CN105186004A - Copper current collector for lithium-ion battery anodes as well as preparation method and application of copper current collector - Google Patents
Copper current collector for lithium-ion battery anodes as well as preparation method and application of copper current collector Download PDFInfo
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- CN105186004A CN105186004A CN201510647862.8A CN201510647862A CN105186004A CN 105186004 A CN105186004 A CN 105186004A CN 201510647862 A CN201510647862 A CN 201510647862A CN 105186004 A CN105186004 A CN 105186004A
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- ion battery
- current collector
- copper current
- negative electrode
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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
- 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
- H01M4/64—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 belongs to the technical field of lithium-ion batteries, and particularly relates to a copper current collector for lithium-ion battery anodes as well as a preparation method and an application of the copper current collector. A copper foil surface is modified with a graphene layer and a metal nanoparticle layer sequentially, and to be specific, the copper current collector is obtained through steps of pretreatment of copper foil, annealing treatment, formation of the graphene layer, vacuum evaporation of a metal film and quenching treatment. The copper current collector for the lithium-ion battery anodes has good conductivity, can relieve corrosion caused by electrolytes and has large binding force with active material coatings.
Description
Technical field
The invention belongs to technical field of lithium ion, be specifically related to a kind of used as negative electrode of Li-ion battery copper current collector and its preparation method and application.
Background technology
Lithium ion battery is considered to one of clean energy resource of most environmental protection, has been widely used on portable type electronic product now, has been considered to very promising hybrid electric vehicle and the power source of pure electric vehicle simultaneously.Lithium ion battery is primarily of parts compositions such as active material, battery case, collector, barrier film, electrolyte.Wherein, collector is one of important component part of lithium ion battery, surface carry active matter and and electrolyte contacts, simultaneously by both positive and negative polarity active material produce electronics by it be pooled to external circuit formed electric current.
Copper has enough mechanical strengths, good conductivity, not easily with advantages such as lithium generation alloyings, is usually used in the collector of lithium ion battery negative.Present business-like lithium ion battery negative Cu collector mainly adopts electrolysis Cu paper tinsel, is divided into the several types such as dual light, two-sided hair, one side hair, double-sided coarsening and high-elongation.But Cu collection liquid surface easily generates oxide-film, and oxide-film belongs to semiconductor, the conductivity of collector can be affected; Cu collector in battery charge and discharge process easily and the solvent of electrolyte and impurity react and dissolve, make Cu unstable, meanwhile, the oxide on Cu surface easily and lithium ion generation deintercalation react, the volumetric expansion produced is shunk, and the coating layer of active substance on Cu surface is come off; In addition, take silicon as high-capacity cathode material volume generation great variety in charge and discharge cycles of representative, cause being separated of electrode material and Cu collector.
Summary of the invention
For overcoming above-mentioned defect, an object of the present invention is to provide a kind of used as negative electrode of Li-ion battery copper current collector, has good conductivity, can alleviate the erosion of electrolyte, strong with coating layer of active substance adhesion.
Second object of the present invention is also the preparation method providing a kind of used as negative electrode of Li-ion battery copper current collector.
3rd object of the present invention is also to provide the application of a kind of copper current collector in lithium ion battery.
For achieving the above object, the present invention adopts following technical scheme:
A kind of used as negative electrode of Li-ion battery copper current collector, grapheme modified layer and metal nano-particle layer successively on copper current collector surface.
According to above-mentioned used as negative electrode of Li-ion battery copper current collector, described metal is one or several the alloy in Cu, Au, Ag.
According to above-mentioned used as negative electrode of Li-ion battery copper current collector, described graphene layer thickness is 0.5 ~ 2nm.
According to above-mentioned used as negative electrode of Li-ion battery copper current collector, the average grain diameter of described metal nanoparticle is 10 ~ 100nm.
A preparation method for above-mentioned used as negative electrode of Li-ion battery copper current collector, comprises the steps:
(1) polishing or pickling Cu paper tinsel, 40 ~ 60 DEG C of vacuumize 30 ~ 60min, obtain dry Cu paper tinsel;
(2) by dry for step (1) Cu paper tinsel, CVD tube furnace is placed in, under reducing atmosphere, 950 ~ 1060 DEG C of calcining 20 ~ 70min;
(3) anoxic reactor put into by the Cu paper tinsel after step (2) being calcined, and is heated to 950 ~ 1060 DEG C, in reactor, is filled with carbon source, constant temperature 5 ~ 60min, cool to room temperature under reducing atmosphere, obtain the Cu paper tinsel that graphite linings alkene is modified, graphene layer thickness is 0.5 ~ 2nm;
(4) at graphene layer surface vacuum deposited metal film, thickness is 4 ~ 20nm;
(5) under reducing atmosphere, 250 ~ 350 DEG C of Quenching Treatment step (4) metal film 20 ~ 50min, make graphene layer surface form metal nano-particle layer, obtain product copper current collector.
According to the preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, the acid washing method described in step (1) is: the ultrasonic process 5 ~ 15min of acid solution, and described acid solution is acetic acid or oxalic acid solution, and concentration is 0.5 ~ 2molL
-1.
According to the preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, step (2) or the reducing atmosphere described in step (5) are H
2or Ar and H
2gaseous mixture, the reducing atmosphere described in step (3) is H
2.
According to the preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, the carbon source described in step (3) is gaseous carbon sources, liquid carbon source or solid carbon source.
According to the preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, described gaseous carbon sources is methane, acetylene or ethene.
According to the preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, described liquid carbon source is ethanol or benzene.
According to the preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, described solid carbon source is naphthalene or polystyrene.
A kind of application of copper current collector in lithium ion battery of above-mentioned preparation.
positive beneficial effect of the present invention:
1. the present invention has the graphene layer of high conductivity at Cu Grown with chemical vapour deposition technique (CVD), then the metal film that evaporation conductivity is good on graphene layer, after Quenching Treatment, metal film to break contraction due to capillary existence, form metal nano-particle layer, metal nanoparticle and the Cu substrate of Graphene and good conductivity can form good conductive network.
Adopt the graphene layer of CVD growth can well cover the surface of full Cu substrate, the erosion of electrolyte to Cu collector can be alleviated like this, and Graphene is that a kind of carbon atom is according to sp
2hydridization is arranged, and is interconnected to cellular network configuration, and it has the excellent properties such as high permeability, high conductivity, high mechanical properties and bigger serface, can improve the electric conductivity of Cu collector; Metal nanoparticle can increase specific area and the degree of roughness of Cu collector, like this can the contact area of enhanced activity material and collector and bonding force, and then can improve reversible specific capacity and the cycle performance of lithium ion battery.
2. Graphene passes into reducibility gas in growth course, the oxide on surface of Cu substrate is made to be reduced to Cu simple substance, and then reduce the resistance of Cu substrate, the Cu paper tinsel of this structure can be reduced the Charge-transfer resistance at active matter and collector interface as collector used for negative pole of lithium ion battery, thus be conducive to the performance of lithium ion battery chemical property.
3. used as negative electrode of Li-ion battery copper current collector preparation method of the present invention is simple, significantly improves the chemical property of lithium ion battery, can be widely used in lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the structural representation of used as negative electrode of Li-ion battery copper current collector of the present invention;
Fig. 2 is that embodiment 1 lithium ion battery is at 2Ag
-1first charge-discharge curve chart under electric current;
Fig. 3 is that embodiment 1 lithium ion battery is at 2Ag
-1cycle performance figure under electric current;
Fig. 4 is that embodiment 1 lithium ion battery is at 4Ag
-1and 6Ag
-1cycle performance figure under electric current;
Fig. 5 is the section S EM figure of embodiment 1 lithium ion battery negative electrode;
Fig. 6 is the section S EM figure of contrast lithium ion battery negative electrode;
Fig. 7 is the SEM figure of embodiment 2 copper current collector;
Fig. 8 is the SEM figure of embodiment 2 copper current collector after ultrasonic process 15min;
Fig. 9 is that embodiment 2 lithium ion battery circulates the section S EM figure of cathode pole piece after 200 times under 1C electric current;
Figure 10 is that the contrast lithium ion battery section S EM of cathode pole piece after 200 times that circulate under 1C electric current schemes;
Figure 11 is that the lithium ion battery of embodiment 3 preparation is at 0.5Ag
-1cycle performance figure under electric current.
Embodiment
Below in conjunction with some embodiments, the present invention is further described.
Embodiment 1
See Fig. 1 ~ 6, a kind of used as negative electrode of Li-ion battery copper current collector, at copper foil surface successively grapheme modified layer and Au nano-particle layer, graphene layer thickness is the average grain diameter of 1nm, Au nano particle is 27nm.
The preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, comprises the steps:
(1) 1molL is adopted
-1acetum ultrasonic process Copper Foil 10min, then use water and ethanol rinse, vacuum 50 DEG C of dry 30min, obtain dry Cu paper tinsel;
(2) the Cu paper tinsel that step (1) is dry is placed in CVD tube furnace at H
2in 1045 DEG C of calcinings 60min, H under air-flow
2flow is 10sccm;
(3) CH is adopted
4for carbon source, pass into CH at 1045 DEG C
4and H
2, CH
4flow is 1sccm, H
2
Flow is 2sccm, and constant temperature 15min, at H
2cool to room temperature under atmosphere, H
2flow is 10sccm, and obtain the Cu paper tinsel that graphene layer is modified, graphene layer thickness is 1nm;
(4) at graphene layer surface vacuum evaporation Au film, Au film thickness is 8nm;
(5) Au film is at H
2300 DEG C Quenching Treatment 30mins lower to Ar Buchholz protection, make graphene layer surface form Au nano-particle layer, H
2flow is 600sccm, Ar flow 600sccm, obtains products C u collector.
Adopt button half-cell to detect Cu collector of the present invention to the impact of battery performance, the Cu paper tinsel that lithium ion battery adopts embodiment 1 to prepare is collector, lithium titanate zinc (Li
2znTi
3o
8, LZTO) and be active material, lithium ion battery is labeled as Cu-G-Au-LZTO.
Lithium ion battery is not to use Graphene and the nano-particle modified Cu paper tinsel of Au for collector in contrast, lithium titanate zinc (Li
2znTi
3o
8, LZTO) and be active material, lithium ion battery is labeled as Cu-LZTO.
Fig. 2 is that the present embodiment lithium ion battery is at 2Ag
-1first charge-discharge curve chart under electric current, the specific discharge capacity of Cu-LZTO and Cu-G-Au-LZTO lithium ion battery is respectively 212.2 and 242.1mAhg
-1, the Cu collector that visible the present invention's Graphene and Au nano particle are modified jointly significantly improves the specific discharge capacity of battery.
Fig. 3 is that the present embodiment lithium ion battery is at 2Ag
-1cycle performance figure under electric current, Cu-LZTO and Cu-G-Au-LZTO lithium ion battery is respectively 160.0 and 219.4mAhg at secondary specific discharge capacity
-1, the specific capacity after 200 times that circulates is respectively 136.1 and 204.9mAhg
-1, be respectively 85.1% and 93.4% relative to secondary capability retention, the Cu collector that the present invention's Graphene and Au nano particle are modified jointly significantly improves the cycle performance of battery.
Fig. 4 is that the present embodiment lithium ion battery is at 4Ag
-1and 6Ag
-1cycle performance figure under electric current, the specific discharge capacity of battery after 100 times that circulates is respectively 172.2 and 130.0mAhg
-1, lithium ion battery of the present invention shows good high rate during charging-discharging.
Fig. 5 is the section S EM figure of the Cu-G-Au-LZTO lithium ion battery negative electrode prepared with the present embodiment, and as can be seen from the figure coating layer of active substance is very little with the space between collector, illustrates to have good bonding force between the two; Fig. 6 is the section S EM figure of contrast Cu-LZTO lithium ion battery negative electrode, and as can be seen from the figure active matter matter coatings is comparatively large with the space between collector, and poor adhesion is between the two described.
Embodiment 2
See Fig. 1, Fig. 7 ~ 10, a kind of used as negative electrode of Li-ion battery copper current collector, at copper foil surface successively grapheme modified layer and alloy nanoparticle layer, graphene layer thickness is 1nm, and described alloy is Au and Ag alloy, both mass ratioes are 1:1, and alloy nanoparticle average grain diameter is 50nm.
The preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, comprises the steps:
(1) 1molL is adopted
-1oxalic acid solution ultrasonic process Cu paper tinsel 15min, then use water and ethanol rinse, vacuum 60 DEG C of dry 40min, obtain dry Cu paper tinsel;
(2) the Cu paper tinsel of drying is placed in CVD tube furnace at H
2in 1050 DEG C of calcinings 20min, H under air-flow
2flow is 10sccm;
(3) CH is adopted
4for carbon source, pass into CH at 1060 DEG C
4and H
2, CH
4flow is 1sccm, H
2flow is 2sccm, and constant temperature 10min, at H
2protection drops to room temperature, H
2flow is 10sccm, and obtain the Cu paper tinsel that graphene layer is modified, graphene layer thickness is 1nm;
(4) at graphene layer surface vacuum evaporation Au and Ag alloy film, alloy film thickness is 12nm;
(5) Au and Ag alloy film is at H
2the lower 250 DEG C of Quenching Treatment alloy film 50min of Buchholz protection, make graphene layer surface form alloy nanoparticle layer, H
2flow is 700sccm, obtains products C u collector.
Adopt button half-cell to detect Cu collector to the impact of battery performance, the Cu paper tinsel that lithium ion battery is prepared with embodiment 2 for collector, lithium titanate (Li
4ti
5o
12, LTO) and be active material, lithium ion battery is labeled as Cu-G-Au/Ag-LTO.
Lithium ion battery is not to use the Cu paper tinsel of Graphene and the modification of Au/Ag alloy nanoparticle for collector in contrast, lithium titanate (Li
4ti
5o
12, LTO) and be active material, lithium ion battery is labeled as Cu-LTO.
Fig. 7 is the SEM figure of Cu collector prepared by the present embodiment, Fig. 8 is the SEM figure of Cu collector after ultrasonic process 15min prepared by the present embodiment, can find out ultrasonic process from Fig. 7 and Fig. 8 after, Graphene and alloy nanoparticle do not come off, and illustrate that Graphene prepared by employing the present invention and alloy nanoparticle decorative layer and Cu have good adhesion.
Fig. 9 is that the present embodiment Cu-G-Au/Ag-LTO lithium ion battery circulates the section S EM figure of cathode pole piece after 200 times under 1C electric current, Figure 10 is that the contrast Cu-LTO lithium ion battery section S EM of cathode pole piece after 200 times that circulate under 1C electric current schemes, after the circulation of contrast Cu-LTO lithium ion battery, negative electrode active material coating is serious with collector segregation phenomenon, Cu-G-Au/Ag-LTO lithium ion battery negative pole active materials coating of the present invention, with having good bonding force between collector, does not have obvious segregation phenomenon both circulate after 100 times.
Embodiment 3
See Fig. 1 and 11, a kind of used as negative electrode of Li-ion battery copper current collector, at copper foil surface successively grapheme modified layer and Ag nano-particle layer, graphene layer thickness is the average grain diameter of 2nm, Ag nano particle is 22nm.
The preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, comprises the steps:
(1) adopt mechanical polisher polishing, vacuum 40 DEG C of dry 30min, obtain dry Cu paper tinsel;
(2) the Cu paper tinsel of drying is placed in CVD tube furnace at Ar and H
2calcining 70min, Ar flows in 1060 DEG C under air-flow is 200sccm, H
2flow is 20sccm;
(3) adopt polystyrene to be carbon source, pass into H at 950 DEG C
2, H
2flow is 2sccm, and constant temperature 30min, at H
2protection drops to room temperature, H
2flow is 15sccm, and obtain the Cu paper tinsel that graphene layer is modified, graphene layer thickness is 2nm;
(4) at graphene layer surface vacuum evaporation Ag film, Ag film thickness is 4nm;
(5) Ag metal film is at H
2350 DEG C Quenching Treatment 20mins lower to Ar Buchholz protection, make graphene layer surface form Ag nano-particle layer, H
2flow is 500sccm, Ar flow is 500sccm, obtains products C u collector.
Adopt button half-cell to detect Cu collector to the impact of battery performance, the Cu paper tinsel that lithium ion battery is prepared with embodiment 3 is for collector, and graphite is active material, and lithium ion battery is labeled as Cu-G-Ag-graphite.
Lithium ion battery is not to use Graphene and the nano-particle modified Cu of Ag for collector in contrast, and graphite is active material, and lithium ion battery is labeled as Cu-graphite.
The resistance of the Cu of the modification adopting four-point probe blank testing Cu and the present embodiment to prepare is respectively 50 and 27m Ω, and visible the present invention adopts Graphene and the nano-particle modified Cu paper tinsel of Ag to significantly improve the conductivity of Cu collector.
Figure 11 is that the present embodiment Cu-G-Ag-graphite lithium ion battery is at 0.5Ag
-1cycle performance figure under electric current, in whole cyclic process, Cu-G-Ag-graphite lithium ion battery has larger specific capacity, can find out that Cu collector that Graphene and Ag nano particle are modified jointly can significantly improve the reversible specific capacity of battery.
Claims (10)
1. a used as negative electrode of Li-ion battery copper current collector, is characterized in that, at copper foil surface successively grapheme modified layer and metal nano-particle layer.
2. used as negative electrode of Li-ion battery copper current collector according to claim 1, is characterized in that, described metal is one or several the alloy in Cu, Au, Ag.
3. used as negative electrode of Li-ion battery copper current collector according to claim 1, is characterized in that, described graphene layer thickness is 0.5 ~ 2nm.
4. the used as negative electrode of Li-ion battery copper current collector according to any one of claims 1 to 3, is characterized in that, the average grain diameter of described metal nanoparticle is 10 ~ 100nm.
5. a preparation method for used as negative electrode of Li-ion battery copper current collector according to claim 1, is characterized in that, comprise the steps:
(1) polishing or pickling Cu paper tinsel, 40 ~ 60 DEG C of vacuumize 30 ~ 60min, obtain dry Cu paper tinsel;
(2) by dry for step (1) Cu paper tinsel, CVD tube furnace is placed in, under reducing atmosphere, 950 ~ 1060 DEG C of calcining 20 ~ 70min;
(3) anoxic reactor put into by the Cu paper tinsel after step (2) being calcined, and is heated to 950 ~ 1060 DEG C, in reactor, is filled with carbon source, constant temperature 5 ~ 60min, cool to room temperature under reducing atmosphere, obtain the Cu paper tinsel that graphene layer is modified, graphene layer thickness is 0.5 ~ 2nm;
(4) at graphene layer surface vacuum deposited metal film, thickness is 4 ~ 20nm;
(5) under reducing atmosphere, 250 ~ 350 DEG C of Quenching Treatment step (4) metal film 20 ~ 50min, make graphene layer surface form metal nano-particle layer, obtain product copper current collector.
6. the preparation method of used as negative electrode of Li-ion battery copper current collector according to claim 5, it is characterized in that, acid washing method described in step (1) is: the ultrasonic process 5 ~ 15min of acid solution, and described acid solution is acetic acid or oxalic acid solution, and concentration is 0.5 ~ 2molL
-1.
7. the preparation method of used as negative electrode of Li-ion battery copper current collector according to claim 5, is characterized in that, step (2) or the reducing atmosphere described in step (5) are H
2or Ar and H
2gaseous mixture, the reducing atmosphere described in step (3) is H
2.
8. the preparation method of used as negative electrode of Li-ion battery copper current collector according to claim 5, is characterized in that, the carbon source described in step (3) is gaseous carbon sources, liquid carbon source or solid carbon source.
9. the preparation method of used as negative electrode of Li-ion battery copper current collector according to claim 5, it is characterized in that, described gaseous carbon sources is methane, acetylene or ethene, and described liquid carbon source is ethanol or benzene, and described solid carbon source is naphthalene or polystyrene.
10. the application of copper current collector in lithium ion battery prepared by an any one of claim 5 ~ 9.
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| CN106654288A (en) * | 2017-01-19 | 2017-05-10 | 华南理工大学 | Copper micron tube porous current collector used for lithium ion battery and preparation method for copper micron tube porous current collector |
| CN106935794A (en) * | 2017-03-15 | 2017-07-07 | 陈熙野 | A kind of preparation method of copper electrode of gilding |
| CN107394138A (en) * | 2017-07-04 | 2017-11-24 | 中国科学院上海高等研究院 | Lithium ion battery negative material structure, lithium ion battery and preparation method thereof |
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| CN112735847A (en) * | 2020-12-23 | 2021-04-30 | 广东风华高新科技股份有限公司 | Lithium ion capacitor negative electrode plate with Cu transition layer and preparation method and application thereof |
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| CN107502870A (en) * | 2016-08-12 | 2017-12-22 | 深圳市烯谷能源控股有限公司 | A kind of method for improving lithium battery anode aluminium foil colelctor electrode electrical property |
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| CN107394138A (en) * | 2017-07-04 | 2017-11-24 | 中国科学院上海高等研究院 | Lithium ion battery negative material structure, lithium ion battery and preparation method thereof |
| CN107394138B (en) * | 2017-07-04 | 2020-03-24 | 中国科学院上海高等研究院 | Lithium ion battery cathode material structure, lithium ion battery and preparation method thereof |
| CN110190286A (en) * | 2019-05-24 | 2019-08-30 | 吉林大学 | A kind of vertical graphene-copper foil composite current collector and preparation method thereof based on growth in situ |
| CN112735847A (en) * | 2020-12-23 | 2021-04-30 | 广东风华高新科技股份有限公司 | Lithium ion capacitor negative electrode plate with Cu transition layer and preparation method and application thereof |
| CN113594466A (en) * | 2021-07-05 | 2021-11-02 | 东莞新能安科技有限公司 | Current collector, battery cell and power utilization device |
| CN116072884A (en) * | 2023-03-20 | 2023-05-05 | 安徽维纳物联科技有限公司 | Composite porous current collector copper foil of lithium battery and preparation method thereof |
| CN116072884B (en) * | 2023-03-20 | 2023-06-13 | 安徽维纳物联科技有限公司 | Composite porous current collector copper foil of lithium battery and preparation method thereof |
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