CN115275118A - Preparation method of three-dimensional metal lithium negative electrode @ carbon-based material adhesive-free electrode - Google Patents

Preparation method of three-dimensional metal lithium negative electrode @ carbon-based material adhesive-free electrode Download PDF

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CN115275118A
CN115275118A CN202210962935.2A CN202210962935A CN115275118A CN 115275118 A CN115275118 A CN 115275118A CN 202210962935 A CN202210962935 A CN 202210962935A CN 115275118 A CN115275118 A CN 115275118A
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carbon
electrode
lithium
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胡笑梅
白茂辉
宾剑
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Hunan Qingfeng New Material Technology Co ltd
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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
    • H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
    • 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
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0438—Processes of manufacture in general by electrochemical processing
    • H01M4/045—Electrochemical coating; Electrochemical impregnation
    • 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
    • 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
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention belongs to the field of lithium ion secondary batteries, and discloses a preparation method of a three-dimensional metal lithium negative electrode @ carbon-based material adhesive-free electrode. The method comprises the following steps: (1) Uniformly dispersing thin-walled porous micron carbon spheres and a carbon-based material in an organic solvent to obtain an organic suspension; (2) Adopting an electrophoretic deposition process, taking the obtained organic suspension as an electrophoretic coating liquid, and depositing the electrophoretic coating liquid on a metal cathode to form a three-dimensional composite electrode; (3) And uniformly depositing lithium on the three-dimensional composite electrode to obtain the three-dimensional metal lithium cathode @ carbon-based material binder-free electrode. The preparation method has the advantages of simple preparation process, easily available raw materials, simple operation, low preparation cost and contribution to realizing large-scale application.

Description

Preparation method of three-dimensional metal lithium cathode @ carbon-based material binder-free electrode
Technical Field
The invention belongs to the field of lithium ion secondary batteries, and particularly relates to a preparation method of a three-dimensional metal lithium negative electrode @ carbon-based material adhesive-free electrode.
Background
Lithium ion secondary batteries can be widely used in portable electronic devices and electric vehicles, and these applications require lithium ion batteries to have the advantages of high energy and power density, long cycle life, low cost, environmental protection, and the like. Despite the great progress made in this field over the last decades, there is still a need to further improve the energy density of the battery, and thus research on metallic lithium negative electrodes is receiving attention.
The lithium metal negative electrode is a switching type electrode, unlike the intercalation and deintercalation mechanism of the graphite negative electrode. Because of the "host-free" deposition, the lithium negative electrode theoretically has infinite volume expansion, and designing a suitable deposition matrix can not only alleviate the huge volume effect, but also greatly slow down or inhibit the generation of dendrites. The time of the dendrite is inversely proportional to the square of the current density, namely, the current density is reduced, the initial time of the dendrite generation is increased, and the three-dimensional structure reduces the local current density of the electrode, namely, the time of the lithium dendrite generation is delayed.
Common three-dimensional lithium cathodes include metal-based three-dimensional lithium cathodes, carbon-based three-dimensional lithium cathodes, polymer three-dimensional lithium cathodes, and novel lithium cathodes. From the practical application point of view, such as cost, preparation process and the like, the carbon-based three-dimensional lithium negative electrode is one of the most promising lithium negative electrodes. However, the conventional carbon-based three-dimensional lithium negative electrode is prepared by following the conventional lithium ion battery electrode coating process, and the lithium negative electrode is prepared by mixing the conventional binder PVDF, conductive carbon black and materials.
Disclosure of Invention
In view of the above problems in the prior art, the present invention aims to provide a method for preparing a three-dimensional lithium metal anode @ carbon based material binderless electrode by electrophoretic deposition.
In order to realize the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a three-dimensional metal lithium negative electrode @ carbon-based material adhesive-free electrode comprises the following steps:
(1) Uniformly dispersing thin-wall porous micron carbon spheres and carbon-based materials in an organic solvent to obtain an organic suspension;
(2) Adopting an electrophoretic deposition process, taking the obtained organic suspension as an electrophoretic coating liquid, and depositing the electrophoretic coating liquid on a metal cathode to form a three-dimensional composite electrode;
(3) And uniformly depositing lithium on the three-dimensional composite electrode to obtain the three-dimensional metal lithium cathode @ carbon-based material adhesive-free electrode.
Preferably, in step (1):
the carbon-based material is one or more of carbon nano tube, carbon fiber, graphene, biomass derived carbon, layered porous carbon and heteroatom doped carbon;
the organic solvent is one or more of ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, 1, 3-dioxolane, ethylene glycol dimethyl ether and tetrahydrofuran;
the aperture of the micron carbon sphere is 1 to 20 microns, and the wall thickness is 10 to 200nm.
Further preferably, in the step (1), the micron carbon spheres are prepared by using a silica template.
Preferably, the concentration of the micron carbon spheres in the organic suspension is 1 to 100mg/ml; the concentration of the carbon-based material is 0.1 to 10mg/ml.
Preferably, step (1) is specifically:
dispersing carbon microspheres in an organic solvent, and performing ultrasonic and stirring treatment to form a micrometer carbon sphere dispersion liquid;
adding the carbon-based material into the micron carbon sphere dispersion liquid, and carrying out ultrasonic and stirring treatment to obtain the organic suspension.
Further preferably, the ultrasonic temperature is 25 to 60 ℃, the ultrasonic power is 100 to 800W, and the ultrasonic time is 0.5 to 5h;
the stirring temperature is 25 to 60 ℃, the stirring speed is 200 to 800r/min, and the stirring time is 1 to 12h.
Preferably, in the step (2), the direct-current voltage intensity of the electrophoretic deposition is 1 to 100V/cm; the deposition time is 10 to 1000s.
Preferably, in the step (2), the metal cathode is copper; the positive electrode adopts one of platinum, gold and graphite carbon.
Preferably, in the step (3), lithium is uniformly deposited on the three-dimensional composite electrode in such a manner that the three-dimensional composite electrode is assembled with the lithium into a half cell.
More preferably, the current density of the half-cell is 0.05 to 20mA cm -2 (ii) a The deposition amount of lithium is 0.5 to 50mAh cm -2 。
Compared with the prior art, the invention has the following beneficial effects:
(1) The electrode for the lithium ion battery without the binder is prepared by the electrophoretic deposition method, and the obtained electrode not only has a plumpy, uniform, flat and smooth coating, but also has excellent hardness, adhesive force, corrosion resistance, impact performance, permeability and the like;
(2) The carbon-based material in the electrode obtained by the method can be used as a conductive material and an electrode protective layer, so that the erosion of electrolyte to the electrode material is prevented, the growth of lithium dendrite is inhibited, the coulombic efficiency of the electrode is improved, the electrochemical performance of the electrode is obviously improved, and the cycling stability of a battery is improved;
(3) The invention has universality, simple preparation process, easily obtained raw materials, simple operation and lower preparation cost, and is beneficial to realizing large-scale application.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a graph of the 10mA cm of an RGO-Li [ L ] RGO-Li symmetric cell assembled with a three-dimensional lithium metal negative electrode prepared using electrophoretic deposition @ graphene electrode in example 1 of the present invention and a Li [ L ] Li symmetric cell (CR 2032) in comparative example 1 -2 Current density,. L mAh cm -2 Cycle performance at deposition capacity is plotted against time.
Fig. 2 is a graph comparing the cycle performance at 1C current density of NCM | | | RGO-Li full cells assembled using three-dimensional metallic lithium negative electrodes prepared using electrophoretic deposition @ graphene electrodes in example 1 of the present invention and NCM | | | Li full cells (CR 2032) in comparative example 1.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
The embodiment provides a method for preparing a thin-wall porous micron carbon sphere @ graphene binder-free electrode through electrophoretic deposition, which specifically comprises the following steps:
s1, preparing thin-wall porous micron carbon spheres by using a template method and a silicon dioxide template, wherein the pore diameter of the micron carbon spheres is 5 microns, the wall thickness of the micron carbon spheres is 20nm, the thin-wall porous carbon spheres are dispersed in a tetrahydrofuran organic solvent for lithium ion battery electrolyte, the concentration of the micron carbon spheres is 10mg/ml, then heating and ultrasonic stirring treatment is carried out, the ultrasonic temperature is 45 ℃, the ultrasonic power is 200W, the ultrasonic time is 1h, the stirring speed is 400r/min, and the stirring time is 2h, so that a thin-wall porous micron carbon sphere tetrahydrofuran organic solvent dispersion liquid is formed;
s2, adding graphene into the thin-wall porous micron carbon sphere dispersion liquid according to the concentration ratio of 1mg/ml, and carrying out treatment at the ultrasonic temperature of 45 ℃, the ultrasonic power of 200W, the ultrasonic time of 1h, the stirring speed of 400r/min and the stirring time of 2h to obtain thin-wall porous micron carbon spheres and graphene suspension, namely the electrophoretic coating liquid;
and S3, adopting metal platinum and copper as plane electrodes, vertically inserting the plane electrodes into the electrophoretic paint, and depositing for 50S under the action of electrophoretic deposition direct-current voltage with the strength of 4.7V/cm to obtain the three-dimensional composite electrode.
S4, assembling a half cell by adopting metal lithium and the three-dimensional composite electrode, wherein the thickness of the half cell is 1 mAcm -2 Current density ofDegree and 1mAh cm -2 The deposition amount of lithium is deposition conditions, and the thin-wall porous micron carbon sphere three-dimensional metal lithium cathode @ graphene binderless electrode is obtained.
Assembling the battery: the thin-wall porous micron carbon sphere three-dimensional metal lithium negative electrode @ graphene binder-free electrode material prepared in the embodiment is assembled into a symmetrical battery RGO-Li | RGO-Li, and the ratio of the thickness of the thin-wall porous micron carbon sphere three-dimensional metal lithium negative electrode @ graphene to the thickness of the thin-wall porous carbon sphere three-dimensional metal lithium negative electrode @ graphene is 1mol/L, liTFSI/DOL: DME (1).
The three-dimensional lithium metal negative electrode @ graphene binderless electrode material prepared in the embodiment and a ternary positive electrode material are assembled into a full-cell NCM (negative electrode matrix) RGO-Li with the molar ratio of 1mol/L, liPF 6 EC: DMC (1.
Comparative example 1
The comparative example used an untreated planar metallic lithium negative electrode that was conventionally used.
The lithium negative electrode is used for assembling a symmetrical battery Li, at a molar ratio of 1mol/L, liTFSI/DOL: DME (1);
the lithium cathode and the ternary cathode material are used for assembling the full-battery NCM Li with the mol/L of 1 and LiPF 6 EC: DMC (1.
The cycle performance of the batteries obtained in example 1 and comparative example 1 were compared as shown in fig. 1 and 2. It can be seen that the cycle performance of the battery assembled by the electrode prepared by electrophoretic deposition is obviously superior to that of the battery using the conventional electrode, the overpotential of the symmetrical battery is always kept at about 30mV in the 200h cycle process, and the NCM (negative control) RGO-Li full battery still has 90.2% of capacity retention rate after 100 cycles;
in contrast, the symmetric battery using the conventional electrode has a short circuit phenomenon after dozens of cycles, and the NCM Li full battery has a capacity retention rate of only 70.6% after 100 cycles. The thin-wall porous micron carbon sphere @ graphene electrode without the adhesive prepared by electrophoretic deposition is stable in coating, and the unique structure of the electrode can effectively prevent the corrosion of electrolyte on an electrode active material and inhibit dendritic crystal growth, so that the performance of the battery is greatly improved.
Example 2
The invention provides a method for preparing a thin-wall porous micron carbon ball @ carbon nano tube binderless electrode by electrophoretic deposition. The concentrations of the thin-wall porous micron carbon spheres and the carbon nano tubes in the methyl ethyl carbonate organic solvent are 20mg/ml and 5mg/ml respectively.
The method for preparing the thin-wall porous micron carbon sphere @ carbon nanotube binderless electrode by electrophoretic deposition comprises the following steps of:
s1, preparing thin-wall porous micron carbon spheres with the aperture of 10 microns and the wall thickness of 50nm by using a template method and a silicon dioxide template, dispersing the thin-wall porous carbon spheres in a methyl ethyl carbonate organic solvent for lithium ion battery electrolyte with the concentration of 20mg/ml, and then carrying out heating ultrasonic stirring treatment, wherein the ultrasonic temperature is 50 ℃, the ultrasonic power is 400W, the ultrasonic time is 2h, the stirring speed is 600r/min, and the stirring time is 2h, so that a thin-wall porous micron carbon sphere methyl ethyl carbonate organic solvent dispersion liquid is formed;
s2, adding the carbon nano tubes into the thin-wall porous micron carbon sphere dispersion liquid according to the concentration ratio of 5mg/ml, and performing treatment at the ultrasonic temperature of 50 ℃, the ultrasonic power of 400W, the ultrasonic time of 2h, the stirring speed of 600r/min and the stirring time of 2h to obtain a thin-wall porous micron carbon sphere and carbon nano tube suspension, namely the electrophoretic coating liquid;
and S3, adopting metal platinum and copper as plane electrodes, vertically inserting the plane electrodes into the electrophoretic paint, and depositing for 30S under the action of electrophoretic deposition direct-current voltage with the strength of 6.3V/cm to obtain the thin-wall porous micron carbon ball @ carbon nanotube binderless electrode.
S4, assembling a half-cell by adopting metal lithium and the three-dimensional composite electrode, wherein the thickness of the half-cell is 2 mAcm -2 Current density of 2mAh cm -2 The deposition amount of the lithium is deposition conditions, and the thin-wall porous micron carbon sphere three-dimensional metal lithium cathode @ carbon nanotube binderless electrode is obtained.
Assembling the battery: the adhesive-free electrode material of the thin-wall porous micron carbon sphere three-dimensional metal lithium cathode @ carbon nanotube prepared in the embodiment is assembled into a symmetrical battery CNT-Li | | | CNT-Li, and the ratio of the carbon material to the adhesive-free electrode material is 1mol/L, liTFSI/DOL: DME (1).
The three-dimensional metal lithium cathode @ carbon nanotube electrode material prepared in the embodiment without the binder and the ternary cathode material are assembled into a full-cell NCM | | | CNT-Li with 1mol/L LiPF 6 EC: DMC (1.
The cycling performance of the battery assembled by the electrode prepared by electrophoretic deposition in the embodiment 2 is that the overpotential of the symmetrical battery is always kept at about 50mV in the 200h cycling process, and the NCM (negative control) CNT-Li full battery still has 88.5% of capacity retention rate after 100 cycles.
Example 3
The invention provides a method for preparing a thin-wall porous micron carbon ball and carbon fiber binderless electrode by electrophoretic deposition. The concentrations of the thin-wall porous micron carbon spheres and the carbon fibers in the glycol dimethyl ether organic solvent are 5mg/ml and 0.1mg/ml respectively.
The method for preparing the thin-wall porous micron carbon sphere @ carbon fiber binderless electrode by electrophoretic deposition comprises the following steps of:
s1, preparing thin-wall porous micron carbon spheres with the aperture of 1 micron and the wall thickness of 10nm by using a template method and a silicon dioxide template, dispersing the thin-wall porous carbon spheres in a glycol dimethyl ether organic solvent for lithium ion battery electrolyte, wherein the concentration of the thin-wall porous carbon spheres is 50mg/ml, and then carrying out heating ultrasonic stirring treatment, wherein the ultrasonic temperature is 30 ℃, the ultrasonic power is 100W, the ultrasonic time is 0.5h, the stirring speed is 200r/min, and the stirring time is 1h, so that a thin-wall porous micron carbon sphere glycol dimethyl ether organic solvent dispersion liquid is formed;
s2, adding carbon fibers into the thin-wall porous micron carbon sphere dispersion liquid according to the concentration ratio of 0.1mg/ml, and performing treatment at the ultrasonic temperature of 30 ℃, the ultrasonic power of 100W, the ultrasonic time of 0.5h, the stirring speed of 200r/min and the stirring time of 1h to obtain a thin-wall porous micron carbon sphere and carbon fiber suspension, namely the electrophoretic coating liquid;
and S3, adopting metal platinum and copper as plane electrodes, vertically inserting the plane electrodes into the electrophoretic paint, and depositing for 10S under the action of electrophoretic deposition direct-current voltage with the strength of 2.7V/cm to obtain the thin-wall porous micron carbon ball @ carbon fiber binderless electrode.
S4, assembling a half-cell by adopting metal lithium and the three-dimensional composite electrode, wherein the thickness of the half-cell is 2 mAcm -2 Current density of 2mAh cm -2 The deposition amount of the lithium is deposition conditions, and the thin-wall porous micron carbon sphere three-dimensional metal lithium cathode @ carbon fiber binderless electrode is obtained.
Assembling the battery: the thin-wall porous micron carbon sphere @ carbon fiber binderless electrode material prepared in the embodiment is assembled into a symmetrical battery CF-Li | | CF-Li, wherein the weight ratio of the thin-wall porous micron carbon sphere @ carbon fiber to the binderless electrode material is 1mol/L, and the weight ratio of the thin-wall porous micron carbon sphere @ carbon fiber to the binderless electrode material is LiTFSI/DOL: DME (1.
The three-dimensional metal lithium cathode @ carbon fiber binderless electrode material prepared in the embodiment and a ternary cathode material are assembled into a full-cell NCM | | | CF-Li with the mol/L of 1 and LiPF 6 EC: DMC (1.
The cycling performance of the battery assembled by the electrode prepared by electrophoretic deposition in the embodiment 3 is that the overpotential of the symmetrical battery is always kept at about 70mV in the 200h cycling process, and the NCM (negative control module) CF-Li full battery still has 84.9% of capacity retention rate after 100 cycles.
The above is only a preferred embodiment of the present invention, and is not intended to limit the present invention, and various modifications and changes will occur to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (10)

1. A preparation method of a three-dimensional metal lithium negative electrode @ carbon-based material binder-free electrode is characterized by comprising the following steps of:
(1) Uniformly dispersing thin-walled porous micron carbon spheres and a carbon-based material in an organic solvent to obtain an organic suspension;
(2) Adopting an electrophoretic deposition process, taking the obtained organic suspension as an electrophoretic coating liquid, and depositing the electrophoretic coating liquid on a metal cathode to form a three-dimensional composite electrode;
(3) And uniformly depositing lithium on the three-dimensional composite electrode to obtain the three-dimensional metal lithium cathode @ carbon-based material adhesive-free electrode.
2. The method of claim 1, wherein in step (1):
the carbon-based material is one or more of carbon nano tube, carbon fiber, graphene, biomass derived carbon, layered porous carbon and heteroatom doped carbon;
the organic solvent is one or more of ethylene carbonate, diethyl carbonate, dimethyl carbonate, ethyl methyl carbonate, propylene carbonate, 1, 3-dioxolane, ethylene glycol dimethyl ether and tetrahydrofuran;
the aperture of the micron carbon sphere is 1 to 20 microns, and the wall thickness is 10 to 200nm.
3. The method according to claim 2, wherein in the step (1), the micron carbon spheres are prepared by using a silica template.
4. The preparation method according to claim 1, wherein the concentration of the carbon microspheres in the organic suspension is 1 to 100mg/ml; the concentration of the carbon-based material is 0.1 to 10mg/ml.
5. The preparation method according to any one of claims 1 to 4, wherein the step (1) is specifically as follows:
dispersing carbon microspheres in an organic solvent, and performing ultrasonic and stirring treatment to form a micrometer carbon sphere dispersion liquid;
adding the carbon-based material into the micron carbon sphere dispersion liquid, and carrying out ultrasonic and stirring treatment to obtain the organic suspension.
6. The preparation method according to claim 5, wherein the ultrasonic temperature is 25 to 60 ℃, the ultrasonic power is 100 to 800W, and the ultrasonic time is 0.5 to 5h;
the stirring temperature is 25 to 60 ℃, the stirring speed is 200 to 800r/min, and the stirring time is 1 to 12h.
7. The method according to claim 1, wherein in the step (2), the DC voltage intensity of the electrophoretic deposition is 1 to 100V/cm; the deposition time is 10 to 1000s.
8. The method according to claim 1, wherein in the step (2), the metal negative electrode is copper; the positive electrode adopts one of platinum, gold and graphite carbon.
9. The method of claim 1, wherein in step (3), lithium is uniformly deposited on the three-dimensional composite electrode in such a manner that the three-dimensional composite electrode is assembled with the lithium into a half-cell.
10. The method of claim 9, wherein the half-cell has a current density of 0.05 to 20mA cm -2 (ii) a The deposition amount of lithium is 0.5 to 50mAh cm -2 。
CN202210962935.2A 2022-08-11 2022-08-11 Preparation method of three-dimensional metal lithium negative electrode @ carbon-based material adhesive-free electrode Pending CN115275118A (en)

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