CN105470487B - A kind of copper/tin/graphite sandwich construction lithium ion battery negative material and preparation method thereof - Google Patents
A kind of copper/tin/graphite sandwich construction lithium ion battery negative material and preparation method thereof Download PDFInfo
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- CN105470487B CN105470487B CN201511022663.4A CN201511022663A CN105470487B CN 105470487 B CN105470487 B CN 105470487B CN 201511022663 A CN201511022663 A CN 201511022663A CN 105470487 B CN105470487 B CN 105470487B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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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
- H01M4/58—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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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 kind of copper/tin/graphite sandwich construction lithium ion battery negative material and preparation method thereof, belong to lithium ion battery negative material field.The present invention is simultaneously being overplated with tin, and coating graphite obtains two-layer film configuration successively using coarse copper foil or porous copper foil as substrate；Copper foil after electrolytic degreasing activates, is first prepared one layer of tin coating with the method for impulse jet, one layer of graphite is then coated on tin coating by the present invention, finally carries out 80 150 DEG C of heat treatment, copper/tin/graphite sandwich construction negative material is prepared.Compared with prior art, the invention has cycle performance more more preferable than tin negative pole material, the specific capacity higher than graphite cathode material, while technological process is simple；Therefore, application prospect is very wide.
Description
Technical field
Present invention relates particularly to a kind of copper/tin/graphite sandwich construction lithium ion battery negative material and preparation method thereof, category
In lithium ion battery negative material and its preparing technical field.
Background technology
The characteristics of lithium ion battery possesses high-energy-density, high power density, has a safety feature, has extended cycle life, and
The polluters such as lead, cadmium, mercury are not contained, are a kind of ideal energy storage devices.As the high electricity such as current electric automobile needs
The high speed development of the portable electronics such as the electric tool and notebook computer asked, its capacity to lithium ion battery propose more next
Higher requirement.The capacity of positive and negative pole material is the key for influenceing lithium ion battery energy density, in order that current lithium-ion electric
The energy density in pond is improved, and people have turned to sight the materials such as the tin of high power capacity, silicon.Kamash alloy material is with respect to silicon material
For material, though less than capacity has, at present in essence, its toughness is higher than silicon materials, thus cycle performance is more excellent
It is good, it can more meet the requirement of the multiple cycle charge-discharge of lithium ion battery, therefore become in current negative electrode of lithium ion battery field
The object to receive much concern.
The Tin-base Binary Alloys being widely studied at present mainly have Sn-Cu, Sn-Sb, Sn-Ni, Sn-Co etc., but due to material
Expect the limitation (during as lithium ion battery negative material, its cycle performance is no more than carbon negative pole material) of nature, tinbase closes
The market application of golden negative material still has certain distance, is mainly shown as that irreversible capacity is larger first, multiple charge and discharge cycles
During, because inlaying repeatedly for lithium ion and deintercalation make it that alloy material of cathode Volume Changes are very big so that cycle performance is owed
Lack.In order to solve the above problems, method main at present is to prepare the alloy material of cathode of nanostructured or to alloy anode material
Material is doped or carried out with other materials the carbon materials such as compound, such as incorporation third phase metal, silicon materials, CNT (CNTs)
Material.Carbon can prevent the direct contact between tin particles, suppress the reunion of tin particles and grow up, play a part of cushion, with tin
Based alloy carries out compound tense, and the lifting to tin base alloy anode material performance serves very big effect.Such as Leigang Xue et al.
[Leigang Xue,Zhenghao Fu,Yu Yao,Tao Huang,Aishui Yu,Three-dimensional porous
Sn-Cu alloy anode for lithium-ion batteries,Electrochimica Acta,55(2010)7310-
7314], tin layers are electroplated on three-dimensional foam copper so that it is under 0.1C multiplying power, and after cycle-index 100 times, specific capacity also has
404mAh/g.Xinghui Wang et al. [Xinghui Wang, Leimeng Sun, Xiaonan Hu, Rahmat Agung
Susantyoko,Qing Zhang,Ni-Si nanosheet network as high performance anode for
Li-ion batteries, Journal of Power Sources, 280 (2015) 393-396], prepare a kind of silicon
Structure so that it is under 2C multiplying power, and specific capacity also has 655mAh/g after cycle-index 1000 times.
The A of Chinese patent CN 102185131, porous copper current collector is first prepared with bubble hydrogen template, then using compound
Electrodeposition process, which deposits to kamash alloy and CNT on collector, to be obtained porous current collector/tin-base alloy/carbon nano-tube and answers
Composite electrode, improve tin base alloy anode material specific capacity and cycle performance.The A of Chinese patent CN 10457075, lithium-ion electric
Pond graphitization mesoporous carbon/tin composite negative pole material, by the use of mesoporous silica as template, inject stannic chloride and vegetable oil, Ran Houyong
Sodium hydroxide corrodes, and in 900 DEG C of pyrolysis, removes silica template, obtains graphitization mesoporous carbon/tin composite negative pole material, improves
Its cycle performance, to make it capacity has reached 490mAh/g first.Chinese patent ZL 201210562912.9, a kind of carbon-
Cu6Sn5The preparation method of alloy material of cathode, it will be distributed to after CNT and graphene removal of impurities in tin plating and copper plating solution, so
Cause CNT or graphene dispersion after electroplating afterwards in electrodeposited coating, by being thermally treated resulting in carbon-Cu6Sn5Alloy anode material
Material is when as lithium ion battery negative material, excellent in stability.By summarize it is seen that, although these methods so that tin,
The cycle performance of the high-capacity cathode materials such as silicon has great breakthrough, but is all the situation in active material relatively thin (or less)
Lower realization.Due to the influence that enormousness expands in such material charge and discharge process itself, in big thickness, cycle performance is still
It is rare to be lifted to essence.The reason in terms of along with current high-performance tin, the preparation technology of silicon materials and cost, they are all the time not
Practical application can be obtained.
Existing lithium ion battery negative material is reviewed, due to its high circulation performance and preferable security performance, graphite material
Material is still in the absolute dominant position in negative material field.Therefore, it is possible to combine the advantage of existing negative material, and can be in certain journey
Cause the capacity of negative material to obtain certain lifting on degree, negative electrode of lithium ion battery market will also be played greatly to promote and made
With.
However, the above method is difficult to during solving tin base alloy anode production application, tin-based active material efflorescence
Come off the problem of causing its poor circulation, and production cost problem, and the capacity of graphite cathode is also improved not from structure.
Therefore, need badly to prepare and a kind of there is preferable cycle performance, the lithium ion battery negative material of higher capacity.
The content of the invention
The purpose of the present invention is that the specific capacity for the cycle performance deficiency while graphite cathode for being directed to existing kamash alloy is relatively low
Situation, there is provided a kind of copper/tin/graphite sandwich construction negative material and preparation method thereof, this method prepare negative material tool
There are highly conductive, high rate capability and long circulating performance.
To solve above technical problem, the technical solution adopted by the present invention is：
A kind of preparation method of copper/tin/graphite sandwich construction lithium ion battery negative material：
(1) tin coating is electroplated：One layer of tin coating is electroplated in the side of coarse copper foil or porous copper foil；
(2) graphite linings are coated with：One layer of graphite linings are coated on step (1) described tin coating；
(3) it is heat-treated：The material obtained to step (2) is heat-treated.
The surface roughness of step (1) the coarse copper foil is 0.4~3.0 μm, and the aperture of the porous copper foil is 1~5 μ
M, the thickness of coarse copper foil and porous copper foil is 12~35 μm.
The thickness of tin coating is 0.2~0.8 μm in step (1).
Step (1) plating tin coating uses impulse jet electric plating method, and electroplate liquid formulation and technological parameter are as follows：
Impulse jet electroplating technological parameter：Current density：5~15A/dm2；
PH value：3~4；
Temperature：45~55 DEG C；
Time：5~20s.
The thickness of graphite linings is 80~150 μm in step (2).
Graphite linings described in step (2) include the mass ratio of conductive agent and binding agent mixing composition, conductive agent and binding agent
For (9~12):1；The conductive agent is graphite, or for expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, lead
The one or more of electric carbon black combine the mixture to be formed with graphite, and wherein graphite accounts for the mass percent of conductive agent and is more than
60%.Described graphite linings are by conductive agent, bonding agent (PVDF) and organic solvent (styrene, perchloroethylene, trichloro ethylene
One or more combination) mix slurry coating form.
The temperature of step (3) heat treatment is 80~150 DEG C, and preferably 80~100 DEG C, heat treatment time is 10~24 small
When；Preferably 12~18 hours.
The preparation method of copper/tin/graphite sandwich construction lithium ion battery negative material of the present invention, more specifically include such as
Lower process conditions and step：
(1) pre-process：Negative electrode, anode electrolysis oil removing, and coarse copper foil is activated and cleaned；
The formula and condition that described (1) pretreatment uses are as follows：
1) catholyte oil removing
Degreasing fluid temperature：45~65 DEG C；
The oil removing time：30~60s；
Current density：2~8A/dm2。
2) anode electrolysis oil removing
Degreasing fluid temperature：45~65 DEG C；
The oil removing time：15~30s；
Current density：2~5A/dm2。
3) activate and clean
Activator is：H2SO4：20~40ml/L；
Activation temperature：Room temperature；
Soak time：20~40s.
Cleaning：Coarse copper foil or porous copper foil is taken to be cleaned 3-5 times in distilled water.
(2) tin coating is electroplated：On coarse copper foil or porous copper foil one layer of tin coating, tin are prepared with the method for impulse jet
The thickness of coating is 0.2~0.8 μm.
The tin plating formula and condition that electrotinning uses are as follows：
Pulse plating process parameter：Current density：5~15A/dm2；
PH value：3~4；
Temperature：45~55 DEG C；
Time：5~20s.
(3) it is coated with graphite：One layer of graphite linings are coated on step (2) described tin coating, the thickness of graphite linings is 80~150
μm。
(4) it is heat-treated：Hot place is carried out to the coarse copper foil or porous copper foil that tin coating and graphite linings are plated with step (3)
Reason, obtains the copper/tin/graphite sandwich construction negative material.
Preferably, the raw material of the graphite linings further comprises conductive agent and binding agent, is by conductive agent, bonding agent
(PVDF) and organic solvent (styrene, perchloroethylene, the one or more combination of trichloro ethylene) mix slurry coating
Form.The mass ratio of conductive agent and binding agent is (9~12):1.
The conductive agent is graphite, or is expanded graphite, CNT, carbon fiber, activated carbon, amorphous carbon, conductive charcoal
Black one or more combine the mixture to be formed with graphite, and wherein graphite accounts for the mass percent of conductive agent more than 60%, because
For in the case where volumetric properties and cycle performance are up to standard, the cost of graphite is relatively low.
Preferably, the surface roughness of the coarse copper foil is 0.4~3.0 μm, and thickness is 12~35 μm.
Preferably, the aperture of the porous copper foil is 1~5 μm, and thickness is 12~35 μm.
The present invention proposes a kind of new structure, and prepares a kind of new composite negative pole material, in conventional graphite negative pole material
Between the graphite linings and copper foil current collector layer of material add one layer can with the tin layers of continuous electroplating so that tin layers at 1000 times not
In the case of efflorescence, the capacity of graphite cathode is substantially increased.
The present invention has selected a kind of shaggy copper foil or porous copper foil, coarse copper foil or Porous Cu in structure first
Paper tinsel has the advantages of specific surface area is big, and larger specific surface area and concaveconvex structure can buffer tin well in charge and discharge process
Volumetric expansion, while this structure also acts as good skeleton function, greatly buffers volumetric expansion in charge and discharge process and shrinks
Stress, so as to improve the cycle performance of copper/tin/graphite sandwich construction negative material.
Tin coating thickness control is 0.2~0.8 μm by the present invention, and the cycle performance of tin layers within the specific limits, can be with thickness
Degree increase and reduce, can not lean on the bulk strain in buffer itself charge and discharge process if too thick, cause material efflorescence, and then make
Top layer graphite is obtained to come off.And excessively thin very little the specific capacity of integral material can be caused not high due to tin.
In the present invention, graphite linings uniform fold tin coating, so as to strengthening the intercrystalline binding ability of tin active material, from
And the possibility that active material comes off from matrix is reduced；Simultaneously because the conductive capability that graphite is good so that electronics exists
The speed migrated in active material greatly enhances so that times of the negative material of copper/tin/graphite sandwich construction prepared by the present invention
Rate charge-discharge performance is good.
The temperature and heat treatment time of heat treatment are limited to by the present invention：Temperature is 80~150 DEG C, heat treatment time 10
~24 hours.This is advantageous to the phase counterdiffusion of atom between active material and collector.And in such a situa-tion, it is heat-treated it
Preferable gun-metal Cu can be just obtained afterwards6Sn5, heat treatment time is long, can form more Cu3Sn phases, it is unfavorable for material and follows
Ring performance gives full play to；Heat treatment time is too short, then is unfavorable for the phase counterdiffusion of atom between active material collector.Cause
This, the temperature range that the present invention is heat-treated selection is 80~150 DEG C, and time interval is 10~24 hours, and preferable temperature section is
80~100 DEG C, preferably time interval is 12~18 hours.
Lithium ion battery negative material prepared by the present invention has that charging and discharging capacity is high, strong excellent of cycle performance
Point.Negative pole initial charge quality capacity prepared by the present invention is 460~500mAh/g.Copper/tin/graphite that the present invention prepares is more
The negative pole of Rotating fields, while excellent cycle performance and rate charge-discharge performance are also equipped with, special capacity fade after 1000 circulations
Only 6%~10%.This is the result as caused by following three points factor：1st, the larger specific surface area of coarse copper foil or porous copper foil and
Concaveconvex structure, good skeleton function can be played, while big space can buffer the volumetric expansion of tin active material, reduction is filled
The efflorescence of active material is with coming off in discharge process, the cycle performance of reinforcing material.2nd, graphite material good electric conductivity in itself
And cycle performance, the migration rate of electronics is substantially increased, also functions to the effect of the volumetric expansion of buffering tin material, so that
The high rate charge-discharge excellent performance of material.3rd, kamash alloy can carry out reversible alloy and removal alloying, copper gold with lithium metal
Accessory, when tin atom and copper atom combine to form intermetallic compound, can be for good ductility and thermal conductivity
Tin plays support effect during Lithium-ion embeding with abjection, should caused by lattice variations when buffering Lithium-ion embeding is deviate from
Power, so that in charge and discharge process, repeatedly after embedded abjection, the negative material prepared by the present invention remains unchanged lithium ion
Its original form can be kept.
Compared with other inventive methods, the present invention possesses advantage following prominent：
1st, the larger specific surface area of coarse copper foil or porous copper foil and concaveconvex structure have been used, has improved tin base alloy anode
The shortcomings that cycle performance is bad, and then improve the specific capacity of in the market graphite cathode so that the tin base cathode material of height ratio capacity
Material can apply to market；2nd, production cost is relatively low, and preparation process is simple and easy；3rd, with continuous electroplating, and it is coated with integration system
For lithium ion battery negative material is gone out, be advantageous to the industrialized production of product；4th, the use of non-cyanide solution is electroplating solution, it is right
Environmental nonpollution.5th, during continuous electroplating, the thickness of composite deposite and active material is accurately controlled, improves material
Utilization rate.
Brief description of the drawings
Fig. 1 is the technique stream of copper/tin disclosed by the invention/graphite sandwich construction lithium ion battery negative material preparation method
Cheng Tu；
Fig. 2 is the structural representation of copper/tin disclosed by the invention/graphite sandwich construction lithium ion battery negative material；
Fig. 3 is the scanning of coarse copper foil in copper/tin disclosed by the invention/graphite sandwich construction lithium ion battery negative material
Electron microscope.
Embodiment
Following examples are intended to further illustrate the present invention rather than limitation of the invention.
Embodiment
It it is 15 μm from thickness, roughness is 0.4 μm of coarse copper foil as electroplated substrates.
First, surface preparation before plating：Electrochemical degreasing, activation process are carried out to substrate copper foil；
Electrolytic degreasing current density：5A/dm2
Degreasing fluid temperature：55℃；
The oil removing time：30s；
After oil removing is complete, it is put into activator and activates；
Activator is：H2SO4：30ml/L；
Activation temperature：Room temperature；
Soak time：20s.
2nd, impulse jet electroplating thickness is 0.5 μm of tin coating：
Pulse plating process parameter：Average current density：5A/dm2；
3rd, rinse, dry：The tin plating copper foil after plating is rinsed well with distilled water, then dried.
4th, graphite linings are coated with：The graphite linings of 100 μ m-thicks are coated with coating machine.Graphite linings are by conductive agent, bonding agent
(PVDF) and organic solvent mix slurry coating form.The mass ratio of conductive agent and binding agent is 10:1, conductive agent is
Graphite.
5th, it is heat-treated：80 DEG C in vacuum drying chamber, 24h is dried.
The Alpha-Step IQ step instruments that thickness of coating mentioned in the present invention is produced by KLA Tencor companies of the U.S.
Measurement obtains.
The capacity of lithium ion battery cycle-index table that the present invention mentions is determined by BTS high accuracy batteries detecting system.
Sample is produced by the following method, as a comparison case.
Comparative example 1
From the same terms in embodiment, using coarse copper foil as base material, directly it is coated with graphite linings and is heat-treated, it is not right
Sample carries out the plating of tin coating, obtains comparative example 1.
Comparative example 2
From the same terms in embodiment, using smooth copper foil as base material, carry out plating tin coating to sample, graphite coating and
Heat treatment.
Cycle performance is evaluated
The material of 1 two kinds of techniques of embodiment and comparative example is made into battery pole piece, button cell is dressed up in glove box, is tied
Fruit is as shown in table 1：
The cycle-index of table 1 and specific capacity experimental data table
The ratio of copper/tin/graphite sandwich construction negative material prepared by the embodiment of the present invention is can be seen that by above-mentioned evaluation
Copper/tin/graphite sandwich construction negative pole that capacity is prepared apparently higher than the comparative example 1 being coated with only with graphite, the embodiment of the present invention
The cycle performance of material apparently higher than using smooth copper foil comparative example 2, this for improve battery service life and specific capacity
There is particularly important meaning.
The above embodiment of the present invention is only to illustrate that technical solution of the present invention is used, and only technical solution of the present invention is enumerated,
The technical scheme and its protection domain being not intended to limit the invention, those skilled in the art is according to the above of the invention
Some the nonessential modifications and adaptations made belong to protection scope of the present invention.
Claims (8)
- A kind of 1. preparation method of copper/tin/graphite sandwich construction lithium ion battery negative material, it is characterised in that：(1) tin coating is electroplated：One layer of tin coating is electroplated in the side of coarse copper foil or porous copper foil；(2) graphite linings are coated with：One layer of graphite linings are coated on step (1) described tin coating；(3) it is heat-treated：The material obtained to step (2) is heat-treated；The thickness of tin coating is 0.2~0.8 μm in step (1)；The thickness of graphite linings is 80~150 μm in step (2).
- 2. preparation method according to claim 1, it is characterised in that：The surface roughness of step (1) the coarse copper foil For 0.4~3.0 μm, the aperture of the porous copper foil is 1~5 μm, and the thickness of coarse copper foil and porous copper foil is 12~35 μm.
- 3. preparation method according to claim 1, it is characterised in that：Step (1) plating tin coating is using impulse jet electricity The method of plating, electroplate liquid formulation and technological parameter are as follows：Impulse jet electroplating technological parameter：Current density：5~15A/dm2；PH value：3~4；Temperature：45~55 DEG C；Time：5~20s.
- 4. preparation method according to claim 1, it is characterised in that：The temperature of step (3) heat treatment is 80~150 DEG C, Heat treatment time is 10~24 hours.
- 5. preparation method according to claim 4, it is characterised in that：The temperature of step (3) heat treatment is 80~100 DEG C, Heat treatment time is 12~18 hours.
- 6. preparation method according to claim 1, it is characterised in that：Graphite linings described in step (2) include conductive agent and The mass ratio of binding agent mixing composition, conductive agent and binding agent is (9~12):1；The conductive agent is graphite, or is expansion stone Ink, CNT, carbon fiber, activated carbon, amorphous carbon, the one or more of conductive black combine the mixing to be formed with graphite The mass percent that thing, wherein graphite account for conductive agent is more than 60%.
- 7. preparation method according to claim 6, it is characterised in that：Described graphite linings be by conductive agent, bonding agent and The slurry coating that organic solvent mixes forms.
- A kind of 8. copper/tin that preparation method by described in claim any one of 1-7 is prepared/graphite sandwich construction lithium ion Cell negative electrode material.
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| CN108110222B (en) * | 2017-12-08 | 2020-04-17 | 成都新柯力化工科技有限公司 | Preparation method of multilayer metal-carbon cathode based on lithium battery |
| CN108598361A (en) * | 2018-05-17 | 2018-09-28 | 河南电池研究院有限公司 | A kind of anode plate for lithium ionic cell and preparation method thereof, lithium ion battery |
| CN112151757B (en) * | 2020-09-22 | 2022-04-05 | 浙江锋锂新能源科技有限公司 | Negative plate with multilayer film structure and mixed solid-liquid electrolyte lithium storage battery thereof |
| CN112820860A (en) * | 2021-01-20 | 2021-05-18 | 江西昌大高新能源材料技术有限公司 | Preparation method of silicon-carbon composite cathode |
| CN113991059A (en) * | 2021-11-09 | 2022-01-28 | 河南电池研究院有限公司 | Lithium ion battery negative pole piece and preparation method thereof |
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