CN114122441A - Nickel powder carved carbon fiber thermal battery substrate and preparation method and application thereof - Google Patents
Nickel powder carved carbon fiber thermal battery substrate and preparation method and application thereof Download PDFInfo
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- CN114122441A CN114122441A CN202111310787.8A CN202111310787A CN114122441A CN 114122441 A CN114122441 A CN 114122441A CN 202111310787 A CN202111310787 A CN 202111310787A CN 114122441 A CN114122441 A CN 114122441A
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- nickel
- thermal battery
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- nickel powder
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 140
- 229920000049 Carbon (fiber) Polymers 0.000 title claims abstract description 130
- 239000004917 carbon fiber Substances 0.000 title claims abstract description 130
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 125
- 239000000758 substrate Substances 0.000 title claims abstract description 117
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 58
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 30
- 150000002815 nickel Chemical class 0.000 claims abstract description 22
- 239000011159 matrix material Substances 0.000 claims abstract description 15
- 238000010041 electrostatic spinning Methods 0.000 claims description 61
- 238000009987 spinning Methods 0.000 claims description 48
- 239000011230 binding agent Substances 0.000 claims description 41
- 239000002033 PVDF binder Substances 0.000 claims description 25
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 25
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 238000002156 mixing Methods 0.000 claims description 20
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 12
- 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 10
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- 239000004793 Polystyrene Substances 0.000 claims description 8
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 8
- 229940078494 nickel acetate Drugs 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 7
- 239000004020 conductor Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 229920002223 polystyrene Polymers 0.000 claims description 7
- 229910052786 argon Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000001307 helium Substances 0.000 claims description 6
- 229910052734 helium Inorganic materials 0.000 claims description 6
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- 229910052754 neon Inorganic materials 0.000 claims description 6
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- 208000028659 discharge Diseases 0.000 abstract description 29
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 abstract description 12
- 239000011593 sulfur Substances 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 239000010405 anode material Substances 0.000 abstract description 9
- 238000000354 decomposition reaction Methods 0.000 abstract description 9
- 230000004913 activation Effects 0.000 abstract description 7
- 229910052799 carbon Inorganic materials 0.000 abstract description 4
- 239000012535 impurity Substances 0.000 abstract description 4
- 238000003763 carbonization Methods 0.000 abstract description 3
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 238000011946 reduction process Methods 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 17
- 239000002245 particle Substances 0.000 description 10
- 238000001994 activation Methods 0.000 description 9
- 239000000843 powder Substances 0.000 description 9
- 230000003139 buffering effect Effects 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 7
- 239000010439 graphite Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000000835 fiber Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 238000001523 electrospinning Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Inorganic materials [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000001757 thermogravimetry curve Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000251729 Elasmobranchii Species 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- PPTSBERGOGHCHC-UHFFFAOYSA-N boron lithium Chemical compound [Li].[B] PPTSBERGOGHCHC-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
Images
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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/30—Deferred-action cells
- H01M6/36—Deferred-action cells containing electrolyte and made operational by physical means, e.g. thermal 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
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
Abstract
The invention provides a nickel powder carved carbon fiber thermal battery substrate and a preparation method and application thereof. The nickel powder carved carbon fiber thermal battery substrate is prepared by taking nickel salt as a nickel source and a high molecular compound as a carbon source and adopting an electrostatic spinning-heat treatment carbonization reduction process, and the obtained substrate has high thermal stability and is suitable for a high-temperature discharge environment of a thermal battery; the specific surface area of the carbon fiber matrix is large, and gaps exist in the mutual overlapping mode, so that the heat generated at the instant of battery activation can be effectively dispersed; the nano metallic nickel embedded into the carbon fiber can react with sulfur generated by decomposition of the anode material, so that the phenomenon of voltage spike at the initial discharge stage caused by sulfur impurities is eliminated, and the discharge stability of the thermal battery is improved.
Description
Technical Field
The invention belongs to the technical field of batteries, relates to a thermal battery, and particularly relates to a nickel powder carved carbon fiber thermal battery substrate as well as a preparation method and application thereof.
Background
The thermal battery is a thermally activated reserve battery, and is characterized in that solid inorganic salt is used as electrolyte, and compared with other chemical power sources, the electrolyte of the thermal battery is solid at normal temperature, so that the thermal battery has no self-discharge problem and has a storage life of more than 20 years. In addition, the thermal battery has the advantages of high activation speed, large output power, capability of bearing large-current discharge, wide use temperature range, firm structure, capability of normally working in a harsh environment, high reliability and the like. Therefore, thermal batteries are favored by modern weapons, dominate military power supplies, and have become the power source of choice for many advanced technology weapons systems, including various electrical conductors, space vehicles, artillery, torpedoes, nuclear weapons, aircraft and bombs.
When the thermal battery is used, the temperature in the battery rapidly rises through a heating system of the battery, after the temperature reaches the melting temperature of the molten salt electrolyte, the solid inorganic salt electrolyte is melted into an ion conductor, and the thermal battery is activated to discharge and enters a working state. The heating system of the thermal battery generally adopts a heating plate, and the temperature rises instantly when the heating plate is activated, so that the decomposition of the anode material is caused, and the discharge capacity of the battery is influenced. Therefore, when the thermal battery is assembled, a substrate needs to be added between the heating plate and the positive plate so as to buffer heat brought by the heating plate at the moment of battery activation.
CN 106207213a discloses a composite anode for a rapid-activation thermal battery and a preparation method thereof, wherein the composite anode is formed by physically pressing thermal battery anode powder, heating powder and a wire mesh. Wherein the anode powder is coated by adopting molten salt electrolyte, and the heating powder is 5-60% of the anode powder. The wire mesh in the electrode assembly is embedded in the positive electrode layer, and the diameter of the wire mesh is 60-90% of the diameter of the sheet. In the activation process of the thermal battery, the heating powder in the composite anode is combusted, so that the collecting coating layer can be quickly activated, and the heat transfer intermediate process can be reduced; in addition, excess iron in the wire mesh and heating powder can increase electrode conductivity. The arrangement of the wire mesh can play a role in heat buffering, but the buffering effect is limited due to high heat conductivity coefficient.
CN 110112431A discloses a preparation method of a coating type thermal battery composite electrode plate, which comprises a heating layer, an anode layer and a diaphragm layer. The preparation method uses the graphite paper substrate to buffer heat during the assembled battery test.
However, the graphite paper has a solid structure inside, a large specific surface area, a high thermal conductivity coefficient and a limited buffering effect, and under the impact action of high heat, the graphite substrate with a new structure cannot well isolate the influence of heat, so that the discharge performance of the battery is seriously influenced, the discharge specific capacity of the battery is reduced, and the development of the battery to a large capacity and a large time is not facilitated. In addition, the carbon material with high thermal conductivity causes low temperature gradient between the heating sheet and the anode material, the anode material is decomposed under the action of high temperature for a long time, and sulfur generated by decomposition not only has influence on the discharge precision of the battery; and the generated sulfur exists in the form of steam at a high temperature, which affects the safety of the battery.
Therefore, in order to better exert the thermal buffering function of the substrate in the thermal battery activation process and make up for the defects of the graphite paper substrate, the thermal battery substrate which is high-temperature resistant, large in specific surface area and better in heat buffering needs to be provided.
Disclosure of Invention
The invention aims to provide a nickel powder carved carbon fiber thermal battery substrate and a preparation method and application thereof, wherein the nickel powder carved carbon fiber thermal battery substrate has high thermal stability and is suitable for the discharge environment of a thermal battery; the nickel powder carved carbon fiber thermal battery substrate can effectively disperse the heat at the moment of battery activation, improve the thermal buffering effect, reduce the decomposition rate of the anode material, and improve the output capacity, thereby prolonging the working time of the battery; meanwhile, the nickel powder carved carbon fiber thermal battery substrate can eliminate the occurrence of voltage peak at the initial discharge stage caused by sulfur generated by decomposition of the anode material, and improves the discharge stability of the thermal battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a nickel powder carved carbon fiber thermal battery substrate, which comprises a carbon fiber matrix and nano metal nickel dispersed and embedded in carbon fibers.
The 'carving decoration' in the invention means that nickel powder is embedded into carbon fiber. The carbon fiber substrate has the characteristic of large surface area, and the carbon fibers are overlapped to form gaps, so that the instant heat of battery activation can be effectively dispersed, and the heat buffering effect is improved. And the nano metallic nickel dispersedly embedded in the carbon fiber can react with sulfur generated by decomposition of the anode material, so that the defect of a discharge initial voltage peak caused by impurity sulfur is eliminated, and the discharge stability of the thermal battery is improved.
On the basis of keeping high conductivity of the nano metal nickel and the carbon fiber, the nickel powder carved carbon fiber thermal battery substrate which has high stability and excellent thermal buffering effect and can eliminate discharge peaks is formed by utilizing the characteristics that the carbon fiber has large surface area and gaps and the nano metal nickel can react with sulfur generated by decomposition of a positive electrode material.
Preferably, the carbon fibers in the carbon fiber matrix have a diameter of 0.2 to 5 μm, and may be, for example, 0.2 μm, 0.5 μm, 1 μm, 1.5 μm, 2 μm, 2.5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm or 5 μm, but are not limited to the recited values, and other values not recited in the numerical ranges are equally applicable.
Preferably, the morphology of the nano metallic nickel is hexagonal.
Preferably, the average particle size of the nano-metallic nickel is 100-500nm, and may be, for example, 100nm, 150nm, 200nm, 250nm, 300nm, 350nm, 400nm, 450nm or 500nm, but is not limited to the enumerated values, and other unrecited values within the numerical range are also applicable.
Preferably, the specific surface area of the nickel powder carved carbon fiber thermal battery substrate is 50-500m2Per g, may be, for example, 50m2/g、100m2/g、150m2/g、200m2/g、250m2/g、300m2/g、350m2/g、400m2/g、450m2G or 500m2The values/g are not limited to the values listed, and other values in the numerical range not listed are equally applicable.
Preferably, the nickel powder-decorated carbon fiber thermal battery substrate has a thermal conductivity of 100-.
In a second aspect, the present invention provides a method for preparing the nickel powder-carved carbon fiber thermal battery substrate according to the first aspect, wherein the method comprises the following steps:
(1) mixing a binder, a nickel salt and a solvent to obtain an electrostatic spinning solution;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film;
(3) and (3) drying the cured film obtained in the step (2) in vacuum, and then carrying out heat treatment to obtain the nickel powder carved carbon fiber thermal battery substrate.
The electrostatic spinning process comprises the following steps: the electrostatic spinning solution is charged with high-voltage static electricity, surface tension is overcome under the action of electric field force to form jet trickle, solvent is evaporated in the jet process of the trickle and finally falls on the conductive matrix to form fibers, the fibers are overlapped to form a film, and the film is taken off from the surface of the conductive matrix to obtain the cured film.
Preferably, the mass ratio of the binder to the solvent in step (1) is X (100-X), wherein X ═ 1 to 10, and can be, for example, 1, 3, 5, 7, 9 or 10, but is not limited to the recited values, and other values in the range of values not recited are equally applicable.
When the amount of the binder is small, the viscosity of the obtained electrostatic spinning solution is too low to be used for electrostatic spinning; when the using amount of the binder is too large, the viscosity of the electrostatic spinning solution is too large, the problem of blockage of a spinning needle head is easily caused in the electrostatic spinning process, and the obtained spinning fiber is thick, so that the specific surface area of the nickel powder carved carbon fiber thermal battery substrate is influenced.
Preferably, the mass ratio of the binder to the nickel salt in step (1) is Y (100-Y), wherein Y is 5-15, and may be, for example, 5, 6, 8, 10, 12 or 15, but is not limited to the recited values, and other values not recited in the range of values are also applicable.
When the using amount of the nickel salt is too much, the nickel particle dispersibility on the surface of the carbon fiber obtained by electrostatic spinning is poor; when the amount of nickel salt is too small, the nickel loading on the surface of the carbon fiber obtained by electrostatic spinning is small, and the synergistic effect between the carbon fiber and the nano-metal nickel cannot be exerted.
Preferably, the binder of step (1) comprises any one or a combination of at least two of polyvinylpyrrolidone (PVP), polyvinylidene fluoride (PVDF) or Polystyrene (PS), and typical but non-limiting combinations include PVP and PVDF, PVDF and PS, PVP and PS, or PVP, PVDF and PS.
Preferably, the nickel salt in step (1) includes any one of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate or a combination of at least two thereof, and typical but non-limiting combinations include a combination of nickel sulfate and nickel chloride, a combination of nickel chloride and nickel nitrate, a combination of nickel nitrate and nickel acetate, a combination of nickel sulfate, nickel chloride and nickel nitrate, a combination of nickel chloride, nickel nitrate and nickel acetate, or a combination of nickel sulfate, nickel chloride, nickel nitrate and nickel acetate.
Preferably, the solvent in step (1) comprises any one or a combination of at least two of Dimethylformamide (DMF), N-methylpyrrolidone (NMP) or Dimethylsulfoxide (DMSO), and typical but non-limiting combinations include DMF and NMP, NMP and DMSO, DMF and DMSO, or DMF, NMP and DMSO.
Preferably, the mixing of step (1) comprises: dissolving the binder in a solvent at 50-80 ℃ to obtain a binder solution; and then uniformly mixing the nickel salt and the binder solution to obtain the electrostatic spinning solution.
The temperature of the solvent is 50-80 ℃, for example 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃ or 80 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Under the temperature condition, the binder is favorably dissolved in the solvent.
Preferably, the parameters of the electrostatic spinning in the step (2) comprise: the distance between the spinning needle head and the conductive matrix is 15-30cm, the spinning current is 0.5-1mA, the spinning voltage is 15-50kV, and the spinning speed is 0.03-0.1 rpm.
The invention ensures the uniformity of the carbon fiber obtained by electrostatic spinning by controlling the parameters of the electrostatic spinning, ensures that the diameter of the finally obtained carbon fiber is 0.2-5 mu m, and the specific surface area of the nickel powder carved carbon fiber thermal battery substrate is 50-500m2/g。
In the electrospinning, the distance between the spinning needle and the conductive substrate is 15-30cm, for example, 15cm, 18cm, 20cm, 24cm, 25cm, 27cm, 28cm or 30cm, but is not limited to the values listed, and other values not listed in the range of values are also applicable.
Preferably, the conductive substrate comprises any one of stainless steel, a porous conductive material or a flexible conductive material or a combination of at least two thereof.
The porous conductive material comprises a material consisting of at least 1 of carbon, chromium, titanium, nickel, silver or copper in a foam and/or mesh shape.
The flexible conductive material includes, but is not limited to, flexible graphite.
Preferably, the temperature of the vacuum drying in the step (3) is 180-240 ℃ and the time is 12-24 h.
The temperature of the vacuum drying in step (3) of the present invention is 180-240 ℃, such as 180 ℃, 190 ℃, 200 ℃, 210 ℃, 220 ℃, 230 ℃ or 240 ℃, but not limited to the recited values, and other values not recited in the range of the values are also applicable.
The vacuum drying time in step (3) of the present invention is 12-24h, for example, 12h, 15h, 16h, 18h, 20h or 24h, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the heat treatment in step (3) is performed under a protective atmosphere using a gas including any one or a combination of at least two of helium, argon, neon, or nitrogen, and typical but non-limiting combinations include a combination of helium and argon, argon and neon, neon and nitrogen, or helium, argon, neon and nitrogen.
The protective atmosphere of the present invention is a protective atmosphere formed with a flow rate of 20-50sccm of a protective gas, such as 20sccm, 25sccm, 30sccm, 35sccm, 40sccm, 45sccm or 50sccm, but is not limited to the recited values, and other unrecited values within the range of values are also applicable.
Preferably, the heating rate of the heat treatment in step (3) is 5-15 deg.C/min, such as 5 deg.C/min, 6 deg.C/min, 8 deg.C/min, 10 deg.C/min, 12 deg.C/min or 15 deg.C/min, but not limited to the values listed, and other values not listed in the range of values are equally applicable.
Preferably, the temperature of the heat treatment in step (3) is 600-850 ℃, and may be, for example, 600 ℃, 650 ℃, 700 ℃, 750 ℃, 800 ℃ or 850 ℃, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
The heat treatment temperature is too low, and the fibers obtained by electrostatic spinning cannot be carbonized; if the heat treatment time is too short, the nickel salt cannot be completely reduced.
Preferably, the heat treatment time in step (3) is 2-4h, such as 2h, 2.5h, 3h, 3.5h or 4h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
As a preferable technical solution of the preparation method according to the second aspect of the present invention, the preparation method comprises the steps of:
(1) dissolving the binder in a solvent at 50-80 ℃ to obtain a binder solution; then uniformly mixing nickel salt and a binder solution to obtain an electrostatic spinning solution; the mass ratio of the binder to the solvent is X (100-X), wherein X is 1-10; the mass ratio of the binder to the nickel salt is Y (100-Y), wherein Y is 5-10;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film; the parameters of the electrostatic spinning comprise: the distance between the spinning needle head and the conductive matrix is 15-30cm, the spinning current is 0.5-1mA, the spinning voltage is 15-50kV, and the spinning speed is 0.03-0.1 rpm;
(3) drying the cured film obtained in the step (2) in vacuum at 180 ℃ and 240 ℃ for 12-24h, and then carrying out heat treatment in a protective atmosphere to obtain the nickel powder carved carbon fiber thermal battery substrate; the heat treatment is to heat up to 600-850 ℃ at the heating rate of 5-15 ℃/min, and the temperature is kept for 2-4 h.
In a third aspect, the present invention provides a thermal battery comprising a nickel powder-engraved carbon fiber battery substrate as described in the first aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the nickel powder carved carbon fiber thermal battery substrate is prepared by taking nickel salt as a nickel source and a high molecular compound as a carbon source and adopting an electrostatic spinning-heat treatment carbonization reduction process, and the obtained substrate has high thermal stability and is suitable for a high-temperature discharge environment of a thermal battery;
(2) according to the invention, the large specific surface area of the carbon fiber matrix and the overlapping of the carbon fiber matrix and the gap are utilized, so that the heat generated at the instant of battery activation can be effectively dispersed; the nano metallic nickel embedded into the carbon fiber can react with sulfur generated by decomposition of the anode material, so that the phenomenon of voltage spike at the initial discharge stage caused by sulfur impurities is eliminated, and the discharge stability of the thermal battery is improved.
Drawings
FIG. 1 is a process flow diagram of a nickel powder carved carbon fiber thermal battery substrate preparation method according to the present invention;
FIG. 2 is a thermogravimetric analysis curve of the nickel powder carved carbon fiber thermal battery substrate obtained in example 1;
FIG. 3 is a schematic representation of a nickel powder-engraved carbon fiber thermal battery substrate obtained in example 1;
FIG. 4 is an XRD pattern of the nickel powder carved carbon fiber thermal battery substrate obtained in example 1;
FIGS. 5 and 6 are SEM images of the nickel powder carved carbon fiber thermal battery substrate obtained in example 1;
FIG. 7 is a graph showing the discharge performance of the nickel powder-decorated carbon fiber thermal battery substrate obtained in example 1 for a thermal battery.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a nickel powder carved carbon fiber thermal battery substrate, and a preparation method of the nickel powder carved carbon fiber thermal battery substrate is shown in fig. 1, and the preparation method comprises the following steps:
(1) dissolving polyvinylidene fluoride in N-methyl pyrrolidone at 60 ℃ to obtain a binder solution; then mixing NiCl uniformly2Mixing with a binder solution to obtain an electrostatic spinning solution; the mass ratio of the polyvinylidene fluoride to the N-methyl pyrrolidone is 5: 95; the polyvinylidene fluoride and NiCl2In a mass ratio of 10: 90;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film; the parameters of the electrostatic spinning comprise: the distance between the spinning needle head and the stainless steel substrate is 25cm, the spinning current is 0.5mA, the spinning voltage is 30kV, and the spinning speed is 0.04 rpm;
(3) vacuum drying the cured film obtained in the step (2) at 200 ℃ for 12h, and then carrying out heat treatment under the protection of 30sccm nitrogen to obtain the nickel powder carved carbon fiber thermal battery substrate; the heat treatment is to heat up to 800 ℃ at a heating rate of 10 ℃/min and keep the temperature for 2 h.
This implementationThe specific surface area of the nickel powder carved carbon fiber thermal battery substrate obtained in the example is 213m2The thermal conductivity coefficient is 258W/(m.K).
Fig. 2 is a thermogravimetric analysis curve of the nickel powder carved carbon fiber thermal battery substrate obtained in this embodiment, and it can be known from fig. 2 that the nickel powder carved carbon fiber thermal battery substrate obtained in this embodiment has high thermal stability and the thermal stability temperature is greater than 850 ℃.
FIG. 3 is a schematic diagram of a nickel powder-carved carbon fiber thermal battery substrate obtained in this example.
Fig. 4 is an XRD chart of the nickel powder-decorated carbon fiber thermal battery substrate obtained in this example, and as can be seen from fig. 4, the obtained substrate contains characteristic peaks of metallic nickel powder and amorphous carbon, and does not contain other miscellaneous peaks, which indicates that the obtained substrate is a composite of metallic nickel powder and carbon material.
Fig. 5 and 6 are SEM images of the nickel powder carved carbon fiber thermal battery substrate obtained in this embodiment, in which the diameter of the carbon fiber in the obtained nickel powder carved carbon fiber thermal battery substrate is about 2 μm, and the surface of the carbon fiber is carved with hexagonal nano-metallic nickel with a particle size of about 150 nm.
Example 2
The embodiment provides a nickel powder carved carbon fiber thermal battery substrate, and a preparation method of the nickel powder carved carbon fiber thermal battery substrate is shown in fig. 1, and the preparation method comprises the following steps:
(1) dissolving polyvinylidene fluoride in N-methyl pyrrolidone at 65 ℃ to obtain a binder solution; then mixing NiCl uniformly2Mixing with a binder solution to obtain an electrostatic spinning solution; the mass ratio of the polyvinylidene fluoride to the N-methyl pyrrolidone is 3: 97; the polyvinylidene fluoride and NiCl2The mass ratio of (A) to (B) is 8: 92;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film; the parameters of the electrostatic spinning comprise: the distance between the spinning needle head and the stainless steel substrate is 20cm, the spinning current is 0.8mA, the spinning voltage is 40kV, and the spinning speed is 0.06 rpm;
(3) vacuum drying the cured film obtained in the step (2) at 210 ℃ for 18h, and then carrying out heat treatment under the protection of helium gas of 40sccm to obtain the nickel powder carved carbon fiber thermal battery substrate; the heat treatment is to heat up to 750 ℃ at the heating rate of 12 ℃/min and keep the temperature for 3 h.
The specific surface area of the nickel powder carved carbon fiber thermal battery substrate obtained in the embodiment is 479m2(ii)/g, thermal conductivity 109W/(m.K); the diameter of the obtained carbon fiber was 0.6. mu.m, and the average particle diameter of the nano-metallic nickel dispersed and embedded in the carbon fiber was 125 nm.
Example 3
The embodiment provides a nickel powder carved carbon fiber thermal battery substrate, and a preparation method of the nickel powder carved carbon fiber thermal battery substrate is shown in fig. 1, and the preparation method comprises the following steps:
(1) dissolving polyvinylidene fluoride in N-methyl pyrrolidone at 70 ℃ to obtain a binder solution; then mixing NiCl uniformly2Mixing with a binder solution to obtain an electrostatic spinning solution; the mass ratio of the polyvinylidene fluoride to the N-methyl pyrrolidone is 8: 92; the polyvinylidene fluoride and NiCl2The mass ratio of (A) to (B) is 12: 88;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film; the parameters of the electrostatic spinning comprise: the distance between the spinning needle head and the stainless steel substrate is 18cm, the spinning current is 0.9mA, the spinning voltage is 20kV, and the spinning speed is 0.08 rpm;
(3) drying the cured film obtained in the step (2) in vacuum at 220 ℃ for 15h, and then carrying out heat treatment under the protection of helium gas of 35sccm to obtain the nickel powder carved carbon fiber thermal battery substrate; the heat treatment is to heat up to 700 ℃ at the heating rate of 8 ℃/min and keep the temperature for 3.5 h.
The specific surface area of the nickel powder carved carbon fiber thermal battery substrate obtained in the embodiment is 376m2The thermal conductivity coefficient is 224W/(m.K); the diameter of the obtained carbon fiber was 1.2. mu.m, and the average particle diameter of the nano metallic nickel dispersed and embedded in the carbon fiber was 176 nm.
Example 4
The embodiment provides a nickel powder carved carbon fiber thermal battery substrate, and a preparation method of the nickel powder carved carbon fiber thermal battery substrate is shown in fig. 1, and the preparation method comprises the following steps:
(1) dissolving polyvinylidene fluoride in N-methyl pyrrolidone at 80 deg.C to obtain adhesiveA binder solution; then mixing NiCl uniformly2Mixing with a binder solution to obtain an electrostatic spinning solution; the mass ratio of the polyvinylidene fluoride to the N-methyl pyrrolidone is 10: 90; the polyvinylidene fluoride and NiCl2The mass ratio of (A) to (B) is 15: 85;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film; the parameters of the electrostatic spinning comprise: the distance between the spinning needle head and the stainless steel substrate is 30cm, the spinning current is 1mA, the spinning voltage is 50kV, and the spinning speed is 0.1 rpm;
(3) drying the cured film obtained in the step (2) at 240 ℃ in vacuum for 20 hours, and then carrying out heat treatment under the protection of argon of 20sccm to obtain the nickel powder carved carbon fiber thermal battery substrate; the heat treatment is to heat up to 850 ℃ at the heating rate of 15 ℃/min and keep the temperature for 2.5 h.
The specific surface area of the nickel powder carved carbon fiber thermal battery substrate obtained in the embodiment is 189m2The thermal conductivity coefficient is 302W/(m.K); the diameter of the obtained carbon fiber was 2.5. mu.m, and the average particle diameter of the nano-metallic nickel dispersed and embedded in the carbon fiber was 276 nm.
Example 5
The embodiment provides a nickel powder carved carbon fiber thermal battery substrate, and a preparation method of the nickel powder carved carbon fiber thermal battery substrate is shown in fig. 1, and the preparation method comprises the following steps:
(1) dissolving polyvinylidene fluoride in N-methyl pyrrolidone at 50 ℃ to obtain a binder solution; then mixing NiCl uniformly2Mixing with a binder solution to obtain an electrostatic spinning solution; the mass ratio of the polyvinylidene fluoride to the N-methyl pyrrolidone is 1: 99; the polyvinylidene fluoride and NiCl2The mass ratio of (A) to (B) is 5: 95;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film; the parameters of the electrostatic spinning comprise: the distance between the spinning needle head and the stainless steel substrate is 15cm, the spinning current is 0.6mA, the spinning voltage is 15kV, and the spinning speed is 0.03 rpm;
(3) vacuum drying the cured film obtained in the step (2) for 24 hours at 180 ℃, and then carrying out heat treatment under the protection of neon gas of 50sccm to obtain the nickel powder carved carbon fiber thermal battery substrate; the heat treatment is to heat up to 650 ℃ at the heating rate of 5 ℃/min and keep the temperature for 4 h.
The specific surface area of the nickel powder carved carbon fiber thermal battery substrate obtained in the embodiment is 144m2(ii)/g, thermal conductivity is 387W/(m.K); the diameter of the obtained carbon fiber was 3.2. mu.m, and the average particle diameter of the nano-metallic nickel dispersed and embedded in the carbon fiber was 321 nm.
Example 6
The embodiment provides a nickel powder carved carbon fiber thermal battery substrate, and a preparation method of the nickel powder carved carbon fiber thermal battery substrate is shown in fig. 1, and the preparation method comprises the following steps:
(1) dissolving polyvinylpyrrolidone in dimethylformamide at 65 ℃ to obtain a binder solution; then uniformly mixing nickel nitrate and a binder solution to obtain an electrostatic spinning solution; the mass ratio of the polyvinylpyrrolidone to the dimethylformamide is 8: 92; the mass ratio of the polyvinylpyrrolidone to the nickel nitrate is 12: 88;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film; the parameters of the electrostatic spinning comprise: the distance between the spinning needle head and the stainless steel substrate is 30cm, the spinning current is 0.7mA, the spinning voltage is 29kV, and the spinning speed is 0.07 rpm;
(3) vacuum drying the cured film obtained in the step (2) at 210 ℃ for 12h, and then carrying out heat treatment under the protection of nitrogen of 40sccm to obtain the nickel powder carved carbon fiber thermal battery substrate; the heat treatment is to heat up to 750 ℃ at the heating rate of 12 ℃/min and keep the temperature for 4 h.
The specific surface area of the nickel powder carved carbon fiber thermal battery substrate obtained in the embodiment is 97m2(ii)/g, thermal conductivity 496W/(m.K); the diameter of the obtained carbon fiber was 4.1. mu.m, and the average particle diameter of the nano-metallic nickel dispersed and embedded in the carbon fiber was 406 nm.
Example 7
The embodiment provides a nickel powder carved carbon fiber thermal battery substrate, and a preparation method of the nickel powder carved carbon fiber thermal battery substrate is shown in fig. 1, and the preparation method comprises the following steps:
(1) dissolving polystyrene in dimethyl sulfoxide at 65 ℃ to obtain a binder solution; then uniformly mixing nickel acetate and a binder solution to obtain an electrostatic spinning solution; the mass ratio of the polystyrene to the dimethyl sulfoxide is 5: 95; the mass ratio of the polystyrene to the nickel acetate is 10: 90;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film; the parameters of the electrostatic spinning comprise: the distance between the spinning needle head and the stainless steel substrate is 25cm, the spinning current is 0.5mA, the spinning voltage is 30kV, and the spinning speed is 0.04 rpm;
(3) vacuum drying the cured film obtained in the step (2) at 200 ℃ for 12h, and then carrying out heat treatment under the protection of 30sccm nitrogen to obtain the nickel powder carved carbon fiber thermal battery substrate; the heat treatment is to heat up to 800 ℃ at a heating rate of 10 ℃/min and keep the temperature for 2 h.
The specific surface area of the nickel powder carved carbon fiber thermal battery substrate obtained in the embodiment is 57m2The thermal conductivity coefficient is 584W/(m.K); the diameter of the obtained carbon fiber was 4.9. mu.m, and the average particle diameter of the nano-metallic nickel dispersed and embedded in the carbon fiber was 475 nm.
Example 8
This example provides a nickel powder decorated carbon fiber thermal battery substrate, which is the same as example 1 except that the mass ratio of polyvinylidene fluoride to N-methyl pyrrolidone in step (1) is 0.5: 99.5.
The electrospinning solution prepared in this example had a low viscosity, and thus electrospinning could not be performed.
Example 9
The embodiment provides a nickel powder carved carbon fiber thermal battery substrate, which is the same as the embodiment 1 except that the mass ratio of polyvinylidene fluoride to N-methyl pyrrolidone in the step (1) is 12: 88.
The electrostatic spinning solution prepared by the embodiment has high viscosity, and is easy to cause the blockage of a spinning needle, so that electrostatic spinning can not be smoothly carried out.
Example 10
The embodiment provides a nickel powder carved carbon fiber thermal battery substrate, which is prepared by removing polyvinylidene fluoride and NiCl in the step (1)2Is in a mass ratio of 20:80Otherwise, the same procedure as in example 1 was repeated.
In this embodiment, the amount of nickel salt is too small, and the amount of nickel loaded on the surface of the carbon fiber obtained by electrostatic spinning is too small to exert the synergistic effect between the carbon fiber and the nano-metal nickel.
Example 11
The embodiment provides a nickel powder carved carbon fiber thermal battery substrate, which is prepared by removing polyvinylidene fluoride and NiCl in the step (1)2The mass ratio of (A) to (B) was 2:98, and the rest was the same as in example 1.
In this embodiment, too much nickel salt is used, and the dispersibility of nickel particles on the surface of carbon fiber obtained by electrostatic spinning is poor.
Example 12
The present example provides a nickel powder carved carbon fiber thermal battery substrate, which is the same as example 1 except that the temperature increase rate in step (3) is 3 ℃/min.
Example 13
This example provides a nickel powder carved carbon fiber thermal battery substrate, which is the same as example 1 except that the temperature increase rate in step (3) is 18 ℃/min.
Comparative example 1
This comparative example provides a carbon fiber thermal battery substrate, which is the same as example 1 except that nickel chloride is replaced with an equimolar amount of cobalt chloride.
Comparative example 2
This comparative example provides a carbon fiber thermal battery substrate, which was the same as example 1 except that the vacuum drying as described in step (3) was not performed.
Comparative example 3
This comparative example provides a conventional commercially available thermal battery graphite substrate.
The substrate provided in example 1 and comparative example 3 were assembled into a battery, the unit cells were assembled using cobalt disulfide as the positive electrode, LiF-LiCl-LiBr as the electrolyte, and lithium boron as the negative electrode, and then 40 unit cells were assembled into a thermal battery for discharge performance comparison, to obtain a discharge performance comparison graph as shown in fig. 7, as can be seen from fig. 7, the substrate provided in example 1 can effectively weaken the voltage spike at the initial stage of discharge, improve the discharge stability of the thermal battery, and thus prolong the discharge life of the battery.
Performance testing
The substrates provided in examples 1 to 13 and comparative examples 1 to 3 were tested for thermal stability. The test method comprises the following steps: the weight change of the substrate was recorded by heating from room temperature to 900 ℃ at a heating rate of 10 ℃/min under a nitrogen atmosphere using a thermogravimetric analyzer, and the results are shown in table 1. Wherein the obtained thermal stability temperature is a temperature at which the weight is 99% of the original weight.
TABLE 1
| Temperature of thermal stability (. degree.C.) | |
| Example 1 | >850 |
| Example 2 | >850 |
| Example 3 | >850 |
| Example 4 | >850 |
| Example 5 | >850 |
| Example 6 | >850 |
| Example 7 | >850 |
| Example 8 | - |
| Example 9 | - |
| Example 10 | 843 |
| Example 11 | 846 |
| Example 12 | 834 |
| Example 13 | 831 |
| Comparative example 1 | 840 |
| Comparative example 2 | 845 |
| Comparative example 3 | >850 |
As is apparent from Table 1, in comparison with examples 10-11 and example 1, when the amount of nickel salt used was too large or too small, the heat-stable temperature of the resulting nickel powder-decorated carbon fiber thermal battery substrate was lowered. As can be seen from the comparison of examples 12-13 with example 1, when the temperature increase rate described in step (3) is too fast or too slow, the thermal stability temperature of the resulting nickel powder-decorated carbon fiber thermal battery substrate decreases.
As can be seen from comparison of comparative example 1 with example 1, replacing nickel with cobalt is also not conducive to ensuring the thermal stability of the resulting nickel powder-decorated carbon fiber thermal battery substrate.
As can be seen from the comparison of comparative example 2 with example 1, the absence of vacuum drying also affects the thermal stability temperature of the nickel powder decorated carbon fiber thermal battery substrate finally obtained.
The substrates provided in examples 1 to 13 and comparative examples 1 to 3 were assembled into a battery, and the unit cells were assembled by using cobalt disulfide as a positive electrode, LiF-LiCl-LiBr as an electrolyte, and li-b as a negative electrode, and then 40 unit cells were assembled into a thermal battery to compare discharge properties, and the peak voltage and the voltage holding ratio at 1min were measured, and the obtained results are shown in table 2.
TABLE 2
As can be seen from Table 2, in comparison with examples 10-11 and example 1, when the amount of nickel salt is too much or too little, the peak voltage of the obtained nickel powder decorated carbon fiber thermal battery substrate is higher, and the voltage holding ratio is lower. As can be seen from the comparison between examples 12-13 and example 1, when the temperature increase rate in step (3) is too fast or too slow, the peak voltage of the nickel powder-decorated carbon fiber thermal battery substrate is slightly reduced, but the voltage holding ratio is low.
It can be seen from the comparison between comparative example 1 and example 1 that the replacement of nickel with cobalt is also not favorable for reducing the peak voltage of the nickel powder carved carbon fiber thermal battery substrate, and the voltage holding ratio of the obtained substrate is low.
As can be seen from the comparison between comparative example 2 and example 1, the absence of vacuum drying also affects the peak voltage of the nickel powder decorated carbon fiber thermal battery substrate, and the voltage holding ratio of the substrate is low.
As can be seen from comparison of comparative example 3 with example 1, the graphite substrate for the conventional commercial battery has a high thermal stability temperature, but has a high voltage spike and a low voltage holding ratio.
In conclusion, the nickel powder carved carbon fiber thermal battery substrate is prepared by taking nickel salt as a nickel source and a high molecular compound as a carbon source and adopting an electrostatic spinning-heat treatment carbonization reduction process, and the obtained substrate has high thermal stability and is suitable for a high-temperature discharge environment of a thermal battery; according to the invention, the large specific surface area of the carbon fiber matrix and the overlapping of the carbon fiber matrix and the gap are utilized, so that the heat generated at the instant of battery activation can be effectively dispersed; the nano metallic nickel embedded into the carbon fiber can react with sulfur generated by decomposition of the anode material, so that the phenomenon of voltage spike at the initial discharge stage caused by sulfur impurities is eliminated, and the discharge stability of the thermal battery is improved.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.
Claims (10)
1. The nickel powder carved carbon fiber thermal battery substrate is characterized by comprising a carbon fiber matrix and nano metal nickel which is dispersedly embedded into carbon fibers.
2. The nickel powder-engraved carbon fiber thermal battery substrate according to claim 1, wherein the diameter of the carbon fibers in the carbon fiber matrix is 0.2 to 5 μm;
preferably, the morphology of the nano metallic nickel is hexagonal.
3. The nickel powder carved carbon fiber thermal battery substrate according to claim 1 or 2, wherein the specific surface area of the nickel powder carved carbon fiber thermal battery substrate is 50-500m2/g；
Preferably, the nickel powder carved carbon fiber thermal battery substrate has a thermal conductivity of 100-600W/(m.K).
4. A method for preparing the nickel powder-engraved carbon fiber thermal battery substrate as claimed in any one of claims 1 to 3, comprising the steps of:
(1) mixing a binder, a nickel salt and a solvent to obtain an electrostatic spinning solution;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film;
(3) and (3) drying the cured film obtained in the step (2) in vacuum, and then carrying out heat treatment to obtain the nickel powder carved carbon fiber thermal battery substrate.
5. The preparation method according to claim 4, wherein the mass ratio of the binder to the solvent in the step (1) is X (100-X), wherein X is 1-10;
preferably, the mass ratio of the binder to the nickel salt in the step (1) is Y (100-Y), wherein Y is 5-15.
6. The method according to claim 4 or 5, wherein the binder of step (1) comprises any one or a combination of at least two of polyvinylpyrrolidone, polyvinylidene fluoride, or polystyrene;
preferably, the nickel salt in step (1) comprises any one of nickel sulfate, nickel chloride, nickel nitrate or nickel acetate or a combination of at least two of the nickel sulfate, the nickel chloride, the nickel nitrate and the nickel acetate;
preferably, the solvent in step (1) comprises any one of or a combination of at least two of dimethylformamide, N-methylpyrrolidone or dimethylsulfoxide.
7. The method according to any one of claims 4 to 6, wherein the mixing of step (1) comprises: dissolving the binder in a solvent at 50-80 ℃ to obtain a binder solution; then uniformly mixing nickel salt and a binder solution to obtain an electrostatic spinning solution;
preferably, the parameters of the electrostatic spinning in the step (2) comprise: the distance between the spinning needle head and the conductive matrix is 15-30cm, the spinning current is 0.5-1mA, the spinning voltage is 15-50kV, and the spinning speed is 0.03-0.1 rpm;
preferably, the conductive substrate comprises any one of stainless steel, a porous conductive material or a flexible conductive material or a combination of at least two thereof.
8. The method according to any one of claims 4 to 7, wherein the temperature of the vacuum drying in step (3) is 180 ℃ and 240 ℃ for 12 to 24 hours;
preferably, the heat treatment in step (3) is performed under a protective atmosphere, wherein the gas used in the protective atmosphere comprises any one or a combination of at least two of helium, argon, neon or nitrogen;
preferably, the heating rate of the heat treatment in the step (3) is 5-15 ℃/min;
preferably, the temperature of the heat treatment in the step (3) is 600-850 ℃;
preferably, the time of the heat treatment in the step (3) is 2-4 h.
9. The method according to any one of claims 4 to 8, characterized by comprising the steps of:
(1) dissolving the binder in a solvent at 50-80 ℃ to obtain a binder solution; then uniformly mixing nickel salt and a binder solution to obtain an electrostatic spinning solution; the mass ratio of the binder to the solvent is X (100-X), wherein X is 1-10; the mass ratio of the binder to the nickel salt is Y (100-Y), wherein Y is 5-10;
(2) performing electrostatic spinning by using the electrostatic spinning solution obtained in the step (1) to obtain a cured film; the parameters of the electrostatic spinning comprise: the distance between the spinning needle head and the conductive matrix is 15-30cm, the spinning current is 0.5-1mA, the spinning voltage is 15-50kV, and the spinning speed is 0.03-0.1 rpm;
(3) drying the cured film obtained in the step (2) in vacuum at 180 ℃ and 240 ℃ for 12-24h, and then carrying out heat treatment in a protective atmosphere to obtain the nickel powder carved carbon fiber thermal battery substrate; the heat treatment is to heat up to 600-850 ℃ at the heating rate of 5-15 ℃/min, and the temperature is kept for 2-4 h.
10. A thermal battery comprising the nickel powder-engraved carbon fiber battery substrate of any of claims 1-3.
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| CN102522568A (en) * | 2011-12-10 | 2012-06-27 | 中国科学院金属研究所 | Method for preparing electrode material for all-vanadium flow battery |
| KR20150024034A (en) * | 2013-08-26 | 2015-03-06 | 주식회사 동진쎄미켐 | Core-shell filler and method for preparing core-shell filler |
| CN109037554A (en) * | 2018-06-26 | 2018-12-18 | 长沙矿冶研究院有限责任公司 | A kind of Ni/C composite nano-fiber membrane applied to lithium-sulfur cell and preparation method thereof and lithium-sulfur cell |
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