CN105489872B - A kind of copper/CNTs tin/graphite sandwich construction lithium ion battery negative material and preparation method thereof - Google Patents

A kind of copper/CNTs tin/graphite sandwich construction lithium ion battery negative material and preparation method thereof Download PDF

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CN105489872B
CN105489872B CN201511024662.3A CN201511024662A CN105489872B CN 105489872 B CN105489872 B CN 105489872B CN 201511024662 A CN201511024662 A CN 201511024662A CN 105489872 B CN105489872 B CN 105489872B
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tin
cnts
graphite
copper foil
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CN105489872A (en
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雷维新
崔俊葳
潘勇
高攀
罗振亚
万娇
李文虎
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Xiangtan University
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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
    • 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
    • H01M4/36—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
    • 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
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of copper/CNTs 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 using coarse copper foil or porous copper foil as substrate, by copper foil after electrolytic degreasing activates, first one layer of CNTs tin coating is prepared with the method for impulse jet, then one layer of graphite is coated on CNTs tin coatings, 80 150 DEG C of heat treatment is finally carried out, copper/CNTs tin/graphite sandwich construction negative material is prepared.Compared with prior art, the invention has preferable cycle performance and higher specific capacity, CNTs in tin layers can play a part of connecting graphite and copper foil current collector, the volumetric expansion of tin also be alleviated with the structure of tin material formation " reinforced concrete ", and tin and copper can generate Cu6Sn5Alloy, so that the negative material cycle performance is further lifted；Therefore, application prospect is very wide.

Description

A kind of copper/CNTs- tin/graphite sandwich construction lithium ion battery negative material and its system Preparation Method
Technical field
Present invention relates particularly to a kind of copper/CNTs- tin/graphite sandwich construction lithium ion battery negative material and its preparation side Method, more particularly to a kind of preparation method that commercialization graphite cathode capacity is improved using tin-based material, is belonged to lithium ion battery and born Pole 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 negative material of industrialized production is carbons material at present, and its theoretical specific capacity is 372mAh/g, because This, has the emphasis that the alloy materials such as tin-based material and the silicon materials of high-energy-density become current material supplier's author investigation.
For kamash alloy material is with respect to silicon materials, though less than capacity has, at present in essence, its toughness is high In silicon materials, thus cycle performance is more excellent, can more meet the requirement of the multiple cycle charge-discharge of lithium ion battery, therefore turns into The object to be received much concern in current negative electrode of lithium ion battery field.The Tin-base Binary Alloys being widely studied at present mainly have Sn-Cu, Sn-Sb, Sn-Ni, Sn-Co etc..
But (during as lithium ion battery negative material, its cycle performance is no more than carbon due to the limitation of material nature Negative material), the application of the market of tin base alloy anode material still has certain distance, be mainly shown as first irreversible capacity compared with Greatly, during multiple charge and discharge cycles, because inlaying repeatedly for lithium ion and deintercalation cause alloy material of cathode Volume Changes pole Greatly so that cycle performance is short of.In order to solve the above problems, method main at present is to prepare the alloy anode material of nanostructured Material is doped to alloy material of cathode or compound, such as incorporation third phase metal, silicon materials, carbon nanometer is carried out with other materials Manage carbon materials such as (CNTs).Carbon can prevent the direct contact between tin particles, suppress the reunion of tin particles and grow up, play buffering The effect of layer, compound tense is carried out with kamash alloy, 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], electroplate tin layers on three-dimensional foam copper so that it is under 0.1C multiplying power, cycle-index After 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], a kind of silicon structure has been prepared so that it is under 2C multiplying power, and specific capacity also has after cycle-index 1000 times 655mAh/g。
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.
Based on this, we replace original copper foil material using the copper foil for being overplated with very thin CNTs-Sn composite deposites so that Collector also possesses the function of a part of active material, and existing high circulation performance graphite cathode material is coated thereon, A kind of new copper-tin-graphite multilayer negative pole has been obtained, the capacity of electrode is improved on the premise of cycle performance is ensured, should Electrode has extremely wide application prospect.
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/CNTs- tin/graphite sandwich construction negative material and preparation method thereof, this method prepare negative pole material Material has 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/CNTs- tin/graphite sandwich construction lithium ion battery negative material：
(1) CNTs- tin coatings are electroplated：One layer of CNTs- 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) the CNTs- tin coatings；
(3) it is heat-treated：The material obtained in 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 9~40 μm.
0.1~1.0 μm of CNTs- tin coatings in step (1).
Step (1) plating CNTs- tin coatings use 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 be by conductive agent, bonding agent and organic solvent (styrene, perchloroethylene, trichloro ethylene one kind or Several combinations) 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 of the present invention/CNTs- tin/graphite sandwich construction lithium ion battery negative material, is more specifically wrapped Include following 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) CNTs- tin coatings are electroplated：On coarse copper foil or porous copper foil one layer is prepared with the method for impulse jet CNTs- tin coatings, the thickness of CNTs- tin coatings is 0.1~1.0 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) the CNTs- tin coatings, the thickness of graphite linings is 80 ~150 μm.
(4) it is heat-treated：The coarse copper foil or porous copper foil that CNTs- tin coatings and graphite linings are plated with step (3) are entered Row heat treatment, obtains the copper/CNTs- 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 9~40 μm.
Preferably, the aperture of the porous copper foil is 1~5 μm, and thickness is 9~40 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 One layer is added between the graphite linings and copper foil current collector layer of material can be with the CNTs- tin layers of continuous electroplating, so that tin layers exist In the case of 1000 times non-chalking, 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/CNTs- tin/graphite sandwich construction negative material.
The present invention replaces original copper foil material using the copper foil for being overplated with very thin CNTs-Sn composite deposites so that afflux Body also possesses the function of a part of active material, and existing high circulation performance graphite cathode material is coated thereon, obtains A kind of new copper-CNTs- tin-graphite multilayer negative poles, the capacity of electrode is improved on the premise of cycle performance is ensured.
The control of CNTs- tin coating thickness is 0.1~1.0 μm by the present invention.The CNTs- tin coatings play in whole negative pole Main function the effect of collector and Activated Graphite is connected while be as active material, while in CNTs- tin layers CNTs can play a part of connecting graphite and copper foil current collector, and the structure that " reinforced concrete " is formed with tin material also alleviates The volumetric expansion of tin.The difference of CNTs- tin thicknesses, connection function and volumetric expansion situation are also different, therefore will the company of avoiding Connecing that layer is excessively thin, do not play the specific capacity for improving simple graphite cathode so that the negative material loses the meaning of its industrialization, if Articulamentum is blocked up, and the volumetric expansion problem of tin material just cannot be solved reasonably, loses the value of the marketization.
In the present invention, graphite linings uniform fold CNTs- tin layers, so as to strengthening the intercrystalline combination energy of tin active material Power, so that the possibility that active material comes off from matrix reduces.Simultaneously because graphite and the good conduction of CNT Ability so that the speed that electronics migrates in active material greatly enhances so that high power capacity superelevation cyclicity prepared by the present invention The rate charge-discharge excellent performance of energy CNTs- tin/graphite double-decker negative material.
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 480~530mAh/g.The copper that the present invention prepares/CNTs- tin/ The negative pole of graphite sandwich construction, while excellent cycle performance and rate charge-discharge performance are also equipped with, specific volume after 1000 circulations Amount decay only 6%~10%.This is the result as caused by following three points factor：1st, the larger ratio table of coarse copper foil or porous copper foil Area and concaveconvex structure, good skeleton function can be played, while big space can buffer the volumetric expansion of tin active material, The efflorescence of active material in charge and discharge process is reduced with coming off, the cycle performance of reinforcing material.2nd, graphite material is good in itself Electric conductivity and cycle performance, the migration rate of electronics is substantially increased, also function to the effect of the volumetric expansion of buffering tin material, from And cause the high rate charge-discharge excellent performance of material.3rd, graphite linings uniform fold CNTs- tin coatings, so as to strengthen tin activity Binding ability between material grains, so that the possibility that active material comes off from matrix reduces；Simultaneously because graphite is good Good conductive capability so that the speed that electronics migrates in active material greatly enhances so that copper/CNTs- prepared by the present invention The rate charge-discharge of the negative material of tin/graphite sandwich construction is functional.
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 copper disclosed by the invention/CNTs- tin/graphite sandwich construction lithium ion battery negative material preparation method Process chart；
Fig. 2 is the structural representation of copper disclosed by the invention/CNTs- tin/graphite sandwich construction lithium ion battery negative material Figure；
Fig. 3 is coarse copper foil in copper disclosed by the invention/CNTs- tin/graphite sandwich construction lithium ion battery negative material Scanning electron microscope (SEM) photograph.
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 CNTs- tin coatings：
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 CNTs- tin coatings, obtains comparative example 1.
Comparative example 2
From the same terms in embodiment, using smooth copper foil as base material, plating CNTs- tin coatings, graphite are carried out to sample 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
Copper/CNTs- tin/graphite sandwich construction negative pole material of preparation of the embodiment of the present invention is can be seen that by above-mentioned evaluation For the specific capacity of material apparently higher than the comparative example 1 being coated with only with graphite, copper/CNTs- tin/graphite prepared by the embodiment of the present invention is more For the cycle performance of Rotating fields negative material apparently higher than the comparative example 2 using smooth copper foil, this uses the longevity for raising battery Life and specific capacity have 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)

  1. A kind of 1. preparation method of copper/CNTs- tin/graphite sandwich construction lithium ion battery negative material, it is characterised in that：
    (1) CNTs- tin coatings are electroplated：One layer of CNTs- 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) the CNTs- tin coatings；
    (3) it is heat-treated：The material obtained in step (2) is heat-treated；
    0.1~1.0 μm of CNTs- tin coatings in step (1)；The thickness of graphite linings is 80~150 μm in step (2).
  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 9~40 μm.
  3. 3. preparation method according to claim 1, it is characterised in that：Step (1) is electroplated CNTs- tin coatings and sprayed using pulse Electric plating method is penetrated, 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. 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. 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. 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. 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.
  8. A kind of 8. copper that preparation method by described in claim any one of 1-7 is prepared/CNTs- tin/graphite sandwich construction Lithium ion battery negative material.
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CN108866412B (en) * 2017-05-08 2020-09-29 清华大学 Preparation method of three-dimensional porous composite material
CN108206285B (en) * 2017-12-12 2021-08-24 中国科学院物理研究所 Composite coated nano tin anode material and preparation method and application thereof
CN110965085B (en) * 2019-12-30 2021-10-12 中国科学院青海盐湖研究所 Graphite composite copper foil and preparation method thereof
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
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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