CN114784225A - Composite cathode structure and application thereof in lithium ion battery - Google Patents

Composite cathode structure and application thereof in lithium ion battery Download PDF

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CN114784225A
CN114784225A CN202210594490.7A CN202210594490A CN114784225A CN 114784225 A CN114784225 A CN 114784225A CN 202210594490 A CN202210594490 A CN 202210594490A CN 114784225 A CN114784225 A CN 114784225A
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active material
electrode layer
carbon
composite
graphite
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孙永明
李春浩
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Huazhong University of Science and Technology
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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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/36—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
    • H01M4/386—Silicon or alloys based on silicon
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/58—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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals

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Abstract

The invention belongs to the technical field of new energy, and discloses a composite negative electrode structure and application thereof in a lithium ion battery. According to the invention, the structure of the negative electrode is improved, the multilayer structure is arranged, the high-specific-capacity active material which has an alloy reaction with Li is limited in the inner electrode layer, and the carbon-based active material is limited in the outer electrode layer, so that the problem of poor cycle stability of the high-capacity composite electrode which is made of alloy negative electrode materials including pure silicon and carbon-based negative electrode materials including graphite as active materials can be effectively solved.

Description

Composite cathode structure and application thereof in lithium ion battery
Technical Field
The invention belongs to the technical field of new energy, and particularly relates to a composite cathode structure and application thereof in a lithium ion battery, which can particularly improve the cycle stability of the lithium ion battery.
Background
Nowadays, the energy crisis and environmental problems are increasingly prominent, and the storage of new clean energy and energy has become a focus of research. Under the background, the lithium ion battery basically occupies the market of portable consumer electronic products due to the characteristics of high energy density, high power density, long service life, environmental friendliness and the like, and has wide application prospects in the fields of electric automobiles, large-scale energy storage equipment, distributed mobile power supplies and the like.
However, with the increase in demand, especially in the field of electric vehicles, which have been vigorously developed in recent years, the demand for high endurance mileage urgently demands the development of high energy density batteries. The energy density of the battery is improved, and more problems are involved, if high-capacity anode and cathode materials with excellent performance need to be developed. In the aspect of negative electrode materials, the theoretical capacity of the graphite negative electrode material which is most widely applied at present is 372mAh g-1And the actual measurement capacity of the commercialized high-end graphite material reaches 365mAh g-1And the technology is mature. The alloy active material capable of generating alloy reaction with Li has extremely high theoretical specific capacity (such as silicon-based, tin-based, germanium-based and antimony-based active materials and the like), and the theoretical specific capacity of the alloy active material is often higher than that of graphite (372mAh g)-1) Taking pure silicon as an example, pure silicon has high capacity (room temperature theoretical capacity 3579mAh g)-1) The lithium ion battery cathode material has the advantages of low lithium removal potential, low cost, environmental friendliness and the like, and is considered to be a cathode material with great potential for next-generation lithium ion batteries. However, the scaling of pure silicon anode materials faces the following challenges: the pure silicon particles are subjected to volume expansion and contraction during lithium intercalation and lithium deintercalation, so that the particles are pulverized, fall off and have invalid electrochemical performance; the continued growth of the solid electrolyte layer (SEI) on the surface of the pure silicon particles is an irreversible depletion of the electrolyte and lithium source from the positive electrode. It is therefore now difficult to realize a practical application of pure silicon/high silicon anodes.
At present, a plurality of researchers and anode material production enterprises at home and abroad begin to develop and commercialize the silicon-based composite anode. For example, 5% to 25% silicon is mixed in graphite in an attempt to improve the mass and volumetric energy density of existing battery systems. However, the conventional composite negative electrode prepared by uniformly mixing graphite and silicon has poor cycle stability and serious capacity attenuation. It was found that the lithium ions are inhibited from being intercalated into graphite by the stress accumulation caused by the volume change accompanying the deintercalation of lithium by the silicon particles in the conventional composite negative electrode, resulting in the decline of the graphite capacity. Meanwhile, the large volume change of the dispersedly distributed silicon particles during lithium intercalation and deintercalation can also damage the overall structure of the electrode, and influence the cycle performance of the electrode. Junhyuk Moon et al, a company of Samsung, Korea, proposed to reduce the influence of silicon particles on the properties of graphite by increasing the hardness of graphite, and this method, although having some effect, did not solve the above-mentioned problems from the electrode structure.
Disclosure of Invention
In view of the above drawbacks or needs for improvement in the prior art, an object of the present invention is to provide a composite anode structure and an application thereof in a lithium ion battery, in which a structure of an anode is improved, and a multi-layer structure is provided to limit a high specific capacity active material (having a high capacity characteristic) capable of performing an alloy reaction with Li in an inner electrode layer and limit a carbon-based active material (having a high stability characteristic) in an outer electrode layer, so as to effectively solve a problem of poor cycle stability of a high capacity composite electrode manufactured using an alloy-based anode material including pure silicon (i.e., an anode active material capable of performing an alloy reaction with Li) and a carbon-based anode material including graphite as active materials.
To achieve the above object, according to one aspect of the present invention, there is provided a composite anode characterized by comprising a current collector, an inner electrode layer and an outer electrode layer, wherein,
the inner electrode layer is closely attached to the current collector, and the active material in the inner electrode layer is a high-specific-capacity active material capable of performing alloy reaction with Li so as to improve the total specific capacity of the electrode; wherein the high specific capacity active material capable of alloying with Li has a theoretical specific capacity higher than that of graphite (372mAh g)-1)；
The outer electrode layer is tightly adhered to the inner electrode layer, and the active material in the outer electrode layer is a carbon-based active material.
As a further preference of the present invention, the high specific capacity active material capable of alloying with Li comprises one or more of silicon, silicon oxygen, silicon carbon, silicon oxygen carbon, tin oxide;
the carbon-based active material comprises one or more of natural graphite, artificial graphite, a composite material of the natural graphite and the artificial graphite, soft carbon, hard carbon, mesocarbon microbeads, graphene and graphite alkyne.
In a further preferred embodiment of the present invention, the thickness of the inner electrode layer is 5 to 100 μm, and the thickness of the outer electrode layer is 10 to 200 μm.
As a further preferable aspect of the present invention, the inner electrode layer includes a conductive agent and a binder in addition to the active material; the outer electrode layer includes a conductive agent and a binder in addition to the carbon-based active material.
As a further preferable aspect of the present invention, the inner electrode layer comprises the following components by mass: 50 to 99 percent of active material, 0.5 to 30 percent of conductive agent and 0.5 to 20 percent of binder;
the outer electrode layer comprises the following components in percentage by mass: 50-99% of carbon-based active material, 0.5-30% of conductive agent and 0.5-20% of binder.
As a further preferred of the present invention, the conductive agent comprises one or more of Ketjen Black (KB), conductive carbon black (SP), Acetylene Black (AB), conductive graphite, Carbon Nanotubes (CNTs), graphene materials;
the binder comprises one or more of polyvinylidene fluoride, polyacrylic acid, lithium polyacrylate, polyethylene oxide, polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose, sodium alginate and styrene butadiene rubber.
According to another aspect of the present invention, there is provided a method for producing the above composite anode, comprising the steps of:
(1) uniformly mixing an inner layer electrode active material, a conductive agent, a binder and a solvent to obtain slurry for an inner layer electrode; then coating the slurry on a current collector, and drying to obtain an inner electrode layer on the current collector;
(2) uniformly mixing an outer electrode active material, a conductive agent, a binder and a solvent to obtain slurry for an outer electrode; and then coating the slurry on the inner electrode layer, and drying to obtain the composite cathode.
As a further preferred embodiment of the present invention, the solvent includes one of deionized water, 1-methyl-2-pyrrolidone, N-dimethylformamide, and dimethylsulfoxide.
According to another aspect of the invention, the invention provides the application of the composite negative electrode as a battery negative electrode in a lithium ion battery.
According to another aspect of the present invention, the present invention provides a lithium ion battery, wherein the negative electrode plate is the composite negative electrode.
Through the technical scheme, the composite cathode structure is different from a traditional composite cathode structure in which a plurality of active materials are uniformly mixed, the invention provides a layered-distributed multilayer structure which can avoid mutual interference of an active material capable of alloying (namely, the active material with high specific capacity and capable of performing alloy reaction with Li) and a carbon-based active material, the active material with high capacity and capable of performing alloy reaction with lithium is limited in an inner-layer electrode of the multilayer structure, and the outer-layer electrode is a high-stability carbon-based active material, so that the electrode structure stability of the composite cathode can be effectively improved, the side reaction of the active material capable of alloying and an electrolyte is reduced, the cycle stability of the composite cathode is greatly improved, and the energy density of a lithium ion battery is remarkably increased. In the present invention, the stability of the inner layer active material is lower than that of the outer layer active material (i.e., carbon-based active material), and the carbon-based active material can still function as an active negative electrode material in addition to a protective effect.
The preparation method of the composite cathode is simple, the multilayer structure composite cathode with the inner layer of the alloy active material layer and the outer layer of the carbon-based active material layer which are in direct contact with the current collector can be obtained through the traditional electrode coating process, the industrial production can be realized, the matching performance with the existing electrode production process is good, and the composite cathode has wide application prospects in the field of lithium ion batteries.
Drawings
FIG. 1 is a schematic structural diagram of the present invention; the active material of the alloy electrode layer is an alloy active material (i.e., a high specific capacity active material capable of performing an alloy reaction with Li), and the active material of the carbon-based electrode layer is a carbon-based negative electrode material. For example, the current collector may be coated with an inner electrode layer and an outer electrode layer on both the upper and lower surfaces.
FIG. 2 is a scanning electron microscope image of a cross section of a composite electrode fabricated according to an embodiment of the present invention.
FIG. 3 is a graph comparing the long cycle performance of the first and second inventive examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in 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 addition, the technical features involved in the respective embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Generally speaking, the composite negative electrode in the invention is composed of a multilayer structure of an inner electrode and an outer electrode, the active material of the inner electrode is an active material capable of generating alloy reaction with Li, which can bring high capacity characteristics (taking Si as an example, 1 Si atom can generate alloy reaction with 4.4 Li atoms, and the specific capacity is high); the outer electrode active material is a carbon-based active material and has the characteristic of high stability. Taking graphite as an example, lithium ions are intercalated between layers of graphite, and the volume change of the graphite active material is small.
That is, the composite negative electrode structure of the present invention includes an inner electrode and an outer electrode, the inner electrode active material is a high-capacity active material that can undergo an alloying reaction with lithium, and the outer electrode active material is a high-stability carbon-based active material. During preparation, the alloy negative electrode layer and the carbon-based negative electrode layer can be sequentially coated to form a multilayer electrode structure comprising an inner electrode and an outer electrode. The inner electrode (alloy active material cathode layer) is tightly adhered to the current collector, and the outer electrode (carbon-based cathode layer) is tightly adhered to the inner electrode.
Example one
(1) Mixing nano silicon powder, conductive carbon black and lithium polyacrylate according to the weight ratio of 80: 10: 10, and specifically, mixing the following components in percentage by mass: 0.08g of nano silicon powder, 0.01g of conductive carbon black and 0.01g of sodium carboxymethyl cellulose, dispersing in 0.25g of deionized water, and stirring for 10min to obtain uniformly mixed slurry for an inner layer electrode;
(2) coating the inner layer slurry on a 25 μm copper foil with a doctor blade to obtain an inner layer coating layer, drying the inner layer coating layer at 60 ℃ for 1h to obtain an inner layer electrode with a loading of 0.42mg cm-2The thickness is 5 mu m;
(3) mixing graphite, conductive carbon black and lithium polyacrylate according to the weight ratio of 90: 5: 5, uniformly mixing the components in a mass ratio of: 0.72g of graphite, 0.04g of conductive carbon black and 0.04g of sodium carboxymethylcellulose are dispersed in 1g of deionized water and stirred for 10min to obtain uniformly mixed slurry for the outer-layer electrode;
(4) coating the outer layer slurry on the inner layer electrode obtained in the step (2) by using a scraper, drying for 1h at 60 ℃, then transferring to a vacuum oven for drying for 12h at 80 ℃, wherein the thickness of the obtained outer layer electrode is 70 mu m, and preparing the double-layer structure composite electrode, wherein the total loading capacity of the electrode is 6.5mg cm-2，；
(5) And (4) assembling a 2032 type button cell by taking the pole piece obtained in the step (4) as an electrode and a commercial lithium piece as a counter electrode, wherein the cell shell is made of stainless steel material, the diaphragm is commercial Celgard 2300, and the electrolyte is commercial lithium ion battery electrolyte.
Fig. 2 is a scanning electron microscope image of a cross section of an electrode fabricated in the first embodiment, from which the multi-layer structure of the electrode can be clearly distinguished, in which the current collector is at the lowest layer, the silicon layer is at the layer next to the current collector, and the graphite layer is at the uppermost layer.
Example two
The difference from the first embodiment is that the nano silicon powder in the step (1) is replaced by silicon oxygen, and the amount of the deionized water can be adjusted according to the state of the slurry.
EXAMPLE III
The difference from the first embodiment is that the graphite in the step (3) is replaced by hard carbon, and the amount of deionized water can be adjusted according to the state of the slurry.
Example four
The difference from the first embodiment is that the thickness of the blade coating setup is changed such that: the thickness of the inner layer electrode obtained after drying in the step (2) is 20 μm, and the thickness of the outer layer electrode obtained after drying in the step (4) is 10 μm.
EXAMPLE five
The difference from the first embodiment is that the thickness of the blade coating setup is changed such that: the thickness of the inner layer electrode obtained after drying in the step (2) is 100 μm, and the thickness of the outer layer electrode obtained after drying in the step (4) is 200 μm.
Example six
The difference from the first embodiment is that the mass ratio of the nano silicon powder, the conductive carbon black and the lithium polyacrylate in the step (1) is 50: 30: 20, in the step (3), the mass ratio of the graphite to the conductive carbon black to the lithium polyacrylate is 50: 30: and (20) adjusting the dosage of the deionized water in the step (1) and the step (3) according to the state of the slurry.
EXAMPLE seven
The difference from the first embodiment is that the mass ratio of the nano silicon powder, the conductive carbon black and the lithium polyacrylate in the step (1) is 99: 0.5: 0.5, wherein the mass ratio of the graphite to the conductive carbon black to the lithium polyacrylate in the step (3) is 99: 0.5: 0.5, the dosage of the deionized water in the step (1) and the step (3) can be adjusted according to the state of the slurry.
Example eight
The difference from the first embodiment is that the conductive carbon black in the steps (1) and (3) is replaced by acetylene black, and the amount of deionized water can be adjusted according to the state of the slurry.
Example nine
The difference from the first embodiment is that the lithium polyacrylate in the step (1) and the step (3) is replaced by polyacrylic acid, and the amount of deionized water can be adjusted according to the state of the slurry.
Example ten
The difference from the first embodiment is that the deionized water in the steps (1) and (3) is replaced by 1-methyl-2-pyrrolidone, and the amount of the deionized water can be adjusted according to the state of the slurry.
Comparative example
(1) Weighing the component materials with the same mass as the embodiment, wherein the mass of each component is as follows: 0.08g of nano silicon powder, 0.72g of graphite, 0.05g of conductive carbon black and 0.05g of lithium polyacrylate, dispersing in 1.25g of deionized water, and uniformly mixing to obtain conventional composite electrode slurry;
(2) coating mixed electrode slurry on a copper foil with the thickness of 25 mu m, drying for 1h at the temperature of 60 ℃, then transferring to a vacuum oven for drying for 12h at the temperature of 80 ℃ to obtain a composite electrode with a mixed structure, wherein the total loading capacity of the electrode is 6.5mg cm-2；
(3) And (3) assembling a 2032 type button cell by taking the pole piece obtained in the step (2) as an electrode and a commercial lithium piece as a counter electrode, wherein the cell shell is made of stainless steel material, the diaphragm is commercial Celgard 2300, and the electrolyte is commercial lithium ion battery electrolyte.
Fig. 3 is a graph comparing the cycle performance of the lithium battery prepared in the first example with that of the lithium battery prepared in the comparative example, and it can be seen from the graph that the capacity of the first example still has a retention rate of 94.6% after 100 cycles while the capacity of the comparative example has a retention rate of 85.4% when the lithium battery is charged at a rate current of 0.2C. Therefore, when the composite double-layer structure cathode is applied to a lithium ion battery, the cycle performance of the battery can be effectively improved.
The respective starting materials used in the above examples were commercially available.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that 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 composite negative electrode is characterized by comprising a current collector, an inner electrode layer and an outer electrode layer, wherein,
the inner electrode layer is closely attached to the current collector, and the active material in the inner electrode layer is a high-specific-capacity active material capable of performing alloy reaction with Li so as to improve the total specific capacity of the electrode; wherein the high specific capacity active material capable of alloying with Li has a theoretical specific capacity higher than that of graphite;
the outer electrode layer is tightly adhered to the inner electrode layer, and the active material in the outer electrode layer is a carbon-based active material.
2. The composite anode of claim 1, wherein the high specific capacity active material capable of alloying with Li comprises one or more of silicon, silicon oxygen, silicon carbon, silicon oxygen carbon, tin oxide;
the carbon-based active material comprises one or more of natural graphite, artificial graphite, a composite material of the natural graphite and the artificial graphite, soft carbon, hard carbon, mesocarbon microbeads, graphene and graphite alkyne.
3. The composite negative electrode according to claim 1, wherein the inner electrode layer has a thickness of 5 μm to 100 μm, and the outer electrode layer has a thickness of 10 μm to 200 μm.
4. The composite anode according to claim 1, wherein the inner electrode layer comprises a conductive agent and a binder in addition to the active material; the outer electrode layer includes a conductive agent and a binder in addition to the carbon-based active material.
5. The composite anode according to claim 4, wherein the inner electrode layer comprises the following components in percentage by mass: 50 to 99 percent of active material, 0.5 to 30 percent of conductive agent and 0.5 to 20 percent of binder;
the outer electrode layer comprises the following components in percentage by mass: 50-99% of carbon-based active material, 0.5-30% of conductive agent and 0.5-20% of binder.
6. The composite anode according to claim 4, wherein the conductive agent comprises one or more of Ketjen Black (KB), conductive carbon black (SP), Acetylene Black (AB), conductive graphite, Carbon Nanotubes (CNTs), graphene materials;
the binder comprises one or more of polyvinylidene fluoride, polyacrylic acid, lithium polyacrylate, polyethylene oxide, polyvinyl alcohol, polyacrylonitrile, carboxymethyl cellulose, sodium alginate and styrene butadiene rubber.
7. The method for producing a composite anode according to any one of claims 1 to 6, characterized by comprising the steps of:
(1) uniformly mixing the inner-layer electrode active material, the conductive agent, the binder and the solvent to obtain slurry for the inner-layer electrode; then coating the slurry on a current collector, and drying to obtain an inner electrode layer on the current collector;
(2) uniformly mixing an outer electrode active material, a conductive agent, a binder and a solvent to obtain slurry for an outer electrode; and then coating the slurry on the inner electrode layer, and drying to obtain the composite negative electrode.
8. The method of preparing the composite anode according to claim 7, wherein the solvent comprises one of deionized water, 1-methyl-2-pyrrolidone, N-dimethylformamide, and dimethylsulfoxide.
9. Use of the composite negative electrode according to any one of claims 1 to 6 as a battery negative electrode in a lithium ion battery.
10. A lithium ion battery, characterized in that, the negative pole piece is the composite negative pole of any one of claims 1 to 6.
CN202210594490.7A 2022-05-27 2022-05-27 Composite cathode structure and application thereof in lithium ion battery Pending CN114784225A (en)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105185995A (en) * 2015-09-10 2015-12-23 中天储能科技有限公司 Lithium ion battery graphite-silicon carbon composite negative electrode
CN107528044A (en) * 2017-07-25 2017-12-29 深圳市沃特玛电池有限公司 A kind of lithium ion battery negative electrode and preparation method thereof
CN211045593U (en) * 2019-12-27 2020-07-17 陕西煤业化工技术研究院有限责任公司 Elastic layered silicon-based negative electrode plate and lithium battery comprising same
WO2021037266A1 (en) * 2019-08-29 2021-03-04 孚能科技(赣州)股份有限公司 Negative plate and manufacturing method thereof and lithium ion battery as well as preparation method and application thereof
CN113497224A (en) * 2020-04-01 2021-10-12 深圳格林德能源集团有限公司 Silicon-carbon negative pole piece of lithium ion battery

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105185995A (en) * 2015-09-10 2015-12-23 中天储能科技有限公司 Lithium ion battery graphite-silicon carbon composite negative electrode
CN107528044A (en) * 2017-07-25 2017-12-29 深圳市沃特玛电池有限公司 A kind of lithium ion battery negative electrode and preparation method thereof
WO2021037266A1 (en) * 2019-08-29 2021-03-04 孚能科技(赣州)股份有限公司 Negative plate and manufacturing method thereof and lithium ion battery as well as preparation method and application thereof
CN211045593U (en) * 2019-12-27 2020-07-17 陕西煤业化工技术研究院有限责任公司 Elastic layered silicon-based negative electrode plate and lithium battery comprising same
CN113497224A (en) * 2020-04-01 2021-10-12 深圳格林德能源集团有限公司 Silicon-carbon negative pole piece of lithium ion battery

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