CN113690402A - Lithium ion battery, lithium ion battery cathode and preparation method thereof - Google Patents

Lithium ion battery, lithium ion battery cathode and preparation method thereof Download PDF

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CN113690402A
CN113690402A CN202110910250.9A CN202110910250A CN113690402A CN 113690402 A CN113690402 A CN 113690402A CN 202110910250 A CN202110910250 A CN 202110910250A CN 113690402 A CN113690402 A CN 113690402A
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lithium ion
ion battery
gadolinium
film layer
battery cathode
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CN113690402B (en
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贺丹琪
毛明恒
赵文俞
桑夏晗
翟鹏程
张清杰
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Wuhan University of Technology WUT
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/0688—Cermets, e.g. mixtures of metal and one or more of carbides, nitrides, oxides or borides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • 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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • 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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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention discloses a lithium ion battery, a lithium ion battery cathode and a preparation method thereof, and belongs to the technical field of metal lithium battery cathode materials. The lithium ion battery cathode comprises a substrate and a thin film layer, wherein the thin film layer is coated on the surface of the substrate, and the thin film layer is made of gadolinium and gadolinium oxides. The preparation method comprises the following steps: fixing the substrate on a base of a vacuum chamber of vacuum evaporation coating equipment, placing gadolinium powder on an evaporation boat, and fixing the evaporation boat between two electrodes of the vacuum chamber; and vacuumizing to keep the vacuum chamber in a vacuum environment, and heating the gadolinium powder under the current of 180-220A to obtain the lithium ion battery cathode. In addition, the invention also provides a lithium ion battery, which comprises the lithium ion battery cathode or the lithium ion battery cathode prepared by the preparation method. The lithium ion battery cathode can effectively improve the coulombic efficiency of the lithium ion battery and can improve the cycle stability of the lithium ion battery.

Description

Lithium ion battery, lithium ion battery cathode and preparation method thereof
Technical Field
The invention relates to the technical field of metal lithium battery cathode materials, in particular to a lithium ion battery, a lithium ion battery cathode and a preparation method thereof.
Background
Achieving uniform and stable lithium deposition is the key to obtaining an ideal lithium metal negative electrode, which has a high theoretical specific capacity (up to 3860mAh/g), a low redox potential (3.04V relative to a standard hydrogen electrode) and low density, and is expected to be used in next-generation high energy density batteries.
However, the uneven deposition of lithium ions causes dendritic or moss-like dendritic structures to be formed on the surface of the electrode, resulting in a decrease in coulombic efficiency and poor battery cycle stability. When the lithium dendrites continuously grow until the battery penetrates through the separator, thermal runaway of the battery and even fire explosion are caused, and serious safety problems are caused. In addition, unlike graphite and silicon anodes, the relative volume change of metallic lithium anodes is virtually infinite, which in turn can lead to the structure of the electrode collapsing during cycling. In order to solve the above problems, researchers have developed various methods to stabilize lithium deposition during cycling, such as three-dimensional current collectors, modified Solid Electrolyte Interphase (SEI) layers, artificial protective layers, or electrolyte additives, but all of the above methods have the problems of complicated process and unstable quality, and thus a solution to the problem of poor cycling stability of the battery in the lithium ion battery is needed.
Disclosure of Invention
The invention aims to overcome the technical defects, provides a lithium ion battery, a lithium ion battery cathode and a preparation method thereof, and solves the technical problem of poor cycle stability of the lithium ion battery in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention provides a lithium ion battery, a lithium ion battery cathode and a preparation method thereof.
The lithium ion battery cathode comprises a substrate and a thin film layer, wherein the thin film layer is coated on the surface of the substrate, and the thin film layer is made of gadolinium and gadolinium oxides.
Furthermore, the substrate is made of copper.
Further, the substrate is a copper foil, a copper mesh or a copper foam.
Further, the oxide of gadolinium is gadolinium oxide.
Furthermore, the thin film layer is coated on the surface of the substrate in a vacuum evaporation mode.
The invention also provides a preparation method of the lithium ion battery cathode, which comprises the following steps: fixing the substrate on a base of a vacuum chamber of vacuum evaporation coating equipment, placing gadolinium powder on an evaporation boat, and fixing the evaporation boat between two electrodes of the vacuum chamber; and vacuumizing to keep the vacuum chamber in a vacuum environment, and heating the gadolinium powder under the current of 180-220A to obtain the lithium ion battery cathode.
Further, the gadolinium powder is heated for 1-5 min.
Further, the pressure of the vacuum environment is 5 × 10-4-6×10-4Pa。
Further, the gadolinium powder is heated under a current of 190A-210A.
In addition, the invention also provides a lithium ion battery, which comprises the lithium ion battery cathode or the lithium ion battery cathode prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that: according to the lithium ion battery cathode provided by the invention, the surface of the substrate is coated with the film layer, the material of the film layer is gadolinium and gadolinium oxides, the lithium ion battery cathode can induce the uniform deposition of lithium ions, and the growth of lithium dendrites is avoided, so that the coulomb efficiency of the lithium ion battery is effectively improved, the cycle stability of the lithium ion battery can be improved, the cycle is 200 times, and the coulomb efficiency is over 90%.
Drawings
Fig. 1 is a picture of a copper foil used for a negative electrode of a lithium ion battery in an example of the invention;
fig. 2 is an EDS spectrum analysis chart of the negative electrode of the lithium ion battery in example 3 of the present invention.
Fig. 3 is a scanning electron microscope image of the surface of the thin film layer of the negative electrode of the lithium ion battery prepared in example 4 of the present invention.
Fig. 4 is a graph comparing the cyclic coulombic efficiencies in ether electrolytes for lithium ion batteries prepared in example 5 of the present invention and comparative example 1.
Fig. 5 is a graph comparing the cyclic coulombic efficiencies in ether electrolytes for lithium ion batteries prepared in example 6 of the present invention and comparative example 1.
Detailed Description
The specific embodiment provides a lithium ion battery cathode, which comprises a substrate and a thin film layer, wherein the thin film layer is coated on the surface of the substrate in a vacuum evaporation mode, and the thin film layer is made of gadolinium and gadolinium oxides; further, the substrate is made of copper foil, copper mesh or foam copper, and the oxide of gadolinium is gadolinium oxide.
The specific embodiment further comprises a preparation method of the lithium ion battery cathode, which comprises the following steps: fixing the substrate on a base of a vacuum chamber of vacuum evaporation coating equipment, placing gadolinium powder on an evaporation boat, and fixing the evaporation boat between two electrodes of the vacuum chamber; and (3) vacuumizing to keep the vacuum chamber in a vacuum environment, and heating the gadolinium powder for 1min-5min under the current of 180A-220A to obtain the lithium ion battery cathode. Further, the pressure of the vacuum environment is 5 × 10-4-6×10-4Pa, and further heating the gadolinium powder under the current of 190A-210A.
The specific embodiment also provides a lithium ion battery, which comprises the lithium ion battery cathode or the lithium ion battery cathode prepared by the preparation method.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
In the following examples, the purity of gadolinium powder was 99.9%, and the diameter of copper foil was 12 mm.
Example 1
The embodiment provides a lithium ion battery cathode, which comprises a copper foil and a film layer, wherein the film layer is coated on the surface of a substrate in a vacuum evaporation mode, and the film layer is made of gadolinium and gadolinium oxide.
The lithium ion battery cathode provided by the embodiment is prepared by the following steps: fixing a copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, uniformly scattering 0.5505g of gadolinium powder on an evaporation boat, and fixing the evaporation boat between two electrodes of the vacuum chamber; vacuumizing to maintain the vacuum chamber at 6 × 10-4Pa, heating gadolinium powder for 1min under the current of 210A to obtain the lithium ion battery cathode with a uniform film layer, wherein the film layer is peach-red, and the thickness of the film layer is 50 nm.
Example 2
The embodiment provides a lithium ion battery cathode, which comprises a copper foil and a film layer, wherein the film layer is coated on the surface of a substrate in a vacuum evaporation mode, and the film layer is made of gadolinium and gadolinium oxide.
The lithium ion battery cathode provided by the embodiment is prepared by the following steps: fixing a copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, uniformly scattering 0.8405g of gadolinium powder on an evaporation boat, and fixing the evaporation boat between two electrodes of the vacuum chamber; vacuumizing to make the vacuum chamber maintain the pressure of 5 x 10-4And Pa, heating the gadolinium powder for 5min under the current of 180A to obtain the lithium ion battery cathode with a uniform film layer, wherein the film layer is light yellow, and the thickness of the film layer is 75 nm.
Example 3
The embodiment provides a lithium ion battery cathode, which comprises a copper foil and a film layer, wherein the film layer is coated on the surface of a substrate in a vacuum evaporation mode, and the film layer is made of gadolinium and gadolinium oxide.
The lithium ion battery cathode provided by the embodiment is prepared by the following steps: fixing a copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, uniformly scattering 0.5304g of gadolinium powder on an evaporation boat, and fixing the evaporation boat between two electrodes of the vacuum chamber; vacuumizing to make the vacuum chamber maintain the pressure of the vacuum environment at 5.5 x 10-4And Pa, heating the gadolinium powder for 2min under the current of 190A to obtain the lithium ion battery cathode with a uniform film layer. The obtained copper foil containing gadolinium and gadolinium oxide was analyzed by EDS, and as shown in FIG. 2, the result of EDS analysis showed that the copper foil contained Gd and O elements, which also indicates that gadolinium oxide, which is an oxide of gadolinium, was deposited on the surface of the copper foil, and the thickness of the thin film layer was 45 nm.
Example 4
The embodiment provides a lithium ion battery cathode, which comprises a copper foil and a film layer, wherein the film layer is coated on the surface of a substrate in a vacuum evaporation mode, and the film layer is made of gadolinium and gadolinium oxide.
The lithium ion battery cathode provided by the embodiment is prepared by the following steps: fixing a copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, uniformly scattering 0.5304g of gadolinium powder on an evaporation boat, and fixing the evaporation boat between two electrodes of the vacuum chamber; vacuumizing to make the vacuum chamber maintain the pressure of the vacuum environment at 5.5 x 10-4And Pa, heating the gadolinium powder for 2min under the current of 190A to obtain the lithium ion battery cathode with a uniform film layer, wherein the thickness of the film layer is 45 nm. The obtained copper foil containing gadolinium and oxides thereof is observed by a field emission scanning electron microscope, and as shown in fig. 3, the surface microstructure shows that the modified material is uniformly deposited on the surface of the copper foil. As can be seen from fig. 1, the surface of the copper foil before plating was smooth.
Example 5
The embodiment provides a lithium ion battery cathode, which comprises a copper foil and a film layer, wherein the film layer is coated on the surface of a substrate in a vacuum evaporation mode, and the film layer is made of gadolinium and gadolinium oxide.
The lithium ion battery cathode provided by the embodiment is prepared by the following steps: fixing a copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, uniformly scattering 0.5306g of gadolinium powder on an evaporation boat, and fixing the evaporation boat between two electrodes of the vacuum chamber; vacuumizing to make the vacuum chamber maintain the pressure of the vacuum environment at 5.5 x 10-4And Pa, heating the gadolinium powder for 2min under the current of 190A to obtain the lithium ion battery cathode with a uniform film layer, wherein the thickness of the film layer is 75 nm.
Example 6
The embodiment provides a lithium ion battery cathode, which comprises a copper foil and a film layer, wherein the film layer is coated on the surface of a substrate in a vacuum evaporation mode, and the film layer is made of gadolinium and gadolinium oxide.
The lithium ion battery cathode provided by the embodiment is prepared by the following steps: fixing a copper foil on a base of a vacuum chamber of vacuum evaporation coating equipment, uniformly scattering 0.8306g of gadolinium powder on an evaporation boat, and fixing the evaporation boat between two electrodes of the vacuum chamber; vacuumizing to make the vacuum chamber maintain the pressure of the vacuum environment at 5.5 x 10-4And Pa, heating the gadolinium powder for 3min under the current of 190A to obtain the lithium ion battery cathode with a uniform film layer, wherein the thickness of the film layer is 50 nm.
Comparative example 1
The negative electrode of the lithium ion battery proposed in this comparative example was a copper foil for a commercial lithium battery, which was punched to obtain a copper foil having a diameter of 12mm (actually, a copper foil before evaporation of gadolinium powder).
Application example
The lithium ion battery cathodes in examples 5 to 6 and comparative example 1 were used to prepare a lithium ion battery, specifically, the lithium ion battery cathode was assembled with a 12mm lithium sheet to form a battery, the electrolyte was an organic ether electrolyte, and the separator was a polypropylene separator used in a commercial lithium battery. The organic ether electrolyte is DOL/DME.
It can be seen from fig. 4 that in example 5, the modified material containing gadolinium and gadolinium oxide can effectively prevent the growth of lithium dendrite, and improve the cycle stability of the lithium ion battery, and the coulombic efficiency is significantly higher than that of comparative example 1, the cycle stability is also better than that of comparative example 1, the coulombic efficiency is over 90% after 200 cycles, and the coulombic efficiency is significantly reduced after 50 cycles of comparative example 1.
It can be seen from fig. 5 that the modified material containing gadolinium and gadolinium oxide in example 6 can effectively prevent the growth of lithium dendrite, improve the cycle stability of the lithium ion battery, and the coulombic efficiency is significantly higher than that of comparative example 1, and the cycle stability is also better than that of comparative example 1. Compared to example 5, the cycling stability of example 6 is lower than that of example 5, indicating that the magnitude of the thickness of the modified material affects the cycling stability of the battery.
Other beneficial effects are as follows:
1. the copper cathode containing gadolinium and gadolinium oxide prepared by the invention is suitable for assembling various lithium ion batteries, such as lithium iron phosphate batteries, lithium manganate batteries and sodium cobalt oxygen batteries, and can induce the uniform deposition of lithium ions and avoid the growth of lithium dendrites, thereby effectively improving the coulombic efficiency of the lithium ion batteries and improving the cycle stability of the lithium ion batteries.
2. The invention adopts a vacuum evaporation coating method to deposit a layer of gadolinium and gadolinium oxide compact film on the surface of the copper substrate, the process is simple and the large-scale production can be realized, and the deposited gadolinium and gadolinium oxide modified material and the substrate copper single material have high interface bonding strength, thereby avoiding the falling-off condition between the substrate copper single material and the gadolinium and gadolinium oxide modified material, improving the mechanical deformation stability of the modified material and being beneficial to the normal use of the battery in severe environment.
3. In the preparation process, the raw material powder is heated by applying current under the condition of selectively protecting the raw material powder in a vacuum environment, and sublimed gaseous particles are deposited on the surface of the copper simple substance, so that the gadolinium and the oxide modified material thereof are uniformly distributed on the surface of the copper simple substance material.
The above-described embodiments of the present invention should not be construed as limiting the scope of the present invention. Any other corresponding changes and modifications made according to the technical idea of the present invention should be included in the protection scope of the claims of the present invention.

Claims (10)

1. The lithium ion battery cathode is characterized by comprising a substrate and a thin film layer, wherein the thin film layer is coated on the surface of the substrate, and the thin film layer is made of gadolinium and gadolinium oxides.
2. The negative electrode of claim 1, wherein the substrate is made of copper.
3. The lithium ion battery negative electrode of claim 2, wherein the substrate is a copper foil, a copper mesh, or a copper foam.
4. The lithium ion battery negative electrode of claim 1, wherein the oxide of gadolinium is gadolinium oxide.
5. The negative electrode of a lithium ion battery according to claim 1, wherein the thin film layer is applied to the surface of the substrate by vacuum evaporation.
6. A method for preparing the negative electrode of the lithium ion battery according to any one of claims 1 to 5, which is characterized by comprising the following steps: fixing the substrate on a base of a vacuum chamber of vacuum evaporation coating equipment, placing gadolinium powder on an evaporation boat, and fixing the evaporation boat between two electrodes of the vacuum chamber; and vacuumizing to keep the vacuum chamber in a vacuum environment, and heating the gadolinium powder under the current of 180-220A to obtain the lithium ion battery cathode.
7. The method for preparing the lithium ion battery cathode according to claim 6, wherein the gadolinium powder is heated for 1min to 5 min.
8. The method of claim 6, wherein the vacuum environment is at a pressure of 5 x 10-4-6×10-4Pa。
9. The method of claim 6, wherein the gadolinium powder is heated at a current of 190A-210A.
10. A lithium ion battery, comprising the lithium ion battery negative electrode according to any one of claims 1 to 5 or the lithium ion battery negative electrode prepared by the preparation method according to any one of claims 6 to 9.
CN202110910250.9A 2021-08-09 2021-08-09 Lithium ion battery, lithium ion battery cathode and preparation method thereof Active CN113690402B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105226258A (en) * 2015-11-06 2016-01-06 杭州电子科技大学 A kind of lithium ion battery negative composite film material and preparation method thereof
CN106159169A (en) * 2016-07-11 2016-11-23 湖南立方新能源科技有限责任公司 A kind of lithium ion battery and preparation method thereof
CN111370691A (en) * 2020-01-03 2020-07-03 华中科技大学 Lithium ion battery cathode and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105226258A (en) * 2015-11-06 2016-01-06 杭州电子科技大学 A kind of lithium ion battery negative composite film material and preparation method thereof
CN106159169A (en) * 2016-07-11 2016-11-23 湖南立方新能源科技有限责任公司 A kind of lithium ion battery and preparation method thereof
CN111370691A (en) * 2020-01-03 2020-07-03 华中科技大学 Lithium ion battery cathode and preparation method thereof

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