CN112909234A - Preparation method and application of lithium cathode or sodium cathode - Google Patents
Preparation method and application of lithium cathode or sodium cathode Download PDFInfo
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- CN112909234A CN112909234A CN202110072786.8A CN202110072786A CN112909234A CN 112909234 A CN112909234 A CN 112909234A CN 202110072786 A CN202110072786 A CN 202110072786A CN 112909234 A CN112909234 A CN 112909234A
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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
- H01M4/36—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
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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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 belongs to the technical field of new energy materials and devices, and particularly relates to a preparation method and application of a lithium cathode or a sodium cathode. The preparation method comprises the following steps: soaking the carbon fiber cloth after acid washing in a nickel nitrate water solution; then drying and calcining the carbon fiber cloth with the surface adsorbed with the nickel nitrate in inert atmosphere to obtain a three-dimensional porous current collector, wherein the surface of the carbon fiber forming the current collector is in a porous structure and is embedded with nano nickel particles in a dispersing way; and introducing metal lithium or metal sodium into the three-dimensional porous current collector by adopting a melting method to obtain a lithium negative electrode or a sodium negative electrode. Because the porous structure on the surface of the carbon fiber can provide a solid confinement effect for lithium or sodium metal, the dispersed nickel particles can endow the three-dimensional current collector with lithium or sodium affinity and reduce the deposition overpotential of the metal lithium or sodium. Therefore, the prepared lithium or sodium negative electrode exhibits excellent electrochemical properties, high safety, and long life.
Description
Technical Field
The invention relates to the technical field of new energy materials and devices, in particular to a preparation method and application of a lithium cathode or a sodium cathode.
Background
The lithium ion battery has the advantages of high energy density, long cycle life, small self-discharge, no memory effect, environmental friendliness and the like, and is widely applied to the fields of movable electronic equipment, electric automobiles, aerospace, power storage and the like. The lithium ion battery mainly comprises a positive electrode, a negative electrode, electrolyte, a diaphragm and the like, wherein the selection of the negative electrode material is directly related to the energy density of the battery. However, graphite-based negative electrode materials have evolved over the years and have approached their theoretical energy density limit. In order to further increase the energy density of the battery, it is highly desirable to develop a negative electrode material with high energy density.
Metallic lithium has an extremely high specific mass capacity (theoretical capacity 3860mA h g)-1) And extremely low redox potential (-3.040V vs. standard hydrogen electrode), are one of the most desirable negative electrode materials in next generation high energy density lithium batteries. The theoretical energy density of the lithium-sulfur battery formed by combining the metal lithium cathode and the sulfur anode is up to 2576Wh/kg, and the long-term endurance requirement of the automobile power battery can be completely met. However, the lithium metal negative electrode has problems of uneven mass transfer at an electrolyte interface, dendritic growth and 'dead lithium' caused by a charge transfer process, and problems of SEI film breakage, irreversible consumption of lithium metal and continuous reduction of coulombic efficiency caused by volume change of the lithium metal negative electrode during charge and discharge. In addition, the continuous growth of lithium dendrites in the cyclic charge and discharge process can finally puncture the diaphragm to directly contact with the positive electrode to cause short circuit of the battery, thereby causing safety accidents. Similar to the problems of lithium metal anodes, sodium metal anodes also suffer from dendrite growth and "dead sodium" problems, as well as problems of SEI film cracking and irreversible consumption of sodium metal during cycling. Therefore, finding a method for effectively inhibiting the growth of lithium dendrites or sodium dendrites is a hot problem to be solved.
In order to solve the above problems, researchers have proposed various solutions, such as stabilizing the properties of an SEI film on the surface of a lithium negative electrode or a sodium negative electrode using an electrolyte additive, and modifying the surface of the lithium negative electrode to promote uniform deposition and peeling of lithium. In recent years, researchers have found that three-dimensional porous current collectors have a significant inhibitory effect on the growth of lithium dendrites or sodium dendrites: on one hand, the three-dimensional structure with high specific surface area can reduce local current density, is beneficial to reducing the growth speed of dendrites and regulating and controlling the surface charge distribution, so that the deposition of lithium ions is more uniform; on the other hand, the porous structure can provide a physical confinement effect for the deposited lithium, inhibit the relatively infinite volume expansion of the lithium cathode and stabilize the mechanical strength of the electrode. Therefore, using a three-dimensional current collector as a host for lithium metal is a very effective way to achieve high capacity and long cycle lithium metal or sodium metal negative electrodes. Carbon-based materials have received much attention from researchers due to their light weight, good electrical conductivity, chemical stability, and good mechanical properties. However, the poor wettability of the non-polar carbon material with lithium metal or sodium metal can cause difficulty in lithium melting or sodium melting, so researchers try to modify the surface of the carbon material to introduce lithium-philic or sodium-philic sites to improve the lithium-philic or sodium-philic property of the carbon material.
Disclosure of Invention
The invention aims to: the prepared electrode has the advantages of stable structure, good flexibility and high mechanical strength, and the three-dimensional porous carbon fiber current collector can effectively inhibit the growth of dendritic crystals of lithium (sodium) and improve the cycling stability of the battery.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing a lithium negative electrode or a sodium negative electrode comprises the steps of introducing metal lithium or metal sodium into a three-dimensional porous current collector, enabling the surface of carbon fiber forming the three-dimensional current collector to be in a porous structure and to be embedded with metal nickel nano particles in a dispersion mode, enabling the metal nickel nano particles in the dispersion mode to serve as lithium-philic and sodium-philic sites, and enabling the metal lithium and the metal sodium to be uniformly distributed in the three-dimensional porous current collector during melting.
Further, a method for preparing a lithium anode or a sodium anode comprises the following steps:
(1) placing carbon fibers in a mixed solution of concentrated nitric acid and concentrated sulfuric acid for reflux treatment;
(2) sequentially carrying out ultrasonic treatment on the carbon fiber cloth obtained in the step (1) in acetone, absolute ethyl alcohol and deionized water respectively;
(3) soaking the carbon fiber cloth obtained in the step (2) in a nickel nitrate aqueous solution, and then drying in the air;
(4) calcining the carbon fiber cloth obtained in the step (3) in an inert atmosphere to obtain a three-dimensional porous current collector, wherein the surface of the carbon fiber forming the current collector is of a porous structure and is embedded with metallic nickel nano particles in a dispersing manner;
(5) and (3) heating metal lithium or metal sodium to a molten state, and then immersing the three-dimensional porous current collector obtained in the step (4) into the molten state to obtain a lithium negative electrode or a sodium negative electrode.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
the step (1) is specifically as follows: the volume ratio of 65-68% concentrated nitric acid to 95-98% concentrated sulfuric acid is 1: 3, the reflux temperature is 80-100 ℃, and the reflux time is 2-4 h.
The step (2) is specifically as follows: and (3) sequentially carrying out ultrasonic treatment on the carbon fiber cloth in acetone, absolute ethyl alcohol and deionized water for 15-20 min, and repeating for 1-3 times.
The step (3) is specifically as follows: the concentration of the nickel nitrate aqueous solution is 0.5-1.0 mol/L, the dipping temperature is 40-80 ℃, the dipping time is 1-5 h, the drying temperature is 50-80 ℃, and the drying time is 1-3 h.
The step (4) is specifically as follows: the calcination inert atmosphere is argon, the calcination temperature is 800-900 ℃, the heating rate is 3-5 ℃/min, the heat preservation time is 4-6 h, and the cooling mode is natural cooling.
The step (5) is specifically as follows: heating metal lithium or metal sodium to a molten state in a vacuum glove box, wherein the atmosphere in the glove box is argon, the temperature of the molten lithium is 300-400 ℃, and the temperature of the molten sodium is 230-380 ℃.
The preparation method and the application of the lithium cathode or the sodium cathode have the beneficial effects that:
(1) the lithium negative electrode or the sodium negative electrode based on the carbon fiber cloth has the advantages of stable structure, high mechanical strength, good flexibility and the like.
(2) The porous structure on the surface of the three-dimensional porous current collector can effectively improve the specific surface area, and the large specific surface area can reduce the local current density of metal lithium or metal sodium in the deposition and stripping processes, inhibit the growth of lithium (sodium) dendrites, and improve the safety performance and the cycling stability of the battery.
(3) The metal nickel nanoparticles on the surface of the porous carbon fiber skeleton have a good lithium (sodium) affinity effect, and the nickel particles in dispersion distribution can be used as lithium (sodium) affinity sites, so that the metal lithium (sodium) is uniformly distributed during melting, and the melting process can be completed within 10-60 s.
(4) The source of the required raw materials is rich, the cost is low, the preparation method is simple and efficient, and the method is suitable for large-scale production and application.
Drawings
In fig. 1, (a) is an SEM topography of an original carbon fiber cloth, (b-c) is an SEM topography of a three-dimensional porous current collector prepared in example 1 under different magnification, and (d) is a digital photograph of a lithium negative electrode prepared after molten lithium is injected into the three-dimensional porous current collector in example 1.
Fig. 2 is an XRD spectrum of the three-dimensional porous current collector prepared in example 1.
FIG. 3 is a graph showing 0.5mA/cm in example 1 and comparative example 12And (5) carrying out coulomb efficiency test on the half cell under the current density.
FIG. 4 shows the results of the comparative examples 1 and 1mA/cm for the symmetrical cells2Current density of 1mAh/cm2And (4) testing the cycle performance under the area capacity.
Fig. 5 is a cycle performance test of the full cells at 0.5C in example 1 and comparative example 1.
FIG. 6 shows the current density of 0.5mA/cm for the symmetrical cell of example 52The area capacity is 0.5mAh/cm2And (5) carrying out cycle performance test.
Fig. 7 is a cycle performance test of the full cell at 1C in example 5.
Detailed Description
Embodiments of the present invention will be described in further detail with reference to the accompanying drawings and specific embodiments.
Example 1
The embodiment provides a preparation method of a lithium negative electrode, which comprises the following steps:
(1) placing carbon fibers in a mixed solution of concentrated nitric acid and concentrated sulfuric acid for reflux treatment;
(2) sequentially carrying out ultrasonic treatment on the carbon fiber cloth obtained in the step (1) in acetone, absolute ethyl alcohol and deionized water respectively;
(3) soaking the carbon fiber cloth obtained in the step (2) in a nickel nitrate aqueous solution, and then drying in the air;
(4) calcining the carbon fiber cloth obtained in the step (3) in an inert atmosphere to obtain a three-dimensional porous current collector, wherein the surface of the carbon fiber forming the current collector is of a porous structure and is embedded with metallic nickel nano particles in a dispersing manner;
(5) and (3) heating the metal lithium to a molten state, and then immersing the three-dimensional porous current collector obtained in the step (4) into the metal lithium to obtain the target lithium negative electrode.
The step (1) is specifically as follows: the volume ratio of the concentrated nitric acid (68%) to the concentrated sulfuric acid (98%) is 1: 3, the reflux temperature is 80 ℃, and the reflux time is 2 hours.
The step (2) is specifically as follows: and sequentially carrying out ultrasonic treatment on the carbon fiber cloth for 15min by using acetone, absolute ethyl alcohol and deionized water respectively, and repeating for 3 times.
The step (3) is specifically as follows: the concentration of the nickel nitrate aqueous solution is 0.8mol/L, the temperature of the nickel nitrate aqueous solution is 60 ℃, the dipping time is 5 hours, the drying temperature is 60 ℃, and the drying time is 2 hours.
The step (4) is specifically as follows: the calcination inert atmosphere is argon, the temperature is 800 ℃, the heating rate is 5 ℃/min, the heat preservation time is 5h, and the cooling mode is natural cooling.
The step (5) is specifically as follows: the operation of heating the metallic lithium to a molten state was performed in a vacuum glove box, the atmosphere in the glove box being argon, and the temperature of the molten lithium being 300 ℃.
Fig. 1a is an SEM topography of an original carbon fiber cloth, fig. 1b-c are SEM topography of a three-dimensional porous current collector under different magnification, and fig. 1d is a digital photograph of a lithium negative electrode prepared after molten lithium is injected into the three-dimensional porous current collector. As can be seen from FIG. 1a, the diameter of the carbon fiber is about 8-10 μm, and the surface is smooth and flat. Fig. 1b-c show that porous structures exist on the surfaces of carbon fibers and metal nickel particles are uniformly distributed on the surfaces of the porous carbon fibers, as can be seen from the prepared three-dimensional porous current collectors. As can be seen from fig. 1d, the surface of the carbon cloth after lithium melting is uniform and flat, and shows the metallic luster of lithium metal.
FIG. 2 is an XRD (X-ray diffraction) pattern of the prepared three-dimensional porous current collector, wherein a broadened diffraction peak appears near 25.6 degrees in the pattern, and corresponds to a characteristic peak of graphitized carbon; three sharp diffraction peaks appear at 44.6 degrees, 52.0 degrees and 76.6 degrees, which correspond to the diffraction peaks of the crystal faces of the metal nickel (111), (200) and (220), respectively, and the metal nickel is effectively loaded on the surface of the porous carbon fiber.
Assembling a half cell with the three-dimensional porous current collector prepared in example 1; assembling a symmetrical battery with the prepared lithium cathode; the electrochemical performance test of the prepared lithium cathode, the common commercial diaphragm and the lithium iron phosphate anode assembled full battery is carried out, and the method comprises the following specific steps:
(1) preparing a lithium iron phosphate anode: taking lithium iron phosphate powder as a positive active material, respectively weighing lithium iron phosphate, Super P and PVDF according to the mass ratio of 8: 1, grinding and mixing uniformly, adding a proper amount of solvent NMP, grinding and mixing to obtain slurry, scraping the ground slurry on an aluminum foil current collector, drying in vacuum at 60 ℃ for 24 hours to obtain a positive plate, wherein the area capacity of the active material lithium iron phosphate in the prepared positive plate is about 5mg/cm2。
(2) Assembling the battery: assembling a half cell with the three-dimensional porous current collector prepared in example 1 and a commercial lithium sheet in a glove box under an argon atmosphere; assembling a symmetrical battery with the prepared lithium cathode; the prepared lithium cathode and the lithium iron phosphate anode are assembled into a full battery, and all batteries are button batteries of CR2032 type. Wherein the electrolyte of the half cell and the symmetrical cell is 1M LiTFSI/DOL + DME (the volume ratio of DOL to DME is 1: 1, and 2 wt% LiNO is added3) The electrolyte of the full cell is 1.0M LiPF6EC + DEC (EC to DEC volume ratio of 1: 1).
(3) And (3) performance testing: and (3) placing the assembled button cell in a thermostat at 20 ℃, and using a cell test system to test the electrochemical performance of the assembled cell, wherein the voltage window of the full cell test is 2.1-4.2V.
Comparative example 1
For comparison, the lithium negative electrode provided by the invention can effectively inhibit the growth of lithium dendrites and improve the electrochemical performance of the battery, the battery used in the test in the comparative example 1 is basically the same as the battery used in the example 1, except that a half battery is assembled by using original carbon fiber cloth, and a symmetrical battery or a full battery is assembled by using a commercial lithium sheet for testing.
Example 1 in fig. 3 half cell assembled by the prepared three-dimensional porous current collector and commercial lithium sheet was at 0.5mA/cm2The coulombic efficiency of the lower cycle is always kept above 99% in the 400-cycle process; in contrast, comparative example 1, in which the coulombic efficiency of the half-cell assembled with the virgin carbon fiber cloth and the commercial lithium sheet started to decay rapidly around 300 cycles.
In FIG. 4, example 1 is a symmetrical battery assembled by the prepared lithium cathode at 1mA/cm2，1mAh/cm2Carrying out cycle performance test under the condition, and keeping the overpotential of about 18mV after 600h of cycle; as a control, comparative example 1, a symmetrical cell assembled with commercial lithium sheets, was only able to run for 340h with overpotentials as high as 40 mV.
In FIG. 5, the lithium negative electrode of example 1 prepared by the method is used for assembling a full cell, and the full cell is subjected to cyclic charge and discharge under the condition of 0.5C, the initial discharge capacity is 158.7mAh/g, the capacity after 127 circles is 150.7mAh/g, and the average capacity fading rate per circle is 0.039%; as a comparison, in comparative example 1, a commercial lithium sheet was used as a negative electrode to assemble a full cell for cyclic charge and discharge, the specific discharge capacity at the first cycle was 140.1mAh/g, the capacity after 127 cycles was 121.2mAh/g, and the average rate of capacity fade per cycle was 0.106%. Both coulombic efficiencies were close to 100%.
Example 1 the half cell, the symmetrical cell and the full cell using the prepared lithium negative electrode all showed more excellent cycle stability compared to comparative example 1, indicating that the prepared lithium negative electrode was effectively inhibited from dendrite growth during cyclic charge and discharge.
Example 2
The preparation method of this example is substantially the same as that of example 1, except that the calcination temperature in step (4) is 900 ℃, wherein the morphology structure of the obtained three-dimensional current collector is similar to that of example 1, which indicates that the morphology thereof is not greatly affected by the temperature change within a certain temperature range. The electrochemical performance of the lithium negative electrode obtained in this example substantially coincides with that of the lithium negative electrode in example 1.
Example 3
The preparation method of the present example is substantially the same as that of example 1, except that the concentration of the nickel nitrate aqueous solution in step (3) is 1mol/L, and compared with example 1, the size of the metal nickel particles of the obtained three-dimensional current collector is larger, and the pore size of the porous structure on the surface of the carbon fiber is slightly reduced. The electrochemical performance of the lithium negative electrode obtained in this example substantially coincides with that of the lithium negative electrode in example 1.
Example 4
The preparation method of the present example is substantially the same as that of example 1, except that the concentration of the nickel nitrate aqueous solution in step (3) is 0.5mol/L, and compared with example 1, the size of the metal nickel particles of the obtained three-dimensional current collector is slightly reduced, and the pore size of the porous structure on the surface of the carbon fiber is not greatly changed. The electrochemical performance of the lithium negative electrode obtained in this example substantially coincides with that of the lithium negative electrode in example 1.
Example 5
The preparation method of this example is substantially the same as that of example 1, except that in step (5), a sodium block is heated to a molten state in an argon atmosphere glove box, and then the three-dimensional current collector obtained in step (4) is immersed in molten sodium to prepare a metallic sodium negative electrode.
FIG. 6 shows the assembly of a symmetrical cell at 0.5mA/cm with the prepared sodium cathode or commercial sodium blocks2，0.5mAh/cm2Carrying out cycle performance test under the condition, wherein the overpotential of about 160mV is kept after 700h of cycle of the prepared sodium cathode symmetric battery; in contrast, the overpotential after 700h cycling for a symmetrical cell assembled from commercial sodium blocks was as high as 400 mV.
FIG. 7 shows the sodium negative electrode or commercial sodium flake negative electrode, Na, prepared with3V2(PO4)3Positive electrode (Na)3V2(PO4)3Super P, PVDF mass ratio 8: 1) and 1M NaPF6The full battery assembled by the diglyme electrolyte has the cyclic charge and discharge performance. Under the condition of 1C, the initial discharge specific capacity of a full battery assembled by the prepared sodium cathode is 98.5mAh/g, the capacity after 150 circles is 94.4mAh/g, and the capacity retention rate is 95.8%; as a contrast, the commercial sodium block is used as a negative electrode to assemble the full-cell for cyclic charge and discharge, the specific discharge capacity of the first circle is 92.6mAh/g, the capacity after 150 circles is 79.3mAh/g, and the capacity retention rate is 85.6%. Both coulombic efficiencies were close to 100%.
Therefore, compared with a commercial sodium block, the symmetrical battery and the full battery assembled by the sodium cathode prepared in the embodiment show more excellent cycle stability, and the dendritic crystal growth of the prepared sodium cathode is effectively inhibited in the cyclic charge and discharge process.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (8)
1. A method of making a lithium or sodium anode, characterized by: soaking the carbon fiber cloth after acid washing in a nickel nitrate water solution; then drying and calcining the carbon fiber cloth with the surface adsorbed with the nickel nitrate in inert atmosphere to obtain a three-dimensional porous current collector, wherein the surface of the carbon fiber forming the current collector is in a porous structure and is embedded with nano nickel particles in a dispersing way; and introducing metal lithium or metal sodium into the three-dimensional porous current collector by adopting a melting method to obtain a lithium negative electrode or a sodium negative electrode.
2. The method of claim 1, comprising the steps of:
(1) placing carbon fibers in a mixed solution of concentrated nitric acid and concentrated sulfuric acid for reflux treatment;
(2) sequentially carrying out ultrasonic treatment on the carbon fiber cloth obtained in the step (1) in acetone, absolute ethyl alcohol and deionized water respectively;
(3) soaking the carbon fiber cloth obtained in the step (2) in a nickel nitrate aqueous solution, and then drying in the air;
(4) calcining the carbon fiber cloth obtained in the step (3) in an inert atmosphere to obtain a three-dimensional porous current collector, wherein the surface of the carbon fiber forming the current collector is of a porous structure and is embedded with metallic nickel nano particles in a dispersing manner;
(5) and (3) heating metal lithium or metal sodium to a molten state, and then immersing the three-dimensional porous current collector obtained in the step (4) into the molten state to obtain a lithium negative electrode or a sodium negative electrode.
3. The preparation method according to claim 2, wherein the volume ratio of the concentrated nitric acid to the concentrated sulfuric acid in the step (1) is 1: 3, the reflux temperature is 80-100 ℃, and the reflux time is 2-4 h.
4. The preparation method according to claim 2, wherein the carbon fiber cloth in the step (2) is sequentially subjected to ultrasonic treatment in acetone, absolute ethyl alcohol and deionized water for 15-20 min, and the ultrasonic treatment is repeated for 1-3 times.
5. The preparation method according to claim 2, wherein the concentration of the nickel nitrate aqueous solution in the step (3) is 0.5 to 1.0mol/L, the dipping temperature is 40 to 80 ℃, the dipping time is 1 to 5 hours, the drying temperature is 50 to 80 ℃, and the drying time is 1 to 3 hours.
6. The preparation method according to claim 2, wherein the calcination inert atmosphere in the step (4) is argon, the calcination temperature is 800-900 ℃, the temperature rise rate is 3-5 ℃/min, the heat preservation time is 4-6 h, and the cooling mode is natural cooling.
7. The method according to claim 2, wherein the heating of the metallic lithium or the metallic sodium to a molten state in the step (5) is performed in a vacuum glove box, wherein the atmosphere in the glove box is argon, the temperature of the molten lithium is 300 to 400 ℃, and the temperature of the molten sodium is 230 to 380 ℃.
8. Use of a lithium or sodium anode prepared according to the method of any one of claims 1 to 7 in a lithium ion battery anode.
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| CN115036454A (en) * | 2022-06-21 | 2022-09-09 | 天目湖先进储能技术研究院有限公司 | Safe and stable's activation negative pole |
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| CN113422064A (en) * | 2021-06-22 | 2021-09-21 | 广东工业大学 | Lithium metal negative current collector and preparation method and application thereof |
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| CN114551895A (en) * | 2021-07-08 | 2022-05-27 | 万向一二三股份公司 | Manufacturing method of flexible lithium metal battery cathode |
| CN113578222A (en) * | 2021-07-12 | 2021-11-02 | 浙江大学 | Nanocomposite synthesis device based on instantaneous high-temperature Joule heating method, preparation method and application |
| CN113629236A (en) * | 2021-07-15 | 2021-11-09 | 华中科技大学 | Composite metal lithium cathode and preparation method and application thereof |
| CN113629236B (en) * | 2021-07-15 | 2022-08-05 | 华中科技大学 | Composite metal lithium cathode and preparation method and application thereof |
| CN113644267A (en) * | 2021-08-03 | 2021-11-12 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN113644267B (en) * | 2021-08-03 | 2023-09-29 | 西北工业大学 | Multi-element alloy induced flexible sodium metal battery substrate and preparation method thereof |
| CN114628685A (en) * | 2021-08-09 | 2022-06-14 | 万向一二三股份公司 | Super-lithium-philic high-stability metal lithium composite negative plate and battery |
| CN114628685B (en) * | 2021-08-09 | 2023-10-03 | 万向一二三股份公司 | Super-lithium-philic high-stability metal lithium composite negative plate and battery |
| CN113972375A (en) * | 2021-10-21 | 2022-01-25 | 合肥工业大学 | Preparation method and application of porous carbon fiber/tungsten oxide self-supporting lithium-sulfur battery positive electrode material |
| CN113991094A (en) * | 2021-10-27 | 2022-01-28 | 重庆硕盈峰新能源科技有限公司 | Heteroatom in-situ doped porous carbon composite lithium cathode and preparation method and application thereof |
| CN113991094B (en) * | 2021-10-27 | 2023-09-22 | 重庆硕盈峰新能源科技有限公司 | Heteroatom in-situ doped porous carbon composite lithium anode and preparation method and application thereof |
| CN114122332A (en) * | 2021-11-25 | 2022-03-01 | 江苏科技大学 | Method for preparing three-dimensional metal lithium cathode by using MOFs (metal-organic frameworks) derivatives |
| CN114335540A (en) * | 2021-12-29 | 2022-04-12 | 北京卫蓝新能源科技有限公司 | Lithium-philic carbon skeleton composite material and preparation method and application thereof |
| CN114512637A (en) * | 2022-01-20 | 2022-05-17 | 武汉工程大学 | Three-dimensional composite lithium metal cathode with multifunctional interface layer and preparation method thereof |
| CN115036454B (en) * | 2022-06-21 | 2023-06-02 | 天目湖先进储能技术研究院有限公司 | Safe and stable activated negative electrode |
| CN115036454A (en) * | 2022-06-21 | 2022-09-09 | 天目湖先进储能技术研究院有限公司 | Safe and stable's activation negative pole |
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