CN106784856A - A kind of carbon nano-fiber/metal foil double-layer composite material and preparation method thereof - Google Patents
A kind of carbon nano-fiber/metal foil double-layer composite material and preparation method thereof Download PDFInfo
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- CN106784856A CN106784856A CN201611238264.6A CN201611238264A CN106784856A CN 106784856 A CN106784856 A CN 106784856A CN 201611238264 A CN201611238264 A CN 201611238264A CN 106784856 A CN106784856 A CN 106784856A
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/663—Selection of materials containing carbon or carbonaceous materials as conductive part, e.g. graphite, carbon fibres
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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
- H01M4/13—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
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/661—Metal or alloys, e.g. alloy coatings
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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
- H01M4/64—Carriers or collectors
- H01M4/66—Selection of materials
- H01M4/665—Composites
- H01M4/667—Composites in the form of layers, e.g. coatings
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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 carbon nano-fiber/metal foil double-layer composite material and preparation method thereof.The invention is obtained nanofiber with metal foil as receiver board by method of electrostatic spinning, and the metal foil of supporting nanofibres is carried out into in-situ carburization under an inert atmosphere, obtains carbon nano-fiber uniform load in the double-layer composite material of metal foil.The composite is directly used in the assembling of lithium ion battery as cathode pole piece, the tack of its two-layer composite is good, the lithium ion reversible capacity of carbon nano-fiber is high and good conductivity, conductive agent and binding agent need not be added, the negative material for eliminating former pole piece preparation technology is sized mixing, is coated with two steps, greatly simplifies technological process, low cost, efficiency high, workable, pole piece good cycle.The composite can also be used as a kind of new current collector of lithium ion battery, can further lift the capacity and cycle performance of primary electrode material.
Description
Technical field
The present invention relates to a kind of carbon nano-fiber/metal foil double-layer composite material and preparation method thereof, belong to new energy material
Material and electrochemical field.
Background technology
Electrostatic spinning, relative to methods such as pulling method, templates, can be obtained as a kind of special fiber producing processes
Nano-scale fiber；With reference to carbonization etc. processing means can be evenly distributed, the preferable carbon nano-fiber of continuity.At present, with reference to
The conventional fabrication process that carbon nano-fiber prepared by electrostatic spinning technique is used as lithium ion battery negative material is mainly slurrying, applies
The steps such as cloth, cut-parts, assembling, technological process is complicated, efficiency is relatively low, uncontrollable factor is more.
The mesopore that Chinese patent 201510545414.7 discloses doped graphene prepared by a kind of utilization electrostatic spinning is more
The method of hole carbon/silicon nanofiber, Chinese patent 201510900329.8 discloses a kind of utilization and sprays coating by carbon fiber, stone
Ink, binding agent, conductive agent mixed solution are uniformly sprayed to Copper Foil, the method so as to obtain cathode pole piece.But, both approaches
It is required for adding binding agent and conductive agent, process is complicated, does not have technological process substantial simplification.Chinese patent
201510010088.X discloses a kind of pitch and silica flour with heating and melting as raw material, by crush cutting bar, spin cotton and weave cloth and
Carbonization treatment is obtained carbon cloth, for the method is with respect to electrostatic spinning, it is impossible to nano-scale fiber is enough obtained.Chinese patent
201310706990.6 disclose a kind of presoma by Ti and Sn, polymer and original solution obtained in organic solvent passes through electrostatic
Spinning prepares nano fibrous membrane, and Sn composite Tis O is obtained by carbonization treatment2/ C nano tunica fibrosa, but when being used as negative material,
Need with nickel foam as collector, fiber membrane is pressed in nickel foam and dried process is carried out, process is complicated, operability is poor.
Chinese patent 201410648186.1 discloses molten using polyacrylonitrile, two hydration stannous chloride and graphene oxide
Liquid is original solution, and tinbase/carbon fiber felt composite is obtained by electrostatic spinning and carbonization treatment.Chinese patent
201510308966.6 to disclose a kind of be spinning solution using polyacrylonitrile and CNT mixed solution, by electrostatic spinning and
Carbonization treatment obtains carbon fiber/carbon nanotube composite membrane.Chinese patent 201510194862.7 disclose it is a kind of with polyacrylonitrile,
Mineral oil and stannous acetate mixed solution are spinning solution, and it is fine to obtain tin/porous nano carbon by electrostatic spinning and carbonization treatment
Dimension.Above-mentioned three kinds of methods are not used binding agent and conductive agent in preparation process, but carbon fiber and carbon fiber can not be made compound
Material in situ is carried on Copper Foil top layer, i.e., can not obtain the cathode pole piece that can be directly used for lithium ion battery assembling.
Meanwhile, the carbon nano-fiber of uniform load has excellent electric conductivity and adhesion property in metal foil, can be used as work(
Energy coating is lifted and improved to the existing metal foil such as collector such as Copper Foil, aluminium foil.First, carbon nano-fiber is uniformly born
Metal foil surface is loaded in, the polarization of collector burn into is effectively prevent, using the teaching of the invention it is possible to provide splendid static conductive performance, is collected and is lived
The micro-current of property material, such that it is able to the contact resistance between positive/negative material and collector is greatly lowered；Secondly, nanometer
Carbon fiber can improve adhesion property between positive/negative material and collector, it is possible to reduce the use of binding agent, reduce pole piece system
This is caused, lifting multiplying power, specific capacity lift battery performance.
Based on this, electrostatic spinning apparatus, particularly reception device are improved, with business metal foil as reception device
It is used to receive nanofiber, the metal foil of supporting nanofibres is carried out into in-situ carburization under an inert atmosphere, with reference to Nano carbon fibers
The good adhesion property of the electric conductivity and metal foil of dimension, can directly be obtained carbon nano-fiber/metal foil double-layer composite material,
The carbon nano-fiber/metal foil double-layer composite material can as a kind of new current collector or as cathode pole piece be directly used in lithium from
The assembling of sub- battery.
The content of the invention
The technical problem to be solved in the present invention is to provide a kind of carbon nano-fiber/metal foil double-layer composite material and its system
Preparation Method, relative to traditional handicraft, the method eliminate slurrying, coating two steps, simple to operate, low cost, efficiency high, easily
In after industrialization production, direct-assembling lithium ion battery, with height ratio capacity and preferable cyclical stability；Meanwhile, as one
New current collector is planted, the polarization of collector burn into can be solved, between positive/negative material and collector the problems such as adhesion property difference.
In order to solve the above technical problems, the technical solution adopted in the present invention is：
A kind of carbon nano-fiber/metal foil double-layer composite material, including carbon nano-fiber layer and metal foil layer, carbon nano-fiber are equal
Even to be carried on metal foil surface, the carbon nano-fiber/metal foil double-layer composite material can be used as a kind of new current collector or work
The assembling of lithium ion battery is directly used in for cathode pole piece.
Further, a diameter of 50 ~ 500nm of the carbon nano-fiber.
Further, the thickness of the carbon nano-fiber layer is 100 ~ 300 μm.
Further, the metal foil is any one in Copper Foil, aluminium foil or nickel foam.
A kind of preparation method of carbon nano-fiber/metal foil double-layer composite material, it is comprised the following steps that：
（1）Prepared polymer spinning solution first, mass fraction is 10 ~ 50%,；Metal foil as electrostatic spinning reception device,
Voltage is 5 ~ 10kV, spinning flow velocity is 0.2 ~ 2mL/h, receive distance under 8 ~ 20cm, the spinning condition that syringe needle size is 12#
Electrostatic spinning is carried out, uniform load is obtained in the nanofiber of metal foil surface.
（2）The metal foil of supporting nanofibres is pre-oxidized in an oven, first step Pre oxidation is 120 ~ 150 DEG C,
18 ~ 24h of process time；Second step Pre oxidation is 250 ~ 300 DEG C, 1 ~ 3h of process time.
（3）By pre-oxidize back loading nanofiber metal foil be carbonized under an inert gas, carburizing temperature be 500 ~
800 DEG C, soaking time is 1 ~ 4h, after naturally cooling to room temperature, carbon nano-fiber/metal foil double-layer composite material is obtained.
Further, the step（1）In polymer be polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）, it is poly-
Propylene is fine（PAN）And polyamide（PA）In one or more.
Compared with prior art, the invention has the advantages that and feature：
（1）Directly as lithium ion battery electrode piece, carbon nano-fiber uniform load is in metal foil surface, carbon nano-fiber layer
With preferable profile pattern and finish, in cut-parts and cell assembling processes, nano surface carbon fiber layer will not occur
The phenomenons such as fold, bending and contraction.Carbon nano-fiber has preferable electric conductivity, it is not necessary to addition such as conductive carbon black, conductive stone
The conductive agents such as ink.Meanwhile, carbon nano-fiber is evenly distributed, and has preferable adhesion property with metal foil substrate, being capable of uniform load
In metal foil surface, it is not necessary to add any binding agent.With respect to existing process technology, eliminate slurry and prepare, be coated with two big steps
Suddenly, fundamentally simplify and improve technological process, simple to operate, with low cost, efficiency is higher, be easy to industrialization production.Together
When, the influence of conductive agent, binding agent to lithium ion battery specific capacity, cyclical stability and high rate performance is efficiently avoid,
Avoid the destruction of solvent molecule or hydrone to lithium ion battery charge and discharge process, by the cathode pole piece of gained to lithium from
Sub- battery assembling, shows specific capacity and good cyclical stability higher.
（2）The carbon nano-fiber/metal foil double-layer composite material is used as a kind of new current collector of lithium ion battery,
Effectively prevent the polarization of collector burn into, using the teaching of the invention it is possible to provide splendid static conductive performance, collect the micro-current of active material,
Such that it is able to the contact resistance between positive/negative material and collector is greatly lowered, carbon nano-fiber can improve positive/negative
Adhesion property between material and collector, it is possible to reduce the use of binding agent, reduces pole piece manufacturing cost, can further lift original
The capacity and cycle performance of positive/negative material.
Brief description of the drawings
Fig. 1 is the SEM figures of carbon nano-fiber in the embodiment of the present invention 1；
Fig. 2 be the embodiment of the present invention 1 in carbon nano-fiber/Copper Foil double-layer composite material be in current density as cathode pole piece
The cycle performance curve of 100mA/g；
Fig. 3 be the embodiment of the present invention 1 in carbon nano-fiber/Copper Foil double-layer composite material be in current density as cathode pole piece
The charging and discharging curve of 100mA/g；
Fig. 4 be the embodiment of the present invention 5 in carbon nano-fiber/Copper Foil double-layer composite material as collector performance comparison figure.
Specific embodiment
The invention will be further described with reference to the accompanying drawings and examples.
Embodiment 1
40g PVP powder is weighed, is scattered in 60mL deionized waters, accelerate to dissolve by magnetic agitation, PVP dissolvings after 1h
Completely, static 2h finally obtains uniform PVP spinning solutions to the elimination of bubble.From 12 μ m thicks Copper Foil as spinning
The receiver board of silk device, spinning actual conditions：Voltage is 6kV, and spinning flow velocity is 0.5mL/h, and it is 15cm, syringe needle to receive distance
Size is 12#, and uniform load is obtained in the PVP nanofibers of copper foil surface by electrostatic spinning.PVP nanofibers will be loaded
Copper Foil is pre-oxidized in drying box, the volatilization of solidification and solvent for fiber, 120 DEG C of first step Pre oxidation, during treatment
Between 24h；Second step Pre oxidation is 280 DEG C, and process time is 2h.Then it is carbonized under an argon atmosphere, heating rate
It is 5 DEG C/min, carburizing temperature is 600 DEG C, and soaking time is 2h, is taken out after naturally cooling to room temperature, obtains carbon nano-fiber/copper
Paper tinsel double-layer composite material.
Further, by carbon nano-fiber/Copper Foil double-layer composite material directly as lithium ion battery negative electrode, to electricity
Pole lithium piece, lithium is carried out in vacuum glove box to carbon nano-fiber obtained in the present embodiment method/Copper Foil double-layer composite material
Ion battery is assembled, and obtains the fastening lithium ionic cell of model CR2032.Crossing current is carried out using LAND battery test systems to fill
Discharge test.
Fig. 1 is the SEM figures of carbon nano-fiber in the embodiment of the present invention 1, it can be seen that the Nano carbon fibers of Copper Foil load in situ
Dimension has draw ratio higher, and continuity is good, is uniformly dispersed, and fibre diameter is 50 ~ 500nm.
Fig. 2 be the embodiment of the present invention 1 in carbon nano-fiber/Copper Foil double-layer composite material as cathode pole piece in current density
It is the cycle performance curve of 100mA/g, as illustrated, under the current density of 100mA/g, first discharge specific capacity reaches
1822mAh/g, after circulating 20 times, specific capacity is maintained at more than 550mAh/g, with specific capacity and cyclical stability higher.
Fig. 3 be the embodiment of the present invention 1 in carbon nano-fiber/Copper Foil double-layer composite material as cathode pole piece in current density
It is the charging and discharging curve of 100mA/g, it can be seen that without obvious charge and discharge platform, meet the charge-discharge characteristic of carbon material；
During first charge-discharge, charging and discharging curve occurs in that unstable fluctuation, it may be possible to due to SEI films formation caused by.
Embodiment 2
10g PVA powder is weighed, is scattered in 90mL deionized waters, it is molten with glass bar acceleration under 90 DEG C of water bath conditions
Solution, PVA is completely dissolved after 30min, and static 3h finally obtains uniform PVA spinning solutions to the elimination of bubble.From 20 μm
The aluminium foil of thickness as device for spinning receiver board, spinning actual conditions：Voltage is 8kV, and spinning flow velocity is 0.5mL/h, is connect
It is 15cm to receive distance, and syringe needle size is 12#, and uniform load is obtained in the PVA nanofibers of aluminium foil surface by electrostatic spinning.Will
The aluminium foil for loading PVA nanofibers is pre-oxidized in drying box, the volatilization of solidification and solvent for fiber, first step pre-oxidation
120 DEG C of temperature, process time 24h；Second step Pre oxidation is 280 DEG C, and process time is 2h.Then enter under an argon atmosphere
Row carbonization, heating rate is 5 DEG C/min, and carburizing temperature is 600 DEG C, and soaking time is 2h, is taken out after naturally cooling to room temperature, is obtained
To carbon nano-fiber/aluminium foil double-layer composite material.
Embodiment 3
10g PA66 powder is weighed, is scattered in 40g formic acid, accelerate to dissolve by magnetic agitation, PA66 has dissolved after 1h
Entirely, static 1h finally obtains uniform PA66 spinning solutions to the elimination of bubble.From nickel foam connecing as device for spinning
Receive plate, spinning actual conditions：Voltage is 6kV, and spinning flow velocity is 1mL/h, and it is 15cm to receive distance, and syringe needle size is 12#, is led to
Cross electrostatic spinning and uniform load is obtained in the PA66 nanofibers of foam nickel surface.The nickel foam for loading PA66 nanofibers is existed
Pre-oxidized in drying box, the volatilization of solidification and solvent for fiber, 120 DEG C of first step Pre oxidation, process time 24h；
Second step Pre oxidation is 280 DEG C, and process time is 2h.Then be carbonized under an argon atmosphere, heating rate be 5 DEG C/
Min, carburizing temperature is 600 DEG C, and soaking time is 2h, is taken out after naturally cooling to room temperature, obtains nanometer carbon fiber/foam nickel double
Layer composite.
Further, it is right by nanometer carbon fiber/foam nickel double-layer composite material directly as lithium ion battery negative electrode
Electrode lithium piece, lithium ion battery assembling is carried out in vacuum glove box to cathode pole piece obtained in the present embodiment method, is obtained
The fastening lithium ionic cell of model CR2032.Crossing current charge-discharge test is carried out using LAND battery test systems.
The present embodiment method and embodiment 1 are essentially identical, the difference is that only that spinning flow velocity is 1mL/h, polymer
For PA66 and collector are nickel foam.A diameter of 200 ~ the 500nm of carbon nano-fiber obtained by the method, in the electricity of 100mA/g
Under current density, first discharge specific capacity is 1217mAh/g, and after circulating 20 times, capacity is maintained at 558mAh/g.
Embodiment 4
40g PVP powder is weighed, is scattered in 60mL deionized waters, accelerate to dissolve by magnetic agitation, PVP dissolvings after 1h
Completely, static 2h finally obtains uniform PVP spinning solutions to the elimination of bubble.From 12 μ m thicks Copper Foil as spinning
The receiver board of silk device, spinning actual conditions：Voltage is 6kV, and spinning flow velocity is 0.5mL/h, and it is 15cm, syringe needle to receive distance
Size is 12#, and uniform load is obtained in the PVP nanofibers of copper foil surface by electrostatic spinning.PVP nanofibers will be loaded
Copper Foil is pre-oxidized in drying box, the volatilization of solidification and solvent for fiber, 120 DEG C of first step Pre oxidation, during treatment
Between 24h；Second step Pre oxidation is 280 DEG C, and process time is 2h.Then it is carbonized under an argon atmosphere, heating rate
It is 5 DEG C/min, carburizing temperature is 800 DEG C, and soaking time is 2h, is taken out after naturally cooling to room temperature, obtains carbon nano-fiber/copper
Paper tinsel double-layer composite material.
Further, carbon nano-fiber/Copper Foil double-layer composite material is used electrode directly as lithium ion battery negative electrode
Lithium piece, lithium ion battery assembling is carried out in vacuum glove box to cathode pole piece obtained in the present embodiment method, obtains model
The fastening lithium ionic cell of CR2032.Crossing current charge-discharge test is carried out using LAND battery test systems.
The present embodiment method and embodiment 1 are essentially identical, the difference is that only that carburizing temperature is 800 DEG C.The method institute
A diameter of 100 ~ the 400nm of carbon nano-fiber for obtaining, under the current density of 100mA/g, first discharge specific capacity is 1806mAh/
G, after circulating 20 times, capacity is maintained at 609mAh/g.
Embodiment 5
40g PVP powder is weighed, is scattered in 60mL deionized waters, accelerate to dissolve by magnetic agitation, PVP dissolvings after 1h
Completely, static 2h finally obtains uniform PVP spinning solutions to the elimination of bubble.From 12 μ m thicks Copper Foil as spinning
The receiver board of silk device, spinning actual conditions：Voltage is 6kV, and spinning flow velocity is 0.5mL/h, and it is 15cm, syringe needle to receive distance
Size is 12#, and uniform load is obtained in the PVP nanofibers of copper foil surface by electrostatic spinning.PVP nanofibers will be loaded
Copper Foil is pre-oxidized in drying box, the volatilization of solidification and solvent for fiber, 120 DEG C of first step Pre oxidation, during treatment
Between 24h；Second step Pre oxidation is 280 DEG C, and process time is 2h.Then it is carbonized under an argon atmosphere, heating rate
It is 5 DEG C/min, carburizing temperature is 600 DEG C, and soaking time is 4h, is taken out after naturally cooling to room temperature, obtains carbon nano-fiber/copper
Paper tinsel double-layer composite material.
Further, porous carbon in mass ratio：PVDF：Conductive carbon black=8：1：1 carries out slurrying, by the slurry even spread of gained
In carbon nano-fiber/Copper Foil double-layer composite material, obtain can be used for the cathode pole piece of lithium ion battery assembling after drying.
Further, to electrode lithium piece, cathode pole piece obtained in the present embodiment method is carried out in vacuum glove box
Lithium ion battery is assembled, and obtains the fastening lithium ionic cell of model CR2032.Flow over using LAND battery test systems
Charge-discharge test.
Slurry is directly coated on Copper Foil and carbon nano-fiber/Copper Foil two-layer compound material obtained by the present embodiment is coated on
Material, the cycle performance after assembled battery is as shown in figure 4, using carbon nano-fiber/Copper Foil double-layer composite material as afflux respectively
Body, under the current density of 100mA/g, first discharge specific capacity is 1615mAh/g, and after circulating 20 times, capacity is maintained at
590mAh/g；And after being directly coated as collector using Copper Foil, the first discharge specific capacity of battery is 1356mAh/g,
After circulation 20 times, capacity is merely retained in 557mAh/g.
Embodiments of the invention are the foregoing is only, the scope of the claims of the invention is not thereby limited, it is every to utilize this hair
Equivalent structure or equivalent flow conversion that bright specification and accompanying drawing content are made, or directly or indirectly it is used in other related skills
Art field, is included within the scope of the present invention.
Claims (6)
1. a kind of carbon nano-fiber/metal foil double-layer composite material, including carbon nano-fiber layer and metal foil layer, carbon nano-fiber
Uniform load is in metal foil surface, it is characterised in that：The carbon nano-fiber/metal foil double-layer composite material can be used as a kind of new
Type collector is directly used in the assembling of lithium ion battery as cathode pole piece.
2. a kind of carbon nano-fiber/metal foil double-layer composite material according to claim 1, it is characterised in that：It is described to receive
A diameter of 50 ~ 500nm of rice carbon fiber.
3. a kind of carbon nano-fiber/metal foil double-layer composite material according to claim 1, it is characterised in that：It is described to receive
The thickness of rice carbon fiber layer is 100 ~ 300 μm.
4. a kind of carbon nano-fiber/metal foil double-layer composite material according to claim 1, it is characterised in that：The gold
Category paper tinsel is any one in Copper Foil, aluminium foil or nickel foam.
5. the preparation method of the carbon nano-fiber according to claim 1-4 any one/metal foil double-layer composite material, its
It is characterised by, comprises the following steps：
（1）Prepared polymer spinning solution first, mass fraction is 10 ~ 50%, metal foil as electrostatic spinning reception device,
Voltage is 5 ~ 10kV, spinning flow velocity is 0.2 ~ 2mL/h, receive distance under 8 ~ 20cm, the spinning condition that syringe needle size is 12#
Electrostatic spinning is carried out, uniform load is obtained in the nanofiber of metal foil surface；（2）The metal foil of supporting nanofibres is being dried
Pre-oxidized in case, first step Pre oxidation is 120 ~ 150 DEG C, 18 ~ 24h of process time；Second step Pre oxidation be 250 ~
300 DEG C, 1 ~ 3h of process time；（3）The metal foil for pre-oxidizing back loading nanofiber is carbonized under an inert gas, is carbonized
Temperature is 500 ~ 800 DEG C, and soaking time is 1 ~ 4h, after naturally cooling to room temperature, carbon nano-fiber/metal foil two-layer compound is obtained
Material.
6. a kind of preparation method of carbon nano-fiber/metal foil double-layer composite material according to claim 5, its feature exists
In：The step（1）In polymer be polyvinylpyrrolidone（PVP）, polyvinyl alcohol（PVA）, polypropylene it is fine（PAN）And
Polyamide（PA）In one or more.
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| CN108963265A (en) * | 2018-06-25 | 2018-12-07 | 深圳市清新电源研究院 | A kind of lithium metal battery negative current collector and preparation method thereof |
| CN110289383A (en) * | 2019-06-18 | 2019-09-27 | 深圳昌茂粘胶新材料有限公司 | A kind of lithium battery power battery high-temperature resistant micropore thin film material and preparation method thereof |
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| CN112549700A (en) * | 2019-09-25 | 2021-03-26 | 深圳大学 | Metal-polymer composite material and preparation method and application thereof |
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| CN113380986A (en) * | 2021-05-25 | 2021-09-10 | 重庆交通大学绿色航空技术研究院 | Method for preparing integrated lithium battery cathode based on electrostatic spinning method |
| CN113652648A (en) * | 2021-08-16 | 2021-11-16 | 武汉纺织大学 | Method for desublimation compounding of metal material and carbon fiber net in carbonization process |
| CN114628687A (en) * | 2022-03-21 | 2022-06-14 | 中国科学技术大学 | Gradient conductive current collector material, preparation method thereof, negative electrode and battery |
| CN115036151A (en) * | 2022-07-08 | 2022-09-09 | 嘉兴学院 | Preparation method of conductive high polymer-based composite electrode material |
| WO2023245871A1 (en) * | 2022-06-24 | 2023-12-28 | 扬州纳力新材料科技有限公司 | Composite metal foil, and preparation method therefor and use thereof |
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| CN114628687A (en) * | 2022-03-21 | 2022-06-14 | 中国科学技术大学 | Gradient conductive current collector material, preparation method thereof, negative electrode and battery |
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