CN114725316A - Thick electrode with reticular current collector confinement structure, preparation method of thick electrode and lithium battery - Google Patents

Thick electrode with reticular current collector confinement structure, preparation method of thick electrode and lithium battery Download PDF

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Publication number
CN114725316A
CN114725316A CN202210426163.0A CN202210426163A CN114725316A CN 114725316 A CN114725316 A CN 114725316A CN 202210426163 A CN202210426163 A CN 202210426163A CN 114725316 A CN114725316 A CN 114725316A
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current collector
negative electrode
thick
electrode material
electrode
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Chinese (zh)
Inventor
杨辉
张文
桂思炜
李婉铭
孙永明
张云
周华民
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Huazhong University of Science and Technology
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/72—Grids
    • H01M4/74—Meshes or woven material; Expanded metal
    • H01M4/745—Expanded metal
    • 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

Abstract

The invention discloses a thick electrode with a reticular current collector limited domain structure, a preparation method thereof and a lithium battery, wherein the reticular current collector of the thick electrode is provided with a through hole array; the alloying type negative electrode material is filled in the through hole array of the reticular current collector; and the embedded negative electrode material is coated on two surfaces of the reticular current collector so as to carry out limited-range coating on the alloying negative electrode material. The alloying type negative electrode material is filled in the through hole array of the current collector and then coated by the embedded type negative electrode material, and the alloying type negative electrode material is limited by the through hole array and the upper and lower embedded type negative electrode materials, so that the volume expansion of the silicon negative electrode material in the charging and discharging processes can be effectively buffered, and the volume energy density of the electrode is effectively improved.

Description

Thick electrode with reticular current collector confinement structure, preparation method of thick electrode and lithium battery
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a thick electrode with a reticular current collector confinement structure, a preparation method of the thick electrode and a lithium battery.
Background
At present, an embedded negative electrode material such as traditional multipurpose graphite is mainly used as a negative electrode of a common lithium ion battery, but the theoretical specific capacity of the common lithium ion battery is only 372mA h g-1It has become increasingly difficult to meet the market demand for high energy density lithium ion batteries. Therefore, there is a need to further develop new lithium ion battery negative electrode materials. The alloyed negative electrode material has higher theoretical specific capacity, for example, the theoretical specific capacity of a silicon-based (Si) negative electrode is up to 4200mA h g-1And is considered to be a novel anode material most promising for replacing graphite anodes. However, the great volume change (300%) of the alloying negative electrode in the lithiation/delithiation process can cause the negative electrode material particles to break and pulverize, which leads to the negative electrode failure, influences the cycling stability of the battery and restricts the practical application of the alloying negative electrode.
Disclosure of Invention
In view of the above defects or improvement needs in the prior art, the present invention provides a thick electrode with a reticulated current collector confinement structure, a preparation method thereof, and a lithium battery, and aims to alleviate the volume expansion of an alloyed negative electrode during the charging and discharging processes and improve the volume energy density of the electrode.
To achieve the above objects, according to one aspect of the present invention, there is provided a thick electrode having a reticulated current collector confinement structure, comprising:
a mesh current collector having an array of through-holes;
the alloying type negative electrode material is filled in the through hole array of the reticular current collector;
and the embedded negative electrode material is coated on two surfaces of the reticular current collector so as to carry out limited-range coating on the alloying negative electrode material.
In one embodiment, the mesh current collector is a stainless steel mesh.
In one embodiment, the alloyed negative electrode material includes any one of Si, Sn, and Ge.
In one embodiment, the embedded negative electrode material includes any one of carbon nanotubes, graphene, and graphite.
In one embodiment, the mesh number of the mesh-shaped current collector is 100-1000 meshes, and the wire diameter is 1 μm-1 mm.
In one embodiment, the filling depth of the alloying type negative electrode material in the reticular current collector is 2 μm-2 mm.
In one embodiment, the thickness of the insertion type negative electrode material coated on each side of the mesh-shaped current collector is 2 μm to 2 mm.
In one embodiment, in the active material of the thick electrode, the alloying type negative electrode material provides 5-33% of active material content, and the embedding type negative electrode material provides 67-95% of active material content.
According to another aspect of the present invention, there is provided a method for preparing a thick electrode having a reticulated current collector confinement structure, comprising:
preparing alloying type cathode slurry;
filling the alloying type negative electrode slurry into the through hole array of the reticular current collector, drying and rolling;
preparing embedded negative electrode slurry;
and coating embedded negative electrode slurry on two surfaces of the reticular current collector, drying and rolling to obtain the thick electrode.
According to still another aspect of the present invention, there is provided a lithium battery including a positive electrode, a negative electrode, an electrolyte and a separator, the negative electrode being the above-described thick electrode having a reticulated current collector domain structure.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
1. according to the thick electrode with the net-shaped current collector confinement structure, the alloying type negative electrode material is filled in the through hole array of the current collector and then coated by the embedded type negative electrode material, the alloying type negative electrode material is limited by the through hole array and the upper and lower embedded type negative electrode materials, so that the volume expansion of the silicon negative electrode material in the charging and discharging processes can be effectively buffered, the cracking of the upper surface of the negative electrode material caused by large deformation is relieved under the condition that the carrying capacity of the negative electrode material is ensured, the problems of battery performance decline and failure caused by volume expansion are solved, and a negative electrode with good circulation stability is obtained;
2. the invention effectively utilizes the three-dimensional space of the current collector to carry out limited-range storage on the alloying type negative electrode material, has higher compaction density under the condition of the same load or the same thickness, and can effectively improve the volume energy density of the electrode;
3. the invention provides a preparation method of a thick electrode with a reticular current collector confinement structure, which has simple and controllable preparation process, effectively saves time and manufacturing cost, and is suitable for large-scale industrial production and application.
Drawings
FIG. 1 is a schematic illustration of a method for making a thick electrode having a reticulated current collector confinement structure in one embodiment;
FIG. 2 is a graph showing the results of electrochemical performance tests on a battery in one example.
Detailed Description
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 addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Fig. 1 is a schematic diagram of a method for manufacturing a thick electrode with a reticulated current collector domain structure according to an embodiment. In the case of a stainless steel mesh array, the mesh current collector has an array of through holes. Taking silicon as an example, the alloying type negative electrode material is filled in the through hole array of the reticular current collector. Taking graphite as an example, the intercalation type negative electrode material is coated on both sides of a mesh-shaped current collector to perform domain-limited coating on the alloying type negative electrode material. The resulting thick electrode with a reticulated current collector confinement structure as shown.
In an embodiment, the alloying type anode material may also be any one of Sn, Ge, or other alloying type anode materials. The alloying-type negative electrode material herein refers to a material that is charged and discharged in the form of an alloy with lithium, and the process is accompanied by a large volume expansion.
In an embodiment, the embedded negative electrode material may also be any one of carbon nanotubes and graphene, or other embedded negative electrode materials. The intercalation type negative electrode material herein refers to a material that is charged and discharged as a compound with lithium, and the volume expansion occurring in the process is much smaller than that of the alloying type negative electrode material.
The mesh-shaped current collector is not limited to the stainless steel mesh, and may be other mesh-shaped current collectors with a through hole array, such as a copper mesh. Specifically, the mesh number of the reticular current collector is 100-1000 meshes, and the wire diameter is 1 mu m-1 mm. Specifically, the filling depth of the alloying type negative electrode material in the mesh-shaped current collector is 2 microns-2 mm. Specifically, the thickness of the insertion type negative electrode material coated on each surface of the mesh-shaped current collector is 2 μm to 2 mm.
In order to ensure the performance of the electrode, the content of the active substance provided by the alloying type negative electrode material is 5-33%, the content of the active substance provided by the embedded type negative electrode material is 67-95%, and the overall performance of the negative electrode formed according to the proportion is good. It is understood that other auxiliary materials, such as conductive carbon black and binders, may also be added to the alloying type anode material and the intercalation type anode material when preparing the negative electrode.
Accordingly, the present application also provides a method for preparing a thick electrode having a reticulated current collector confinement structure, with continued reference to fig. 1, comprising:
s1: and preparing the alloying type cathode slurry.
Specifically, firstly, grinding and uniformly mixing an active substance in the alloying type negative electrode material and conductive carbon black to obtain solid particles; then, acrylic acid solution (PAA) was added to prepare an alloyed negative electrode slurry. In one embodiment, the mass ratio of the obtained slurry is as follows: conductive carbon black: 70-90% of acrylic acid solution: 5-15: 5-15, specifically 80: 10: 10.
s2: and filling the alloyed negative electrode slurry into the through hole array of the reticular current collector, drying and rolling.
Specifically, the drying temperature can be controlled between 60 ℃ and 70 ℃.
S3: and preparing embedded negative electrode slurry.
Specifically, an active substance in an embedded negative electrode material and conductive carbon black are ground and uniformly mixed to obtain solid particles; an acrylic acid solution (PAA) was then added to make an intercalation-type negative electrode slurry. In one embodiment, the mass ratio of the obtained slurry is as follows: conductive carbon black: 70-90% of acrylic acid solution: 5-15: 5-15, specifically 80: 10: 10. furthermore, the proportion of the embedded negative electrode slurry and the alloying negative electrode slurry is the same.
S4: and coating embedded negative electrode slurry on two surfaces of the reticular current collector, drying and rolling to obtain the negative electrode.
Specifically, the drying temperature can be controlled between 60 ℃ and 70 ℃.
In one embodiment, continuing with the silicon and graphite example, the method includes the steps of:
s1: preparing silicon cathode slurry;
s2: filling the silicon slurry in a stainless steel mesh array, drying and then obtaining a first electrode filled with silicon by simple rolling;
s3: preparing graphite cathode slurry;
s4: and coating the graphite slurry on two surfaces of the first electrode, wherein the thicknesses of the graphite coatings are the same, and then drying and rolling to obtain the thick electrode with the reticular current collector confinement structure.
Accordingly, the present application also relates to a lithium battery comprising a positive electrode, a negative electrode, an electrolyte and a separator, wherein the negative electrode is the above-described thick electrode with a reticulated current collector domain structure. Wherein the positive electrode comprises aluminum foil and a positive active material disposed on the aluminum foil, it is understood that the lithium battery further comprises a housing.
The following specific examples are given by way of illustration:
example 1
Silicon (Si) active particles were mixed with conductive carbon black (Super P) and ground to obtain uniform solid particles. Adding a polyacrylic acid (PAA) solution into the solid particles, and uniformly stirring to prepare Si negative electrode slurry, wherein Si: super P: PAA is 80: 10: 10. and filling the Si slurry into a stainless steel mesh array (500 meshes, the wire diameter is 0.03mm, and the depth is 60 mu m), drying and rolling to obtain the silicon electrode with the filling depth of 60 mu m. Next, a graphite slurry was prepared by the same method, graphite: super P: PAA is 80: 10: 10. coating graphite slurry on one surface of a filled silicon electrode, wherein the thickness of the graphite slurry is 60 microns, then placing the pole piece in a 60 ℃ oven for drying, and coating the graphite slurry (60 microns) on the other surface, wherein the coating thicknesses of the slurry on the two surfaces are the same; and finally, transferring the coated thick electrode with the reticular current collector confinement structure into a vacuum drying oven, carrying out vacuum drying for 12h at 70 ℃, rolling the pole piece subjected to vacuum drying, and cutting the pole piece into an electrode piece, thereby obtaining the thick electrode with the reticular current collector confinement structure.
Example 2
Silicon (Si) active particles were mixed with conductive carbon black (Super P) and ground to obtain uniform solid particles. Adding a polyacrylic acid (PAA) solution into the solid particles, and uniformly stirring to prepare Si negative electrode slurry, wherein Si: super P: PAA is 80: 10: 10. and filling the Si slurry into a stainless steel mesh array (500 meshes, the wire diameter is 0.03mm, and the depth is 60 mu m), drying and rolling to obtain the silicon electrode with the filling depth of 60 mu m. Next, a graphite slurry was prepared by the same method, graphite: super P: PAA is 80: 10: 10. coating graphite slurry on one surface of a filled silicon electrode, wherein the thickness of the graphite slurry is 120 microns, then placing the pole piece in a 60 ℃ oven for drying, and coating the graphite slurry (120 microns) on the other surface, wherein the coating thicknesses of the slurry on the two surfaces are the same; and finally, transferring the coated thick electrode with the reticular current collector confinement structure into a vacuum drying oven, carrying out vacuum drying for 12h at 70 ℃, rolling the pole piece subjected to vacuum drying, and cutting the pole piece into an electrode piece, thereby obtaining the thick electrode with the reticular current collector confinement structure.
Example 3
Silicon (Si) active particles were mixed with conductive carbon black (Super P) and ground to obtain uniform solid particles. Adding a polyacrylic acid (PAA) solution into the solid particles, and uniformly stirring to prepare Si negative electrode slurry, wherein Si: super P: PAA is 80: 10: 10. and filling the Si slurry into a stainless steel mesh array (150 meshes, the wire diameter is 0.06mm, and the depth is 120 mu m), drying and rolling to obtain the silicon electrode with the filling depth of 120 mu m. Next, a graphite slurry was prepared by the same method, graphite: super P: PAA is 80: 10: 10. coating graphite slurry on one surface of a filled silicon electrode, wherein the thickness of the graphite slurry is 120 microns, then placing a pole piece in a drying oven at 60 ℃, drying, and coating graphite slurry (120 microns) on the other surface, wherein the coating thicknesses of the slurry on the two surfaces are the same; and then transferring the coated thick electrode with the reticular current collector confinement structure into a vacuum drying oven, carrying out vacuum drying for 12h at 70 ℃, rolling the pole piece subjected to vacuum drying, and cutting the pole piece into an electrode piece, thereby obtaining the thick electrode with the reticular current collector confinement structure.
Example 4
The tin (Sn) active particles are mixed with conductive carbon black (Super P) and ground to obtain uniform solid particles. Adding a polyacrylic acid (PAA) solution into the solid particles, and uniformly stirring to prepare Sn negative electrode slurry, wherein the mass ratio of Sn: super P: PAA is 80: 10: 10. the Sn slurry is coated and filled into a stainless steel mesh array (500 meshes, the wire diameter is 0.03mm, and the depth is 60 mu m), and the Sn electrode with the filling depth of 60 mu m is obtained after drying and rolling. Next, a graphite slurry was prepared by the same method, graphite: super P: PAA is 80: 10: 10. coating graphite slurry on one surface of a filled silicon electrode, wherein the thickness of the graphite slurry is 60 microns, then placing the pole piece in a 60 ℃ oven for drying, and coating the graphite slurry (60 microns) on the other surface, wherein the coating thicknesses of the slurry on the two surfaces are the same; and then transferring the coated electrode with the reticular current collector confinement structure into a vacuum drying oven, carrying out vacuum drying for 12h at 70 ℃, rolling the electrode piece subjected to vacuum drying, and cutting the electrode piece into an electrode piece, thereby obtaining the thick electrode with the reticular current collector confinement structure.
The cathode material provided in example 1 was assembled into button cells for electrochemical performance testing.
(1) Assembly of battery
Cutting the electrode into electrode pieces with the diameter of 10mm by using a slicer, weighing and calculating the content of active substances, wherein the prepared electrode is used as a working electrode of the button cell, lithium metal is used as a counter electrode, a polypropylene film (PP) is used as a diaphragm, and LiPF is used as electrolyte6For the electrolyte, the button cells were assembled with ethylene carbonate and diethyl carbonate (EC: DEC ═ 1:1) solutions in the presence of 5% fluoroethylene carbonate (FEC).
(2) Electrochemical performance test
The constant current charge and discharge test is completed on a new Wille charge and discharge test system, the charge and discharge are carried out under the multiplying power of 0.1C, the voltage window is 0.01-2.00V, and the cycle step is standing, constant current discharge, transverse current charge, cycle and ending. As shown in FIG. 2, the surface loading of the thick electrode is 5.76mg cm-2Then, the cycle performance test is carried out under the current density of 0.1C, 30 cycles of cycle are carried out, and the surface capacity can reach 5.49mA hcm-2As shown in fig. 2. Therefore, the thick electrode with the reticular current collector confinement structure is a lithium ion battery cathode material with high loading capacity and excellent surface capacity, and has good industrial application prospect.
In summary, according to the thick electrode with the mesh-shaped current collector confinement structure provided by the invention, the alloying type negative electrode material is filled in the through hole array of the current collector and then coated by the embedded type negative electrode material, the alloying type negative electrode material is limited by the through hole array and the upper and lower embedded type negative electrode materials, so that the volume expansion of the silicon negative electrode material in the charging and discharging processes can be effectively buffered, the cracking of the upper surface of the negative electrode material caused by large deformation is relieved under the condition of ensuring the loading capacity of the negative electrode material, the problems of battery performance degradation and failure caused by volume expansion are solved, and the negative electrode with better cycle stability is obtained. In addition, the invention effectively utilizes the three-dimensional space of the current collector to store the alloying type negative electrode material in a limited range, has higher compaction density under the condition of the same load or the same thickness, and can effectively improve the volume energy density of the electrode.
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 thick electrode having a reticulated current collector confinement structure, comprising:
a mesh current collector having an array of through-holes;
the alloying type negative electrode material is filled in the through hole array of the reticular current collector;
and the embedded negative electrode material is coated on two surfaces of the reticular current collector so as to carry out limited-range coating on the alloying negative electrode material.
2. The thick electrode with a reticulated current collector confinement structure of claim 1, wherein the reticulated current collector is a stainless steel mesh.
3. The thick electrode with a reticulated current collector confinement structure of claim 1, wherein the alloyed negative electrode material comprises any one of Si, Sn, Ge.
4. The thick electrode with a reticulated current collector confinement structure of claim 1, wherein the embedded negative electrode material comprises any one of carbon nanotubes, graphene, graphite.
5. The thick electrode with a reticulated current collector confinement structure of claim 1, wherein the reticulated current collector has a mesh count of 100 to 1000 mesh and a wire diameter of 1 μm to 1 mm.
6. The thick electrode with a reticulated current collector confinement structure of claim 1, wherein the alloying-type negative electrode material is filled in the reticulated current collector to a depth of 2 μm to 2 mm.
7. The thick electrode having a reticulated current collector confinement structure of claim 1, wherein the thickness of the intercalation type negative electrode material applied to each side of the reticulated current collector is 2 μm to 2 mm.
8. The thick electrode with a reticulated current collector domain-limiting structure of claim 1, wherein the active material content of the thick electrode is 5% -33% of the active material content provided by the alloying-type negative electrode material and 67% -95% of the active material content provided by the intercalation-type negative electrode material.
9. A method of making a thick electrode having a reticulated current collector confinement structure, comprising:
preparing alloying type cathode slurry;
filling the alloying type negative electrode slurry into the through hole array of the reticular current collector, drying and rolling;
preparing embedded negative electrode slurry;
and coating embedded negative electrode slurry on two surfaces of the reticular current collector, drying and rolling to obtain the thick electrode.
10. A lithium battery comprising a positive electrode, a negative electrode, an electrolyte and a separator, wherein the negative electrode is a thick electrode having a reticulated current collector domain structure according to any one of claims 1 to 8.
CN202210426163.0A 2022-04-21 2022-04-21 Thick electrode with reticular current collector confinement structure, preparation method of thick electrode and lithium battery Pending CN114725316A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013159470A1 (en) * 2012-04-26 2013-10-31 上海杉杉科技有限公司 Three-dimensional porous silicon-based composite negative electrode material of lithium ion cell and preparation method thereof
WO2013159471A1 (en) * 2012-04-26 2013-10-31 宁波杉杉新材料科技有限公司 Porous thin film silicon-based negative electrode material of high-performance lithium ion cell and preparation method thereof
CN104347842A (en) * 2013-07-23 2015-02-11 华为技术有限公司 Composite negative electrode sheet of lithium ion secondary battery, preparation method thereof, and lithium ion secondary battery
CN109546082A (en) * 2018-11-07 2019-03-29 惠州市豪鹏科技有限公司 A kind of cathode pole piece and preparation method thereof and lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013159470A1 (en) * 2012-04-26 2013-10-31 上海杉杉科技有限公司 Three-dimensional porous silicon-based composite negative electrode material of lithium ion cell and preparation method thereof
WO2013159471A1 (en) * 2012-04-26 2013-10-31 宁波杉杉新材料科技有限公司 Porous thin film silicon-based negative electrode material of high-performance lithium ion cell and preparation method thereof
CN104347842A (en) * 2013-07-23 2015-02-11 华为技术有限公司 Composite negative electrode sheet of lithium ion secondary battery, preparation method thereof, and lithium ion secondary battery
CN109546082A (en) * 2018-11-07 2019-03-29 惠州市豪鹏科技有限公司 A kind of cathode pole piece and preparation method thereof and lithium ion battery

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