diaphragm of claim 1, wherein in the fifth step, a vacuum drying oven is adopted for drying for 6-12 hours at the temperature of 60-80 ℃, and the solvent is removed by drying.
9. The cobalt-nickel alloy/carbon nanotube modified membrane prepared by the preparation method of any one of claims 1 to 8, wherein the thickness of the cobalt-nickel alloy/carbon nanotube composite material coating is 2-15 μm.
10. Use of the cobalt nickel alloy/carbon nanotube modified separator of claim 9 in a lithium carbon fluoride cell.
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| CN106669762A (en) * | 2016-12-30 | 2017-05-17 | 华南理工大学 | Nitrogen-doped carbon nanotube/Co composite catalyst and preparation method and application thereof |
| CN110104630A (en) * | 2019-05-16 | 2019-08-09 | 华南师范大学 | A kind of porous carbon composite and its preparation method and application for battery diaphragm |
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| CN106669762A (en) * | 2016-12-30 | 2017-05-17 | 华南理工大学 | Nitrogen-doped carbon nanotube/Co composite catalyst and preparation method and application thereof |
| CN110104630A (en) * | 2019-05-16 | 2019-08-09 | 华南师范大学 | A kind of porous carbon composite and its preparation method and application for battery diaphragm |
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