CN113921759A - Three-dimensional continuous porous nickel/carbon felt negative electrode material and preparation method thereof - Google Patents
Three-dimensional continuous porous nickel/carbon felt negative electrode material and preparation method thereof Download PDFInfo
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- CN113921759A CN113921759A CN202111177856.2A CN202111177856A CN113921759A CN 113921759 A CN113921759 A CN 113921759A CN 202111177856 A CN202111177856 A CN 202111177856A CN 113921759 A CN113921759 A CN 113921759A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 154
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 60
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 20
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 36
- 229910052786 argon Inorganic materials 0.000 claims abstract description 35
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 230000009467 reduction Effects 0.000 claims abstract description 24
- 238000011065 in-situ storage Methods 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 21
- 239000001257 hydrogen Substances 0.000 claims abstract description 17
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012528 membrane Substances 0.000 claims abstract description 12
- 239000007772 electrode material Substances 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims abstract description 9
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims description 24
- 239000000758 substrate Substances 0.000 claims description 17
- 238000001816 cooling Methods 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 10
- 238000005520 cutting process Methods 0.000 claims description 9
- 239000012300 argon atmosphere Substances 0.000 claims description 8
- 230000003197 catalytic effect Effects 0.000 claims description 8
- 239000010405 anode material Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 238000005245 sintering Methods 0.000 claims description 5
- 238000005266 casting Methods 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 238000002791 soaking Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- QBAZWXKSCUESGU-UHFFFAOYSA-N yttrium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QBAZWXKSCUESGU-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 238000007790 scraping Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000012159 carrier gas Substances 0.000 abstract description 4
- 239000010406 cathode material Substances 0.000 abstract description 2
- 239000011230 binding agent Substances 0.000 abstract 1
- 239000002134 carbon nanofiber Substances 0.000 abstract 1
- 239000011261 inert gas Substances 0.000 abstract 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 23
- 238000005229 chemical vapour deposition Methods 0.000 description 11
- 125000004122 cyclic group Chemical group 0.000 description 5
- 229920000049 Carbon (fiber) Polymers 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 239000004917 carbon fiber Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a three-dimensional continuous porous nickel/carbon felt negative electrode material and a preparation method thereof, belonging to the technical field of negative electrode materials of sodium ion batteries and comprising the following steps: firstly, placing a fired porous nickel flat membrane into a central constant-temperature area of a tubular CVD furnace, and heating to a reduction temperature under the protection of inert gas argon; reducing the porous nickel flat membrane in a reducing gas hydrogen atmosphere; and finally, introducing a carrier gas argon and a carbon source gas acetylene in a certain proportion at the growth temperature to grow carbon nanofibers with different shapes in situ, thereby obtaining the three-dimensional continuous porous nickel/carbon felt cathode material. The self-supporting three-dimensional continuous porous nickel/carbon felt electrode material prepared by the invention can realize self-supporting without any current collector or binder; the preparation method is simple and can be used for large-scale production; the prepared porous nickel/carbon felt has the characteristics of high porosity, good structural stability and good conductivity, and is suitable for sodium ion battery electrode materials.
Description
Technical Field
The invention belongs to the technical field of preparation of a negative electrode material of a sodium-ion battery, and particularly relates to a three-dimensional continuous porous nickel/carbon felt negative electrode material and a preparation method thereof.
Background
Sodium ion batteries are considered to be the most potential and most advantageous new generation of energy storage batteries for large-scale energy storage applications, and it is intended that sodium elements are widely distributed, cheap, simple in acquisition method and have many similar physicochemical properties to lithium. However, the large radius of sodium ions causes large volume change of the electrode material during de-intercalation energy storage, resulting in exfoliation of the active material and the current collector, resulting in rapid capacity fade. Therefore, the search for suitable sodium ion battery electrode materials is an important factor for researching and developing sodium ion batteries for large-scale application.
The self-supporting electrode is formed by directly carrying out in-situ growth on an active material on the surface of a catalyst and directly assembling a battery as an electrode after cutting treatment. Wherein the substrate not only acts as a growth catalyst, but also has the function of a current collector.
Aiming at the problem, the invention adopts a simple and efficient production method to prepare the three-dimensional continuous porous nickel/carbon felt cathode material. The carbon fibers with different appearances are regulated and controlled by adopting a simple Chemical Vapor Deposition (CVD) method and regulating the flow rate of a carbon source gas, the growth temperature, a catalyst and other parameters. And then shearing the electrode plates into electrode plates with proper sizes, and assembling the electrode plates into the sodium-ion battery to perform electrochemical test.
Disclosure of Invention
The invention aims to provide a preparation method of a three-dimensional continuous porous nickel/carbon felt with a simple process. An integrated electrode material having excellent uniformity and excellent sodium storage properties is prepared by a Chemical Vapor Deposition (CVD) method. The electrode material has the advantages of simple preparation process, low cost and improved controllability, is suitable for industrial scale production, and can be applied to the field of electrochemical energy storage.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of a three-dimensional continuous porous nickel/carbon felt negative electrode material comprises the following steps:
1) preparation of the catalytic substrate: taking sintered porous nickel with the thickness of 20-40 mu m as a catalyst; simultaneously loading a Y-based catalyst on the porous nickel to obtain a composite catalyst substrate;
2) reduction treatment: putting the catalyst substrate prepared in the step 1) into a central constant-temperature area of a tubular CVD furnace, and heating to 500-700 ℃ at a heating rate of 5-10 ℃/min under the argon flow of 100-150 sccm; introducing 50-150 sccm hydrogen, and performing reduction treatment for 0.5-2 h;
3) in-situ growth: closing hydrogen after reduction in the step 2), introducing mixed gas of argon and acetylene in a volume ratio of 20-40: 1, and preserving heat for 0.5-1.5 h to carry out in-situ growth; then cooling to room temperature at the cooling rate of 3-10 ℃/min under the argon flow of 100-150 sccm to obtain a three-dimensional continuous porous nickel/carbon felt;
4) assembling the battery: cutting the three-dimensional continuous porous nickel/carbon felt material prepared in the step 3) into self-supporting electrode plates with proper sizes, and assembling the self-supporting electrode plates into the sodium ion battery in a glove box filled with argon atmosphere.
Preferably, the preparation method of the porous nickel in the step 1) comprises the following steps: weighing nickel powder, NMP solvent and polyacrylonitrile to prepare a membrane casting solution, then scraping the membrane casting solution to form a membrane, and sintering the membrane to form the porous membrane under the protection of gas.
Preferably, the pore diameter of the porous nickel is 1-3 μm.
Preferably, the preparation method of the composite catalyst substrate in step 1) comprises the following steps: weighing a proper amount of yttrium nitrate hexahydrate Y (NO3) 3.6H 2O to prepare 0.001M Y-based catalyst solution, soaking porous nickel in the 0.001M Y-based catalyst solution for 0.5-3H, and performing vacuum drying at 50-80 ℃ and sintering at 300-500 ℃ for 40-80 min to obtain the composite catalyst-based substrate.
The invention also aims to provide a three-dimensional continuous porous nickel/carbon felt electrode material prepared by the preparation method of the three-dimensional continuous porous nickel/carbon felt anode material as an anode material of a sodium-ion battery.
Compared with the prior art, the invention has the beneficial effects that:
(1) the porous nickel/carbon felt cathode without the adhesive has a three-dimensional interconnected network structure, and the good structural stability can enhance the buffer capacity of the material in the sodium ion charging and discharging process, so that a battery with higher cycle stability can be obtained;
(2) the three-dimensional porous nickel/carbon felt negative electrode material has rich pores and high disorder, greatly shortens the transmission of sodium ions, provides more adsorption sites for the sodium ions and obtains an electrode material with high sodium storage capacity;
(3) the three-dimensional continuous porous nickel/carbon felt self-supporting negative electrode material reduces the resistance of an active material and a current collector, and improves the conductivity of the material;
(4) simple process, convenient operation and low cost, and is suitable for large-scale industrial production.
Drawings
FIG. 1 is a low-magnification SEM electron micrograph of a three-dimensional continuous porous nickel/carbon felt plane obtained by in-situ growth according to the preparation method of the three-dimensional continuous porous nickel/carbon felt electrode described in example 1;
FIG. 2 is a low-magnification SEM electron micrograph of a cross section of a three-dimensional continuous porous nickel/carbon felt obtained by in-situ growth according to the preparation method of the three-dimensional continuous porous nickel/carbon felt electrode described in example 1;
FIG. 3 is a long-cycle charge-discharge curve diagram at 0.1A/g of a three-dimensional continuous porous nickel/carbon felt electrode obtained by in-situ growth according to the preparation method of the three-dimensional continuous porous nickel/carbon felt electrode described in example 6;
fig. 4 is a charge and discharge curve of the first turn, the fifty th turn and the hundred th turn of the three-dimensional continuous porous nickel/carbon felt electrode obtained after in-situ growth according to the preparation method of the three-dimensional continuous porous nickel/carbon felt electrode described in embodiment 6 under 0.1A/g.
Detailed Description
Unless defined otherwise, technical terms used in the following examples have the same meanings as commonly understood by one of ordinary skill in the art to which the present invention belongs. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; the experimental methods are conventional methods unless otherwise specified; the battery test was performed using a battery tester recognized in the art.
The present invention will be described in more detail with reference to the following examples and drawings, which will enable those skilled in the art to more fully understand the present invention, but will not be limited thereto in any way.
Example 1
A preparation method of a three-dimensional continuous porous nickel/carbon felt negative electrode material comprises the following steps:
1) preparation of the catalytic substrate: placing the fired porous nickel with the thickness of 20 mu m as a catalyst in a central constant-temperature area of a tubular CVD furnace, and heating to a reduction temperature at the heating rate of 10 ℃/min under the argon flow of 100 sccm;
2) reduction treatment: when the temperature in the step 1) reaches 600 ℃, closing argon, and introducing 100Sccm hydrogen for reduction treatment for 0.5 h;
3) in-situ growth: after the step 2) is finished, closing hydrogen, introducing carrier gas and carbon source gas, introducing argon of 240Sccm and acetylene of 6Sccm (the ratio is 40:1), and preserving heat for 1.0h to carry out in-situ growth; then cooling to room temperature at the cooling rate of 10 ℃/min under the argon flow of 100sccm to obtain a three-dimensional continuous porous nickel/carbon felt;
4) assembling the battery: cutting the three-dimensional continuous porous nickel/carbon felt material prepared in the step 3) into self-supporting electrode plates with proper sizes, and assembling the self-supporting electrode plates into the sodium ion battery in a glove box filled with argon atmosphere.
FIG. 1 is an electron microscope image of a self-supporting three-dimensional continuous porous nickel/carbon felt negative electrode material in example 1, and it can be seen from the image that carbon fibers with uniform thickness are uniformly grown on the surface of porous nickel to form a whole.
Fig. 2 is a cross-sectional electron microscope image of the self-supporting three-dimensional continuous porous nickel/carbon felt negative electrode material in example 1, and it can be seen from the image that carbon fibers are uniformly grown in the three-dimensional continuous porous nickel.
And (3) electrochemical performance testing: and respectively carrying out constant current charge and discharge test, cyclic volt-ampere test and alternating current impedance test on the assembled sodium ion battery, wherein after the sodium ion battery is cycled for 200 circles, the specific capacity of the battery is still kept above 70%, and the specific discharge capacity of the battery is 182mAh/g when the sodium ion battery is cycled for 200 circles.
Example 2
A preparation method of a three-dimensional continuous porous nickel/carbon felt negative electrode material comprises the following steps:
1) preparation of the catalytic substrate: placing the fired porous nickel with the thickness of 20 mu m as a catalyst in a central constant-temperature area of a tubular CVD furnace, and heating to a reduction temperature at the heating rate of 10 ℃/min under the argon flow of 100 sccm;
2) reduction treatment: when the temperature in the step 1) reaches 650 ℃, closing argon, and introducing 100Sccm hydrogen for reduction treatment for 0.5 h;
3) in-situ growth: after the step 2) is finished, closing hydrogen, introducing carrier gas and carbon source gas, introducing argon of 240Sccm and acetylene of 6Sccm (the ratio is 40:1), and preserving heat for 1.0h to carry out in-situ growth; then cooling to room temperature at the cooling rate of 10 ℃/min under the argon flow of 100sccm to obtain a three-dimensional continuous porous nickel/carbon felt;
4) assembling the battery: cutting the three-dimensional continuous porous nickel/carbon felt material prepared in the step 3) into self-supporting electrode plates with proper sizes, and assembling the self-supporting electrode plates into the sodium ion battery in a glove box filled with argon atmosphere.
And (3) electrochemical performance testing: and respectively carrying out constant current charge and discharge test, cyclic volt-ampere test and alternating current impedance test on the assembled sodium ion battery, wherein after the sodium ion battery is cycled for 250 circles, the specific capacity of the battery is still kept above 73%, and the specific discharge capacity of the battery is 152mAh/g when the sodium ion battery is cycled for 250 circles.
Example 3
A preparation method of a three-dimensional continuous porous nickel/carbon felt negative electrode material comprises the following steps:
1) preparation of the catalytic substrate: placing the fired porous nickel with the thickness of 20 mu m as a catalyst in a central constant-temperature area of a tubular CVD furnace, and heating to a reduction temperature at the heating rate of 10 ℃/min under the argon flow of 100 sccm;
2) reduction treatment: when the temperature in the step 1) reaches 550 ℃, closing argon, and introducing 100Sccm hydrogen for reduction treatment for 0.5 h;
3) in-situ growth: after the step 2) is finished, closing hydrogen and introducing 200Sccm argon, and heating to 600 ℃ at the heating rate of 10 ℃/min; introducing argon of 240Sccm and acetylene of 6Sccm (the ratio is 40:1), and keeping the temperature for 1.0h to carry out in-situ growth; then cooling to room temperature at the cooling rate of 10 ℃/min under the argon flow of 100sccm to obtain a three-dimensional continuous porous nickel/carbon felt;
4) assembling the battery: cutting the three-dimensional continuous porous nickel/carbon felt material prepared in the step 3) into self-supporting electrode plates with proper sizes, and assembling the self-supporting electrode plates into the sodium ion battery in a glove box filled with argon atmosphere.
And (3) electrochemical performance testing: and respectively carrying out constant current charge and discharge test, cyclic volt-ampere test and alternating current impedance test on the assembled sodium ion battery, wherein after the battery is cycled for 300 circles, the specific capacity of the battery is still kept above 75%, and the specific discharge capacity of the battery is 192mAh/g when the battery is cycled for 300 circles.
Example 4
A preparation method of a three-dimensional continuous porous nickel/carbon felt negative electrode material comprises the following steps:
1) preparation of the catalytic substrate: placing the fired porous nickel with the thickness of 20 mu m as a catalyst in a central constant-temperature area of a tubular CVD furnace, and heating to a reduction temperature at the heating rate of 10 ℃/min under the argon flow of 100 sccm;
2) reduction treatment: when the temperature in the step 1) reaches 600 ℃, closing argon, and introducing 100Sccm hydrogen for reduction treatment for 0.5 h;
3) in-situ growth: after the step 2) is finished, closing hydrogen and introducing 200Sccm argon, and preserving heat for 20min at the temperature of 600 ℃; introducing 250Sccm of argon and 10Sccm of acetylene (the ratio is 25:1), and keeping the temperature for 1.0h for in-situ growth; finally, cooling to room temperature at the cooling rate of 10 ℃/min under the argon flow of 100sccm to obtain the three-dimensional continuous porous nickel/carbon felt;
4) assembling the battery: cutting the three-dimensional continuous porous nickel/carbon felt material prepared in the step 3) into self-supporting electrode plates with proper sizes, and assembling the self-supporting electrode plates into the sodium ion battery in a glove box filled with argon atmosphere.
And (3) electrochemical performance testing: and respectively carrying out constant current charge and discharge test, cyclic volt-ampere test and alternating current impedance test on the assembled sodium ion battery, wherein after the sodium ion battery is cycled for 250 circles, the specific capacity of the battery is still kept above 75%, and the specific discharge capacity of the battery is 195mAh/g when the sodium ion battery is cycled for 250 circles.
Example 5
A preparation method of a three-dimensional continuous porous nickel/carbon felt negative electrode material comprises the following steps:
1) preparation of the catalytic substrate: placing the fired porous nickel with the thickness of 20 mu m as a catalyst in a central constant-temperature area of a tubular CVD furnace, and heating to a reduction temperature at the heating rate of 10 ℃/min under the argon flow of 100 sccm;
2) reduction treatment: when the temperature in the step 1) reaches 600 ℃, closing argon, and introducing 100Sccm hydrogen for reduction treatment for 0.5 h;
3) in-situ growth: after the step 2) is finished, closing hydrogen and introducing 200Sccm argon, and preserving heat for 20min at the temperature of 600 ℃; introducing 300Sccm of argon and 10Sccm of acetylene (the ratio is 30:1), and keeping the temperature for 1.0h for in-situ growth; finally, cooling to room temperature at the cooling rate of 10 ℃/min under the argon flow of 100sccm to obtain the three-dimensional continuous porous nickel/carbon felt;
4) assembling the battery: cutting the three-dimensional continuous porous nickel/carbon felt material prepared in the step 3) into self-supporting electrode plates with proper sizes, and assembling the self-supporting electrode plates into the sodium ion battery in a glove box filled with argon atmosphere.
And (3) electrochemical performance testing: and respectively carrying out constant current charge and discharge test, cyclic volt-ampere test and alternating current impedance test on the assembled sodium ion battery, wherein after the sodium ion battery is cycled for 250 circles, the specific capacity of the battery is still kept at about 80%, and the specific discharge capacity of the battery is 235mAh/g when the sodium ion battery is cycled for 200 circles.
Example 6
A preparation method of a three-dimensional continuous porous nickel/carbon felt negative electrode material comprises the following steps:
1) preparation of the catalytic substrate: soaking the sintered porous nickel with the thickness of 20 mu M in 0.001M yttrium nitrate hexahydrate solution for 0.5h, performing vacuum drying at 80 ℃, placing the dried porous nickel in a central constant-temperature area of a tubular CVD furnace, heating to 400 ℃ at the heating rate of 10 ℃/min under the argon flow of 200sccm, and sintering for 60 min; then heating to 600 ℃ at the heating rate of 10 ℃/min;
2) reduction treatment: when the temperature in the step 1) reaches 600 ℃, closing argon, and introducing 100Sccm hydrogen for reduction treatment for 0.5 h;
3) in-situ growth: after the step 2) is finished, closing hydrogen, introducing carrier gas and carbon source gas, introducing argon of 240Sccm and acetylene of 6Sccm (the ratio is 40:1), and preserving heat for 1.0h to carry out in-situ growth; then cooling to room temperature at the cooling rate of 10 ℃/min under the argon flow of 100sccm to obtain a three-dimensional continuous porous nickel/carbon felt;
4) assembling the battery: cutting the three-dimensional continuous porous nickel/carbon felt material prepared in the step 3) into self-supporting electrode plates with proper sizes, and assembling the self-supporting electrode plates into the sodium ion battery in a glove box filled with argon atmosphere.
Fig. 3 is a constant current charge and discharge test chart of the self-supporting three-dimensional continuous porous nickel/carbon felt negative electrode material sodium ion battery in example 6, wherein the capacity retention ratio of the self-supporting electrode material after 250 cycles is more than 80%, and the specific discharge capacity after 250 cycles is 300 mAh/g.
Fig. 4 is a constant current voltage curve of the self-supporting three-dimensional continuous porous nickel/carbon felt negative electrode material sodium ion battery in example 6, and it can be seen that after 50 cycles, the charge and discharge capacities are substantially consistent and no significant change occurs.
The embodiments of the present invention have been described in detail, but the description is only for the preferred embodiments of the present invention and should not be construed as limiting the scope of the present invention. The implementation of the steps can be changed, and all equivalent changes and modifications made within the scope of the present invention should be covered by the present patent.
Claims (5)
1. A preparation method of a three-dimensional continuous porous nickel/carbon felt negative electrode material is characterized by comprising the following steps: the method comprises the following steps:
1) preparation of the catalytic substrate: taking sintered porous nickel with the thickness of 20-40 mu m as a catalyst; simultaneously loading a Y-based catalyst on the porous nickel to obtain a composite catalyst substrate;
2) reduction treatment: putting the catalyst substrate prepared in the step 1) into a central constant-temperature area of a tubular CVD furnace, and heating to 500-700 ℃ at a heating rate of 5-10 ℃/min under the argon flow of 100-150 sccm; introducing 50-150 sccm hydrogen, and performing reduction treatment for 0.5-2 h;
3) in-situ growth: closing hydrogen after reduction in the step 2), introducing mixed gas of argon and acetylene in a volume ratio of 20-40: 1, and preserving heat for 0.5-1.5 h to carry out in-situ growth; then, cooling to room temperature at a cooling rate of 3-10 ℃/min under the argon flow of 100-150 sccm to obtain a three-dimensional continuous porous nickel/carbon felt;
4) assembling the battery: cutting the three-dimensional continuous porous nickel/carbon felt material prepared in the step 3) into self-supporting electrode plates with proper sizes, and assembling the self-supporting electrode plates into the sodium ion battery in a glove box filled with argon atmosphere.
2. The preparation method of the three-dimensional continuous porous nickel/carbon felt anode material as claimed in claim 1, wherein the preparation method comprises the following steps: the preparation method of the porous nickel in the step 1) comprises the following steps: weighing nickel powder, NMP solvent and polyacrylonitrile to prepare a membrane casting solution, then scraping the membrane casting solution to form a membrane, and sintering the membrane to form the porous membrane under the protection of gas.
3. The preparation method of the three-dimensional continuous porous nickel/carbon felt anode material as claimed in claim 2, wherein the preparation method comprises the following steps: the aperture of the porous nickel is 1-3 mu m.
4. The preparation method of the three-dimensional continuous porous nickel/carbon felt anode material as claimed in claim 1, wherein the preparation method comprises the following steps: the preparation method of the composite catalyst substrate in the step 1) comprises the following steps: weighing a proper amount of yttrium nitrate hexahydrate Y (NO3) 3.6H 2O to prepare 0.001M Y-based catalyst solution, soaking porous nickel in the 0.001M Y-based catalyst solution for 0.5-3H, and performing vacuum drying at 50-80 ℃ and sintering at 300-500 ℃ for 40-80 min to obtain the composite catalyst-based substrate.
5. The three-dimensional continuous porous nickel/carbon felt electrode material prepared by the preparation method of the three-dimensional continuous porous nickel/carbon felt anode material according to any one of claims 1 to 4 is used as an anode material of a sodium ion battery.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105720236A (en) * | 2016-03-27 | 2016-06-29 | 华南理工大学 | Foamed nickel self-supported flake-shaped Ni3P/C composite material for sodium ion battery negative electrode and preparation method for composite material |
| CN110061236A (en) * | 2019-04-24 | 2019-07-26 | 陕西科技大学 | A kind of preparation method of the three-dimensional porous carbon negative pole material of self-supporting |
| CN110436436A (en) * | 2019-07-19 | 2019-11-12 | 广东工业大学 | A kind of three-dimensional microstructures self-supporting flexible, porous carbon film and its preparation method and application |
| CN112421055A (en) * | 2020-10-27 | 2021-02-26 | 太原理工大学 | Preparation method and application of oxidized nitrogen-doped carbon nanotube array cluster/flexible carbon fiber material integrated electrode |
-
2021
- 2021-10-09 CN CN202111177856.2A patent/CN113921759A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105720236A (en) * | 2016-03-27 | 2016-06-29 | 华南理工大学 | Foamed nickel self-supported flake-shaped Ni3P/C composite material for sodium ion battery negative electrode and preparation method for composite material |
| CN110061236A (en) * | 2019-04-24 | 2019-07-26 | 陕西科技大学 | A kind of preparation method of the three-dimensional porous carbon negative pole material of self-supporting |
| CN110436436A (en) * | 2019-07-19 | 2019-11-12 | 广东工业大学 | A kind of three-dimensional microstructures self-supporting flexible, porous carbon film and its preparation method and application |
| CN112421055A (en) * | 2020-10-27 | 2021-02-26 | 太原理工大学 | Preparation method and application of oxidized nitrogen-doped carbon nanotube array cluster/flexible carbon fiber material integrated electrode |
Non-Patent Citations (2)
| Title |
|---|
| 任增英: "多孔镍膜-CNTs复合电极的制备与性能研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 康建立 等: "多孔镍/碳纳米管中空纤维膜的制备与结构表征", 《天津工业大学学报》 * |
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