CN105186004B - A kind of used as negative electrode of Li-ion battery copper current collector and its preparation method and application - Google Patents

A kind of used as negative electrode of Li-ion battery copper current collector and its preparation method and application Download PDF

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Publication number
CN105186004B
CN105186004B CN201510647862.8A CN201510647862A CN105186004B CN 105186004 B CN105186004 B CN 105186004B CN 201510647862 A CN201510647862 A CN 201510647862A CN 105186004 B CN105186004 B CN 105186004B
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ion battery
current collector
negative electrode
copper current
preparation
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CN105186004A (en
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王利娟
李新喜
马勤阁
孟召辉
陈宝宽
李艳
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Nanyang Normal University
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Nanyang Normal 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/661—Metal or alloys, e.g. alloy coatings
    • 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
    • H01M4/64—Carriers or collectors
    • H01M4/66—Selection of materials
    • H01M4/665—Composites
    • H01M4/667—Composites in the form of layers, e.g. coatings
    • 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 technical field of lithium ion, and in particular to a kind of used as negative electrode of Li-ion battery copper current collector and its preparation method and application.The present invention is pre-processed especially by copper foil, made annealing treatment, the formation of graphene layer, vacuum evaporation metal film, Quenching Treatment step are obtained in copper foil surface successively grapheme modified layer and metal nano-particle layer.Used as negative electrode of Li-ion battery copper current collector of the present invention, with good electric conductivity, can alleviate the erosion of electrolyte, strong with coating layer of active substance adhesion.

Description

A kind of used as negative electrode of Li-ion battery copper current collector and its preparation method and application
Technical field
The invention belongs to technical field of lithium ion, and in particular 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 as one of most green environmentally friendly clean energy resource, has been widely used now portable On formula electronic product, while being considered as the power source of very promising hybrid electric vehicle and pure electric vehicle.Lithium-ion electric Pond is mainly made up of parts such as active material, battery case, collector, barrier film, electrolyte.Wherein, collector is lithium ion battery One of important component, surface carry active matter and and electrolyte contacts, while both positive and negative polarity active material is produced Electronics is pooled to external circuit formation electric current by it.
Copper has enough mechanical strengths, good electric conductivity, the advantages of being difficult to occur alloying with lithium, be usually used in lithium from The collector of sub- GND.Present commercialized negative electrode of lithium ion battery Cu collectors are divided into double mainly using electrolysis Cu paper tinsels The several types such as face light, two-sided hair, one side hair, double-sided coarsening and high-elongation.But, Cu collection liquid surfaces easily generate oxidation Film, oxide-film belongs to semiconductor, can influence the electric conductivity of collector；Cu collectors in battery charge and discharge process easily with electrolysis The solvent and impurity of liquid react dissolving, make Cu unstable, meanwhile, the oxide on Cu surfaces is easily and lithium ion generation deintercalation Reaction, the volumetric expansion of generation is shunk, and the coating layer of active substance on Cu surfaces is come off；In addition, negative as the high power capacity of representative using silicon Great variety occurs for pole material volume in charge and discharge cycles, causes the separation of electrode material and Cu collectors.
The content of the invention
To overcome drawbacks described above, an object of the present invention is to provide a kind of used as negative electrode of Li-ion battery copper current collector, With good electric conductivity, the erosion of electrolyte can be alleviated, it is strong with coating layer of active substance adhesion.
Second object of the present invention, which is also resided in, provides a kind of preparation method of used as negative electrode of Li-ion battery copper current collector.
Third object of the present invention also resides in the application for providing a kind of copper current collector in lithium ion battery.
To achieve the above object, the present invention is adopted the following technical scheme that：
A kind of used as negative electrode of Li-ion battery copper current collector, on copper current collector surface successively grapheme modified layer and metal nano Stratum granulosum.
According to above-mentioned used as negative electrode of Li-ion battery copper current collector, the metal is the one or several kinds in Cu, Au, Ag Alloy.
According to above-mentioned used as negative electrode of Li-ion battery copper current collector, the graphene layer thickness is 0.5~2 nm.
According to above-mentioned used as negative electrode of Li-ion battery copper current collector, the average grain diameter of the metal nanoparticle for 10~ 100 nm。
A kind of preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, comprises the following steps：
（1）Polishing or pickling Cu paper tinsels, 40~60 DEG C of 30~60 min of vacuum drying, obtain drying Cu paper tinsels；
（2）By step（1）Cu paper tinsels are dried, are placed in CVD tube furnaces, under reducing atmosphere, 950~1060 DEG C of calcinings 20~ 70 min；
（3）By step（2）Cu paper tinsels after calcining are put into anoxic reactor, are heated to 950~1060 DEG C, to reactor In be filled with carbon source, the min of constant temperature 5~60 is cooled to room temperature under reducing atmosphere, obtain graphite linings alkene modification Cu paper tinsels, graphite Alkene thickness degree is 0.5~2 nm；
（4）In graphene layer surface vacuum deposited metal film, thickness is 4~20 nm；
（5）Under reducing atmosphere, 250~350 DEG C of Quenching Treatment steps（4）The min of metal film 20~50, makes graphene layer Surface forms metal nano-particle layer, obtains product copper current collector.
According to the preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, step（1）Described acid washing method is： Ultrasonically treated 5~15 min of acid solution, the acid solution is acetic acid or oxalic acid solution, and concentration is 0.5~2 molL-1。
According to the preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, step（2）Or step（5）Described in Reducing atmosphere be H2Or Ar and H2Gaseous mixture, step（3）Described reducing atmosphere is H2。
According to the preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, step（3）Described in carbon source be gas Body carbon source, 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 are methane, second Alkynes 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 for 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 poly- Styrene.
A kind of application of copper current collector of above-mentioned preparation in lithium ion battery.
The positive beneficial effect of the present invention：
1. the present invention is with chemical vapour deposition technique（CVD）There is the graphene layer of high conductivity in Cu Growns, Then metal film is because the presence of surface tension is broken after metal film with good conductivity, Quenching Treatment are deposited on graphene layer Split contraction, form metal nano-particle layer, the metal nanoparticle and Cu substrates of graphene and good conductivity can form good Good conductive network.
The graphene layer grown using CVD can be very good to cover the surface of full Cu substrates, can so alleviate electrolysis Erosion of the liquid to Cu collectors, and graphene is a kind of carbon atom according to sp2Hydridization is arranged, and is interconnected to cellular Network structure, it has the excellent properties such as high transmittance, high conductivity, high mechanical properties and bigger serface, can improve Cu The electric conductivity of collector；Metal nanoparticle can increase the specific surface area and degree of roughness of Cu collectors, can so increase The contact area and bonding force of strongly active material and collector, and then reversible specific capacity and the circulation of lithium ion battery can be improved Performance.
2. graphene is passed through reducibility gas in growth course, making the oxide on surface of Cu substrates, to be reduced to Cu mono- Matter, and then the resistance of Cu substrates is reduced, the Cu paper tinsels of this structure can be reduced into work as collector used for negative pole of lithium ion battery The Charge-transfer resistance of property thing and afflux body interface, so as to 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, lithium ion battery is significantly improved Chemical property, can be widely applied to lithium ion battery.
Brief description of the drawings
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 the lithium ion battery of embodiment 1 in 2 Ag-1First charge-discharge curve map under electric current；
Fig. 3 is the lithium ion battery of embodiment 1 in 2 Ag-1Cycle performance figure under electric current；
Fig. 4 is the lithium ion battery of embodiment 1 in 4 Ag-1With 6 Ag-1Cycle performance figure under electric current；
Fig. 5 schemes for the section SEM of the lithium ion battery negative electrode of embodiment 1；
Fig. 6 schemes for the section SEM of control lithium ion battery negative electrode；
Fig. 7 schemes for the SEM of the copper current collector of embodiment 2；
Fig. 8 is SEM figure of the copper current collector of embodiment 2 after ultrasonically treated 15 min；
Fig. 9 is the section SEM figures of cathode pole piece after the lithium ion battery of embodiment 2 is circulated 200 times under 1 C electric currents；
The section SEM figures of cathode pole piece after Figure 10 is circulated 200 times for control lithium ion battery under 1 C electric currents；
Figure 11 is the lithium ion battery of the preparation of embodiment 3 in 0.5 Ag-1Cycle performance figure under electric current.
Embodiment
With reference to some embodiments, the present invention is further described.
Embodiment 1
Referring to Fig. 1~6, a kind of used as negative electrode of Li-ion battery copper current collector, in copper foil surface successively grapheme modified layer and Au nano-particle layers, graphene layer thickness is 1 nm, and the average grain diameter of Au nano particles is 27 nm.
The preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, comprises the following steps：
（1）Using 1 molL-1The ultrasonically treated min of copper foil 10 of acetum, then with water and ethanol rinse, vacuum 50 DEG C of 30 min of drying, obtain dry Cu paper tinsels；
（2）By step（1）Dry Cu paper tinsels are placed in CVD tube furnaces in H2Under air-flow 60 min, H are calcined in 1045 DEG C2 Flow is 10 sccm；
（3）Using CH4For carbon source, CH is passed through at 1045 DEG C4And H2, CH4Flow is 1 sccm, H2
Flow is 2 sccm, the min of constant temperature 15, in H2Room temperature, H are cooled under atmosphere2Flow is 10 sccm, obtains graphite The Cu paper tinsels of alkene layer modification, graphene layer thickness is 1 nm；
（4）Au films are deposited in graphene layer surface vacuum, Au film thicknesses are 8 nm；
（5）Au films are in H2With lower 300 DEG C of min of Quenching Treatment 30 of Ar gas shields, graphene layer surface is formed Au and receive Rice grain layer, H2Flow is 600 sccm, the sccm of Ar flows 600, obtains products C u collectors.
Influence of the Cu collectors of the present invention to battery performance is detected using button half-cell, lithium ion battery uses embodiment The 1 Cu paper tinsels prepared are collector, lithium titanate zinc（Li2ZnTi3O8, LZTO）For active material, lithium ion battery is labeled as Cu-G- Au-LZTO。
As control lithium ion battery using the nano-particle modified Cu paper tinsels of unused graphene and Au as collector, lithium titanate zinc （Li2ZnTi3O8, LZTO）For active material, lithium ion battery is labeled as Cu-LZTO.
Fig. 2 is the present embodiment lithium ion battery in 2 Ag-1First charge-discharge curve map under electric current, Cu-LZTO and Cu- The specific discharge capacity of G-Au-LZTO lithium ion batteries is respectively 212.2 and 242.1 mAhg-1, it is seen that present invention graphene The Cu collectors modified jointly with Au nano particles significantly improve the specific discharge capacity of battery.
Fig. 3 is the present embodiment lithium ion battery in 2 Ag-1Cycle performance figure under electric current, Cu-LZTO and Cu-G-Au- LZTO lithium ion batteries are respectively 160.0 and 219.4 mAhg in secondary specific discharge capacity-1, the ratio after circulating 200 times Capacity is respectively 136.1 and 204.9 mAhg-1, it is respectively 85.1% and 93.4%, sheet relative to secondary capability retention The Cu collectors that invention is modified jointly with graphene and Au nano particles significantly improve the cycle performance of battery.
Fig. 4 is the present embodiment lithium ion battery in 4 Ag-1With 6 Ag-1Cycle performance figure under electric current, circulation 100 The specific discharge capacity of secondary rear battery is respectively 172.2 and 130.0 mAhg-1, lithium ion battery of the present invention shows good big Current charge-discharge electrical property.
Fig. 5 is to be schemed with the section SEM of Cu-G-Au-LZTO lithium ion battery negative electrodes manufactured in the present embodiment, from figure It can be seen that coating layer of active substance is with the space very little between collector, illustrate that there is good bonding force between the two；Fig. 6 is The section SEM figures of Cu-LZTO lithium ion battery negative electrodes are compareed, as can be seen from the figure active matter matter coatings are with collector Between space it is larger, illustrate poor adhesion between the two.
Embodiment 2
Referring to Fig. 1, Fig. 7~10, a kind of used as negative electrode of Li-ion battery copper current collector is grapheme modified successively in copper foil surface Layer and alloy nanoparticle layer, graphene layer thickness is 1 nm, and described alloy is Au and Ag alloys, and both mass ratioes are 1:1, Alloy nanoparticle average grain diameter is 50 nm.
The preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, comprises the following steps：
（1）Using 1 molL-1The ultrasonically treated min of Cu paper tinsels 15 of oxalic acid solution, then with water and ethanol rinse, vacuum 60 DEG C of 40 min of drying, obtain dry Cu paper tinsels；
（2）Dry Cu paper tinsels are placed in CVD tube furnaces in H2Under air-flow 20 min, H are calcined in 1050 DEG C2Flow is 10 sccm；
（3）Using CH4For carbon source, CH is passed through at 1060 DEG C4And H2, CH4Flow is 1 sccm, H2Flow is 2 sccm, permanent 10 min of temperature, in H2Protection drops to room temperature, H2Flow is 10 sccm, obtains the Cu paper tinsels of graphene layer modification, graphene thickness Spend for 1 nm；
（4）Au and Ag alloy films are deposited in graphene layer surface vacuum, alloy film thickness is 12 nm；
（5）Au and Ag alloy films are in H2Lower 250 DEG C of Quenching Treatment alloy films 50 min of gas shield, makes graphene layer table Face forms alloy nanoparticle layer, H2Flow is 700 sccm, obtains products C u collectors.
Influence of the Cu collectors to battery performance is detected using button half-cell, lithium ion battery is prepared with embodiment 2 Cu paper tinsels are collector, lithium titanate（Li4Ti5O12, LTO）For active material, lithium ion battery is labeled as Cu-G-Au/Ag-LTO.
As control lithium ion battery using unused graphene and the Cu paper tinsels of Au/Ag alloy nanoparticles modification as collector, Lithium titanate（Li4Ti5O12, LTO）For active material, lithium ion battery is labeled as Cu-LTO.
Fig. 7 is the SEM figures of Cu collectors manufactured in the present embodiment, and Fig. 8 is Cu collectors manufactured in the present embodiment in ultrasound The figures of the SEM after 15 min are handled, it can be seen that ultrasonically treated rear graphene and alloy nanoparticle do not take off from Fig. 7 and Fig. 8 Fall, illustrate that the graphene and alloy nanoparticle decorative layer and Cu that are prepared using the present invention have good adhesion.
Fig. 9 is cathode pole piece after the present embodiment Cu-G-Au/Ag-LTO lithium ion batteries are circulated 200 times under 1 C electric currents Section SEM schemes, and Figure 10 is the section SEM for compareing cathode pole piece after Cu-LTO lithium ion batteries are circulated 200 times under 1 C electric currents Figure, negative electrode active material coating is serious with collector segregation phenomenon after control Cu-LTO lithium ion battery circulations, Cu-G- of the present invention Au/Ag-LTO lithium ion battery negative pole active materials coating between collector have good bonding force, circulation 100 times after both There is no obvious segregation phenomenon.
Embodiment 3
Referring to Fig. 1 and 11, a kind of used as negative electrode of Li-ion battery copper current collector, in copper foil surface successively grapheme modified layer and Ag nano-particle layers, graphene layer thickness is 2 nm, and the average grain diameter of Ag nano particles is 22 nm.
The preparation method of above-mentioned used as negative electrode of Li-ion battery copper current collector, comprises the following steps：
（1）Polished using mechanical polisher, 40 DEG C of 30 min of drying of vacuum obtain dry Cu paper tinsels；
（2）Dry Cu paper tinsels are placed in CVD tube furnaces in Ar and H2Under air-flow 70 min, Ar flows are calcined in 1060 DEG C For 200 sccm, H2Flow is 20 sccm；
（3）Use polystyrene for carbon source, H is passed through at 950 DEG C2, H2Flow is 2 sccm, the min of constant temperature 30, in H2Protect Shield drops to room temperature, H2Flow is 15 sccm, obtains the Cu paper tinsels of graphene layer modification, and graphene layer thickness is 2 nm；
（4）Ag films are deposited in graphene layer surface vacuum, Ag film thicknesses are 4 nm；
（5）Ag metal films are in H2With lower 350 DEG C of min of Quenching Treatment 20 of Ar gas shields, form graphene layer surface Ag nano-particle layers, H2Flow is 500 sccm, and Ar flows are 500 sccm, obtain products C u collectors.
Influence of the Cu collectors to battery performance is detected using button half-cell, lithium ion battery is prepared with embodiment 3 Cu paper tinsels are collector, and graphite is active material, and lithium ion battery is labeled as Cu-G-Ag-graphite.
As control lithium ion battery using the nano-particle modified Cu of unused graphene and Ag as collector, graphite is activity Material, lithium ion battery is labeled as Cu-graphite.
It is respectively 50 and 27 using four-point probe blank testing Cu and the Cu of modification manufactured in the present embodiment resistance M Ω, it is seen that the present invention significantly improves the electric conductivity of Cu collectors using graphene and the nano-particle modified Cu paper tinsels of Ag.
Figure 11 is the present embodiment Cu-G-Ag-graphite lithium ion batteries in 0.5 Ag-1Cycle performance under electric current Figure, Cu-G-Ag-graphite lithium ion batteries have larger specific capacity in whole cyclic process, it can be seen that graphene The Cu collectors modified jointly with Ag nano particles can significantly improve the reversible specific capacity of battery.

Claims (8)

1. a kind of used as negative electrode of Li-ion battery copper current collector, it is characterised in that in copper foil surface successively grapheme modified layer and gold Metal nano-particle layer, the metal is Au and/or Ag, and the average grain diameter of the metal nanoparticle is 10~100 nm.
2. used as negative electrode of Li-ion battery copper current collector according to claim 1, it is characterised in that the graphene layer thickness For 0.5~2 nm.
3. the preparation method of the used as negative electrode of Li-ion battery copper current collector described in a kind of claim 1, it is characterised in that including such as Lower step：
（1）Polishing or pickling Cu paper tinsels, 40~60 DEG C of 30~60 min of vacuum drying, obtain drying Cu paper tinsels；
（2）By step（1）Cu paper tinsels are dried, are placed in CVD tube furnaces, under reducing atmosphere, 950~1060 DEG C of calcinings 20~70 min；
（3）By step（2）Cu paper tinsels after calcining are put into anoxic reactor, are heated to 950~1060 DEG C, are filled into reactor Enter carbon source, the min of constant temperature 5~60 is cooled to room temperature under reducing atmosphere, obtain the Cu paper tinsels of graphene layer modification, graphene layer Thickness is 0.5~2 nm；
（4）In graphene layer surface vacuum deposited metal film, thickness is 4~20 nm；
（5）Under reducing atmosphere, 250~350 DEG C of Quenching Treatment steps（4）The min of metal film 20~50, makes graphene layer surface Metal nano-particle layer is formed, product copper current collector is obtained.
4. the preparation method of used as negative electrode of Li-ion battery copper current collector according to claim 3, it is characterised in that step （1）Described acid washing method is：Ultrasonically treated 5~15 min of acid solution, the acid solution is acetic acid or oxalic acid solution, concentration For 0.5~2 molL-1。
5. the preparation method of used as negative electrode of Li-ion battery copper current collector according to claim 3, it is characterised in that step （2）Or step（5）Described in reducing atmosphere be H2Or Ar and H2Gaseous mixture, step（3）Described reducing atmosphere is H2。
6. the preparation method of used as negative electrode of Li-ion battery copper current collector according to claim 3, it is characterised in that step （3）Described in carbon source be gaseous carbon sources, liquid carbon source or solid carbon source.
7. the preparation method of used as negative electrode of Li-ion battery copper current collector according to claim 6, it is characterised in that described Gaseous carbon sources are methane, acetylene or ethene, and described liquid carbon source is ethanol or benzene, described solid carbon source for naphthalene or Polystyrene.
8. a kind of application of the copper current collector prepared by any one of claim 3~7 in lithium ion battery.
CN201510647862.8A 2015-10-09 2015-10-09 A kind of used as negative electrode of Li-ion battery copper current collector and its preparation method and application Expired - Fee Related CN105186004B (en)

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CN106654288B (en) * 2017-01-19 2023-05-23 华南理工大学 Copper micro-tube porous current collector for lithium ion battery and preparation method thereof
CN106935794B (en) * 2017-03-15 2019-08-06 陈熙野 A kind of preparation method for copper electrode of gilding
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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
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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
CN113594466B (en) * 2021-07-05 2023-07-28 东莞新能安科技有限公司 Current collector, battery core and electricity utilization device
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