CN110190286A - A kind of vertical graphene-copper foil composite current collector and preparation method thereof based on growth in situ - Google Patents
A kind of vertical graphene-copper foil composite current collector and preparation method thereof based on growth in situ Download PDFInfo
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- CN110190286A CN110190286A CN201910437181.7A CN201910437181A CN110190286A CN 110190286 A CN110190286 A CN 110190286A CN 201910437181 A CN201910437181 A CN 201910437181A CN 110190286 A CN110190286 A CN 110190286A
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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
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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
- H01M4/663—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
- 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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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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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
Vertical graphene-copper foil composite current collector preparation method based on growth in situ that the invention discloses a kind of, belong to technical field of lithium ion, vertical graphene-copper foil composite current collector is prepared in situ by plasma enhanced chemical vapor deposition method in the present invention, the graphene prepared-copper foil composite current collector surface has micron order petal-like structures, it is 125-143.5 ° that it, which contacts angular region, with super-hydrophobic oil-wet behavior, the wellability of collector and reactive species interface can effectively be improved, increase contact surface, improve bond strength, keep active material not easily to fall off, to reduce interface impedance；And the infiltration for promoting thus collector obtained cathode and electrolyte, comes into full contact with electrolyte with negative electrode active material, increases contact area, reduce battery polarization.Method of the invention is easy to operate, and cost is relatively low, is suitable for large-scale production.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of vertical graphene-copper based on growth in situ
The preparation method of foil composite current collector.
Background technique
Lithium ion battery because the protrusion such as its energy density and power density are big, have extended cycle life, stability is good advantage
It is widely used in the fields such as communication, automobile, aerospace.But with the development of technology and proposition actually required, lithium from
Sub- battery is also required to further improve and improve.In lithium-ion battery system, collector is essential component part.It
It is not only the carrier of active material, also acts as and collects electric current to form the effect of more High-current output.Therefore it is required that collector with
Active material comes into full contact with, and has stronger binding force, so that it is fully utilized, and keep internal resistance as small as possible.
The smooth copper foil in traditional negative current collector material selection surface, is applied directly to copper foil table for electrode active material
Face, but since copper foil self property is limited, there are still certain shortcomings for copper foil current collector: (1) copper foil is in conjunction with active material
Intensity difference is easy to fall off, so as to cause battery failure；(2) active material contacts unevenly with copper foil surface, mostly point contact,
Therefore poorly conductive and internal resistance it is larger；(3) cathode as made from copper foil and electrolyte wellability are poor, and contact area is small, leads to electricity
Pond polarization is more serious.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of vertical graphene-copper foil Composite Set based on growth in situ
Vertical graphene-copper foil composite current collecting is prepared in situ by plasma enhanced chemical vapor deposition method in the preparation method of fluid
Body improves the bond strength between collector and active material, and cathode and electrolyte is promoted to infiltrate, and reduces the internal resistance of cell and reduces pole
Change phenomenon, this method is easy to operate, and cost is relatively low, is suitable for large-scale production.
The present invention is achieved through the following technical solutions:
A kind of vertical graphene-copper foil composite current collector preparation method based on growth in situ, comprising the following steps:
(1) pretreatment of copper foil: acetone soln and ethanol solution ultrasound will successively be used with a thickness of 20-60 μm of copper foil
10-30min is cleaned, then the copper foil cleaned is placed in the HCl solution that concentration is 0.1-1mol/L, 60 DEG C of water in water-bath
20min is bathed, pretreated copper foil is obtained；
(2) laminar nano copper-copper foil preparation: pretreated copper foil is placed in vacuum evaporation coating machine, lower than 1 ×
10-4Vacuum evaporation is carried out under the conditions of Pa, in the Nanometer Copper of copper foil surface vapor deposition 80-90nm thickness, nano copper particle size range is
300-500nm, repeats vapor deposition 3-5 times, and laminar nano copper-copper foil material is made；
(3) laminar nano copper-copper foil material made from step (2) growth in situ of vertical graphene: is placed in plasma
Body enhances in the reaction chamber of chemical vapor depsotition equipment (PECVD), vacuumizes and heats up according to certain heating rate,
Vacuum degree is evacuated to 1 × 10-4Pa hereinafter, and after reaction chamber warm table reaches set temperature, be passed through argon gas and carbon-source gas, setting pressure
It is reacted with power by force, in the vertical graphene of copper foil surface growth in situ, obtains vertical graphene-copper foil composite current collector.
Further, heating rate described in step (3) is in the section 3-8 DEG C/min, set holding temperature range as
700-1000 DEG C, the carbon-source gas is methane, ethylene or acetylene, and reaction pressure range is 400-600Pa, reaction power range
For 200-350W, reaction time 50-80min.
Further, the volume ratio of carbon-source gas and argon gas described in step (3) is 1:3-6.
Vertical graphene-copper foil composite current collector of the present invention, surface are in micron order petal-like structures, contact
Angular region is 125-143.5 °, has super-hydrophobic oil-wet behavior.
Compared with prior art, advantages of the present invention is as follows:
(1) vertical graphene-copper foil Composite Set is prepared in situ by plasma enhanced chemical vapor deposition method in the present invention
Fluid, surface have micron order petal-like structures, and contact angular region is 125-143.5 °, have super-hydrophobic oil-wet behavior,
The wellability of collector and reactive species interface can effectively be improved, increase contact surface, bond strength is improved, make active material
It is not easily to fall off, to reduce interface impedance；And promote thus collector be made cathode and electrolyte infiltration, make electrolyte with
Negative electrode active material comes into full contact with, and increases contact area, reduces battery polarization.
(2) graphene conductive is good, is capable of forming conductive network to improve overall conductivity, further decreases in battery
Resistance, while stable surface texture can promote cyclical stability and service life.
(3) the vertical graphene prepared through the invention is evenly distributed, and is firmly combined, and defect is few, and easy to operate, ginseng
Number is controllable, is suitable for large-scale production.
Detailed description of the invention
Fig. 1 is graphene-copper foil composite current collector scanning electron microscope image；
Wherein: a is business copper foil current collector, and b is that business applies carbon copper current collector, and c is vertical graphene-prepared by the present invention
Copper foil composite current collector；
Fig. 2 is the surface contact angle picture that three kinds of collectors measure, in which: a is business copper foil current collector, and b is the present invention
Vertical graphene-copper foil composite current collector of preparation, c are that business applies carbon copper current collector；
Fig. 3 is the impedance diagram of the lithium ion battery assembled with three kinds of collectors；Wherein: BC is business copper foil afflux
Body, VG are vertical graphene-copper foil composite current collector prepared by the present invention, and CC is that business applies carbon copper current collector；
Fig. 4 is the discharge capacity curve of the lithium ion battery assembled with three kinds of collectors, in which: BC is business copper foil
Collector, VG are vertical graphene-copper foil composite current collector prepared by the present invention, and CC is that business applies carbon copper current collector.
Fig. 5 is three kinds of batteries forthright test curve again, and wherein BC is business copper foil current collector, and VG is prepared by the present invention hangs down
Straight graphene-copper foil composite current collector, CC are that business applies carbon copper current collector.
Specific embodiment
The present invention is described further with reference to the accompanying drawing.
Embodiment 1
A kind of vertical graphene-copper foil composite current collector preparation method based on growth in situ, comprising the following steps:
(1) pretreatment of copper foil:
Acetone soln and ethanol solution will be successively used to be cleaned by ultrasonic 20min with a thickness of 20-60 μm of copper foil, then will be clear
Washed copper foil is placed in the HCl solution that concentration is 0.25mol/L, and 60 DEG C of water-bath 20min in water-bath are obtained pretreated
Copper foil；
(2) laminar nano copper-copper foil preparation: pretreated copper foil is placed in vacuum evaporation coating machine, lower than 1 ×
10-4Vacuum evaporation is carried out under the conditions of Pa, in the Nanometer Copper of copper foil surface vapor deposition 80nm thickness, nano copper particle size range is
350nm, repeats vapor deposition 5 times, and laminar nano copper-copper foil material is made；
(3) growth in situ of vertical graphene:
Pretreated copper foil is placed in the reaction chamber of plasma enhanced chemical vapor deposition (PECVD), is vacuumized simultaneously
It heats up according to the heating rate of 5 DEG C/min, vacuum degree is evacuated to 1 × 10-4Pa hereinafter, and reaction chamber warm table reach setting
After 890 DEG C of temperature, it is passed through argon gas and methane, volume ratio 1:4 reacts 60min under the conditions of pressure 550Pa and power 300W,
In the vertical graphene of copper foil surface growth in situ, vertical graphene-copper foil composite current collector is obtained.
The present invention provides a kind of half-cell assemble method, and carries out test analysis accordingly, and steps are as follows:
(1) half-cell active material slurry is prepared
By graphite powder, conductive carbon and as binder Kynoar (PVDF) according to 6:1:3 ratio mix, then
It is dissolved in grinding in solvent and uniformly, slurry is made；
(2) the coating preparation of collector:
The slurry prepared is coated uniformly on vertical graphene-copper foil composite current collector, vacuum oven is placed into
In 60 DEG C of dry 12h；
(3) half-cell assembles
Make anode with the sample prepared, cathode is done with business lithium piece, electrolyte is commercial Li-ion electrolyte, is being full of
CR2032 model lithium ion button shape cell is assembled in the glove box of argon gas.
Contrast sample is business copper foil current collector, business painting carbon copper current collector, and the method for assembled battery is identical.
Fig. 1 is business copper foil current collector, business painting carbon copper current collector and the scanning of vertical graphene-copper foil composite current collector
Sem image.It can be seen from the figure that business copper foil current collector surface is smooth, business applies carbon copper current collector surface, and there are nanoscales
There are micron order petal-like structures on fragment, vertical graphene-copper foil composite current collector surface, this shows in copper foil surface growth in situ
Graphene can be effectively improved surface texture, as shown in Fig. 2, the contact angle of three kinds of collectors is measured, it is produced by the present invention to hang down
The contact angle of straight graphene-copper foil composite current collector is 128.1 °, has super-hydrophobic oil-wet behavior, increases and active material
Contact area reduces impedance to increase bond strength.
Fig. 3 is the impedance diagram of the lithium ion battery assembled with three kinds of collectors.It can be seen from the figure that business applies carbon
Copper current collector and vertical graphene-copper foil composite current collector interface resistance are respectively 94.2 Ω and 58.6 Ω.It can be seen that hanging down
The internal resistance of straight graphene-copper foil composite current collector is lower, and the high conductivity for being primarily due to graphene enhances electric conductivity and reduces
Impedance.
Fig. 4 is the discharge capacity curve of the lithium ion battery assembled with three kinds of collectors.It can be seen from the figure that the greatest extent
For pipe in initial cycle, the rate capability of vertical graphene-copper foil current collector applies carbon copper current collector lower than business, but is continuously following
After ring, capacity is obviously reinforced.In 100 cycle periods, the capacity of vertical graphene-copper foil current collector is maintained at
190mAh/g applies the 160mAh/g of carbon copper current collector and the 90mAh/g of business copper foil current collector higher than business.This shows vertical stone
Black alkene-copper foil composite current collector can effectively improve discharge capacity, energy density and power density, be not susceptible to polarize, circulation
Stability is good.
Embodiment 2
A kind of vertical graphene-copper foil composite current collector preparation method based on growth in situ, comprising the following steps:
(1) pretreatment of copper foil:
Acetone soln and ethanol solution will be successively used to be cleaned by ultrasonic 20min with a thickness of 40 μm of copper foil, then will cleaning
The copper foil crossed is placed in the HCl solution that concentration is 0.25mol/L, and 60 DEG C of water-bath 20min in water-bath obtain pretreated copper
Foil；
(2) laminar nano copper-copper foil preparation: pretreated copper foil is placed in vacuum evaporation coating machine, lower than 1 ×
10-4Vacuum evaporation is carried out under the conditions of Pa, in the Nanometer Copper of copper foil surface vapor deposition 85nm thickness, nano copper particle size range is
380nm, repeats vapor deposition 4 times, and laminar nano copper-copper foil material is made；
(3) growth in situ of vertical graphene:
Pretreated copper foil is placed in the reaction chamber of plasma enhanced chemical vapor deposition (PECVD), is vacuumized simultaneously
It heats up according to the heating rate of 5 DEG C/min, vacuum degree is evacuated to 1 × 10-4Pa hereinafter, and reaction chamber warm table reach setting
After 950 DEG C of temperature, it is passed through argon gas and methane, volume ratio 1:5 reacts 80min under the conditions of pressure 500Pa and power 250W,
In the vertical graphene of copper foil surface growth in situ, vertical graphene-copper foil composite current collector is obtained.
Make anode with the sample prepared, cathode is done with business lithium piece, electrolyte is commercial Li-ion electrolyte, is being full of
CR2032 model lithium ion button shape cell is assembled in the glove box of argon gas.
Contrast sample is business copper foil current collector, business painting carbon copper current collector, and the method for assembled battery is identical.
Efficiency tests are carried out to three kinds of batteries, are illustrated in figure 5 the test data of three kinds of batteries forthright test again, as a result table
It is bright that more excellent battery performance is had based on vertical graphene obtained by the present invention-copper foil composite current collector assembled battery, far
It is more than business copper foil current collector, business applies the performance of carbon copper current collector.
In conclusion vertical graphene-copper foil composite current collector based on growth in situ is had excellent performance, can effectively improve existing
There is copper foil current collector surface microstructure, increase its bond strength with active material, improves the wellability of cathode and electrolyte
And reduce impedance.
Examples detailed above is present invention explanation further elucidated above, it should be pointed out that described embodiment is only it
Middle a part can not become limitation of the invention.The present invention is belonged to based on the improvement and modification that the principle of the invention is made
Protection scope within.
Claims (5)
1. a kind of vertical graphene-copper foil composite current collector preparation method based on growth in situ, which is characterized in that including with
Lower step:
(1) pretreatment of copper foil: acetone soln and ethanol solution will be successively used to be cleaned by ultrasonic with a thickness of 20-60 μm of copper foil
10-30min, then the copper foil cleaned is placed in the HCl solution that concentration is 0.1-1mol/L, 60 DEG C of water-baths in water-bath
20min obtains pretreated copper foil；
(2) laminar nano copper-copper foil preparation: pretreated copper foil is placed in vacuum evaporation coating machine, is being lower than 1 × 10- 4Vacuum evaporation is carried out under the conditions of Pa, in the Nanometer Copper of copper foil surface vapor deposition 80-90nm thickness, nano copper particle size range is
300-500nm, repeats vapor deposition 3-5 times, and laminar nano copper-copper foil material is made；
(3) growth in situ of vertical graphene: laminar nano copper-copper foil material made from step (2) is placed in plasma and is increased
In the reaction chamber of extensive chemical vapor deposition apparatus (PECVD), vacuumizes and heat up according to certain heating rate, in vacuum
Degree is evacuated to 1 × 10-4Pa hereinafter, and after reaction chamber warm table reaches set temperature, be passed through argon gas and carbon-source gas, setting pressure with
Power is reacted, and in the vertical graphene of copper foil surface growth in situ, obtains vertical graphene-copper foil composite current collector.
2. a kind of vertical graphene-copper foil composite current collector preparation method based on growth in situ as described in claim 1,
It is characterized in that, heating rate described in step (3) in the section 3-8 DEG C/min, sets holding temperature range as 700-1000
DEG C, the carbon-source gas is methane, ethylene or acetylene, and reaction pressure range is 400-600Pa, and reaction power range is 200-
350W, reaction time 50-80min.
3. a kind of vertical graphene-copper foil composite current collector preparation method based on growth in situ as described in claim 1,
It is characterized in that, the volume ratio of carbon-source gas described in step (3) and argon gas is 1:3-6.
4. a kind of vertical graphene-copper foil composite current collector based on growth in situ, which is characterized in that appointed by claim 1-3
Meaning one is prepared.
5. a kind of vertical graphene-copper foil composite current collector based on growth in situ as claimed in claim 4, feature exist
In the surface of the vertical graphene-copper foil composite current collector is in micron order petal-like structures, and contact angular region is 125-
143.5°。
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Cited By (6)
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| CN111883761A (en) * | 2020-08-05 | 2020-11-03 | 重庆信合启越科技有限公司 | Silicon graphene composite lithium battery negative electrode material and preparation method thereof |
| CN112421026A (en) * | 2020-11-19 | 2021-02-26 | 浙江南都电源动力股份有限公司 | Ni-based alloy-graphene current collector and preparation method and application thereof |
| CN112875684A (en) * | 2021-01-29 | 2021-06-01 | 江西师范大学 | Method for preparing vertical graphene from solid carbon-containing base material and vertical graphene |
| CN113909476A (en) * | 2020-07-10 | 2022-01-11 | 上海新池能源科技有限公司 | Method for growing graphene on structured copper base, cable core material and preparation method thereof |
| CN114156456A (en) * | 2021-12-08 | 2022-03-08 | 西北工业大学 | High-capacity rapid charge-discharge graphene @ hard carbon composite material, preparation method thereof and application of composite material in sodium ion battery |
| CN114566613A (en) * | 2022-03-03 | 2022-05-31 | 电子科技大学 | High-stability composite lithium negative electrode |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN113909476A (en) * | 2020-07-10 | 2022-01-11 | 上海新池能源科技有限公司 | Method for growing graphene on structured copper base, cable core material and preparation method thereof |
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| CN112421026A (en) * | 2020-11-19 | 2021-02-26 | 浙江南都电源动力股份有限公司 | Ni-based alloy-graphene current collector and preparation method and application thereof |
| CN112421026B (en) * | 2020-11-19 | 2022-04-19 | 浙江南都电源动力股份有限公司 | Ni-based alloy-graphene current collector and preparation method and application thereof |
| CN112875684A (en) * | 2021-01-29 | 2021-06-01 | 江西师范大学 | Method for preparing vertical graphene from solid carbon-containing base material and vertical graphene |
| CN114156456A (en) * | 2021-12-08 | 2022-03-08 | 西北工业大学 | High-capacity rapid charge-discharge graphene @ hard carbon composite material, preparation method thereof and application of composite material in sodium ion battery |
| CN114156456B (en) * | 2021-12-08 | 2023-04-14 | 西北工业大学 | High-capacity rapid charge-discharge graphene @ hard carbon composite material, preparation method thereof and application of composite material in sodium ion battery |
| CN114566613A (en) * | 2022-03-03 | 2022-05-31 | 电子科技大学 | High-stability composite lithium negative electrode |
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