CN108063218A - A kind of preparation method of sheet metal lithium base cathode - Google Patents
A kind of preparation method of sheet metal lithium base cathode Download PDFInfo
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- CN108063218A CN108063218A CN201711378721.6A CN201711378721A CN108063218A CN 108063218 A CN108063218 A CN 108063218A CN 201711378721 A CN201711378721 A CN 201711378721A CN 108063218 A CN108063218 A CN 108063218A
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- Prior art keywords
- lithium
- sheet metal
- preparation
- copper foil
- metal lithium
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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
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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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
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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
- H01M4/04—Processes of manufacture in general
- H01M4/0438—Processes of manufacture in general by electrochemical processing
- H01M4/045—Electrochemical coating; Electrochemical impregnation
- H01M4/0452—Electrochemical coating; Electrochemical impregnation from solutions
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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
- H01M4/06—Electrodes for primary cells
- H01M4/08—Processes of manufacture
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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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
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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 present invention relates to modern batteries technical fields, specifically disclose a kind of preparation method of sheet metal lithium base cathode, cathode is first using copper foil current collector as substrate, single-layer graphene film is synthesized on copper foil current collector surface using chemical vapour deposition technique, using this graphene/copper as cathode electrolytic cell is assembled into the rich lithium material or lithium salts as anode lithium source, and it is sealed after injecting electrolyte, electro-deposition is carried out with relatively low current density again, electrolytic cell is disassembled after the suitable reaction time, you can obtains being coated with the lithium base cathode of thin uniform layer lithium metal in cathode portion；Method using the present invention, can realize the uniform deposition of lithium metal, while overcome the generation of a large amount of Li dendrites directly caused by the lithium deposition of copper current collector surface, be applied to the primary and secondary battery of lithium so as to obtain the lithium titanate cathode material of safer stabilization.
Description
Technical field
The invention belongs to field of lithium, and in particular to a kind of preparation method of sheet metal lithium base cathode.
Background technology
With a series of high-tech electricity such as scientific and technical in recent years progress and development, smart mobile phone, intelligent wearable device
Sub- product greatly facilitates the production and living of people, while the electric vehicle using tesla as representative also begins to become people's trip
A big selection.Therefore, higher objective requirement also is proposed to the battery for wherein undertaking energy supply effect.
Traditional lead-acid battery, manganese-zinc battery etc. are unsuitable because of its limited capacity and huge quality volume etc.
Rise applied to these small-sized or high-power electrical equipments instead the lithium battery of high specific energy.However, market
On the miniaturization of equipment, lighting objective demand are also promoted lithium battery than can continuous improvement and technological innovation.
For the graphite cathode in current lithium battery, directly it can be thinned, mitigate significantly using lithium anode
The quality and volume of battery, however Li dendrite can be generated by directly using cathode of lithium charge, and caused to puncture membrane, triggered short circuit
The even serious safety issue such as explosion.
The content of the invention
The present invention is directed to propose a kind of preparation method for solving the problems, such as the charging of Metal Substrate cathode of lithium and generating Li dendrite, can prepare
Obtain uniform sheet metal lithium base cathode.
The technical solution adopted by the present invention to solve the technical problems is：A kind of preparation side of sheet metal lithium base cathode
Method, cathode synthesize mono-layer graphite first using copper foil current collector as substrate, using chemical vapour deposition technique on copper foil current collector surface
Alkene film is assembled into electrolytic cell with the rich lithium material or lithium salts as anode lithium source using this graphene/copper as cathode, and injects
Sealed after electrolyte, then electro-deposition carried out with relatively low current density, disassembled after the suitable reaction time electrolytic cell to get
To the lithium base cathode for being coated with thin uniform layer lithium metal.
Further, the graphene/copper synthesis step is：Copper foil is cut into suitable size to be put into quartz ampoule, in argon
1000 DEG C or so are warming up to diamond heating in gas, hydrogen mixing atmosphere, methane gas is then passed to and carries out graphene growth, warp
30 minutes or so rear closing methane gas are crossed, starts to cool down, obtains the copper foil with graphene film；The electrodeposition step
For：Electrolytic cell is assembled in inert atmosphere glove box, the electrolyte is to contain 1M LiPF6Mass ratio be 1：1：1
EC/DMC/DEC mixed liquors are encapsulated in soft-package battery or button cell, then carry out constant current plating.
A kind of preparation method of sheet metal lithium base cathode, rich lithium material are metal lithium sheet；The lithium salts
For LiCoO2（Cobalt acid lithium）.
A kind of preparation method of sheet metal lithium base cathode, metal lithium sheet thickness are not less than 80 μm, can make
It is standby to obtain thickness up to 20 μm of sheet metal cathode of lithium.
A kind of preparation method of sheet metal lithium base cathode, the metal copper foil polished using surface, the table of copper foil
Surface roughness is less than 200 nm.
A kind of preparation method of sheet metal lithium base cathode is less than 1 mA/cm using current density2Constant current
Electricity carries out plating lithium.
Further, the electro-deposition current density is 0.1-0.5 mA/cm2。
The beneficial effects of the invention are as follows：
Preparation method of the present invention is synthesized using copper foil current collector as raw material using the method for simple chemical vapor deposition above
The thickness uniformly lithium anode material without apparent dendrite can be realized in this, as the substrate of electro-deposition sheet metal lithium in graphene
Material；Method using the present invention, can realize the uniform deposition of lithium metal, while overcome directly in copper current collector surface lithium deposition
The generation of caused a large amount of Li dendrites is applied to the primary and secondary electricity of lithium so as to obtain the lithium titanate cathode material of safer stabilization
Pond；With/without the lithium deposition results of graphene copper foil after being disassembled by comparison, the deposition of the lithium in graphene/copper foil substrate is found
It is apparent more homogeneous, and in electro-deposition, the lower overpotential of graphene/copper foil surface also can prove that lithium is more easy to deposit.
Description of the drawings
Fig. 1 be with/without disassembled after the copper foil surface lithium electro-deposition of graphene picture comparison；
Voltage curve comparison diagram when Fig. 2 is the copper foil surface lithium electro-deposition with/without graphene.
Specific embodiment
The present invention is described in further detail with reference to the accompanying drawings and examples.
Embodiment 1
Fig. 1 be with/without disassembled after the copper foil surface lithium electro-deposition of graphene picture comparison：(a) it is white without graphene copper foil surface
Non-ferrous metal lithium deposition is seldom and uneven；（b）Graphene/copper foil surface white metal lithium deposition is big and uniform.
Voltage curve comparison diagram when Fig. 2 is the copper foil surface lithium electro-deposition with/without graphene：The voltage of graphene/copper foil
Curve is smoother steadily to be raised, and has lower overpotential, illustrates that electro-deposition lithium is evenly stablized
Copper foil is cut into suitable size to be put into quartz ampoule, is warming up in argon gas, hydrogen mixing atmosphere with diamond heating
Near 1000 DEG C, methane gas is passed through afterwards and carries out graphene growth, methane gas was closed after 30 minutes, starts to cool down, obtain
Copper foil with graphene film.
Electrolytic cell is assembled in inert atmosphere glove box afterwards, using graphene/copper foil as cathode, 80 μm of lithium pieces are as sun
Pole, electrolyte are to contain 1M LiPF6Mass ratio be 1：1：1 EC/DMC/DEC mixed liquors, are encapsulated in soft-package battery or button
In formula battery.Then constant current electro-deposition is carried out.
Preferred plan is as follows：The copper foil polished using surface carries out electro-deposition, electrolyte using 80 μm of lithium piece as anode
To contain 1M LiPF6Mass ratio be 1：1：1 EC/DMC/DEC mixed liquors, current density during electro-deposition are 0.1-0.5
mA/cm2。
The embodiment that the above-described embodiments merely illustrate the principles and effects of the present invention and part uses, for
For those of ordinary skill in the art, without departing from the concept of the premise of the invention, can also make it is several deformation and
It improves, these belong to protection scope of the present invention.
Claims (7)
1. a kind of preparation method of sheet metal lithium base cathode, it is characterised in that：First using copper foil current collector as substrate, using change
Learn vapour deposition process and synthesize single-layer graphene film on copper foil current collector surface, using this graphene/copper as cathode with as positive
The rich lithium material or lithium salts of pole are assembled into electrolytic cell, and are sealed after injecting electrolyte, then carry out electricity with relatively low current density and sink
Product disassembles electrolytic cell to get to sheet metal lithium base cathode after the suitable reaction time.
A kind of 2. preparation method of sheet metal lithium base cathode according to claim 1, which is characterized in that the graphite
Alkene/copper synthesis step is：Copper foil is cut into suitable size to be put into quartz ampoule, tube furnace is used in argon gas, hydrogen mixing atmosphere
1000 DEG C or so are heated to, methane gas is then passed to and carries out graphene growth, methane gas was closed by 30 minutes or so, opens
Begin to cool down, obtain the copper foil with graphene film；The electrodeposition step is：Electrolysis is assembled in inert atmosphere glove box
Pond, the electrolyte are to contain 1M LiPF6Mass ratio be 1：1：1 EC/DMC/DEC mixed liquors, are encapsulated in soft-package battery
Or in button cell, constant current plating is then carried out.
A kind of 3. preparation method of sheet metal lithium base cathode according to claim 2, which is characterized in that the rich lithium
Material is metal lithium sheet；The lithium salts is LiCoO2。
A kind of 4. preparation method of sheet metal lithium base cathode according to claim 3, which is characterized in that the metal
Lithium piece thickness is not less than 80 μm.
5. a kind of preparation method of sheet metal lithium base cathode according to claim 1 or 2 or 3 or 4, which is characterized in that
The copper foil polished using surface, the surface roughness of copper foil are less than 200 nm.
6. the preparation method of a kind of sheet metal lithium base cathode according to claim 5, which is characterized in that close using electric current
Degree is less than 1 mA/cm2Constant Electric Current carry out plating lithium.
7. the preparation method of a kind of sheet metal lithium base cathode according to claim 6, which is characterized in that the electricity sinks
Product current density is 0.1-0.5 mA/cm2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201711378721.6A CN108063218A (en) | 2017-12-19 | 2017-12-19 | A kind of preparation method of sheet metal lithium base cathode |
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| CN201711378721.6A CN108063218A (en) | 2017-12-19 | 2017-12-19 | A kind of preparation method of sheet metal lithium base cathode |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109671902A (en) * | 2018-11-28 | 2019-04-23 | 上海空间电源研究所 | A kind of long-life lithium metal battery cathode preparation method and lithium battery |
| CN111416156A (en) * | 2020-03-30 | 2020-07-14 | 武汉中原长江科技发展有限公司 | Non-lithium substrate ASEI for negative electrode of lithium metal secondary battery and preparation method thereof |
| CN112117437A (en) * | 2019-06-20 | 2020-12-22 | 北京航空航天大学 | Lithium metal composite electrode capable of controlling nucleation and growth of lithium metal and preparation method thereof |
| CN114566616A (en) * | 2022-03-03 | 2022-05-31 | 广州鹏辉能源科技股份有限公司 | Lithium ion battery and method for supplementing lithium by graphite material |
| CN114566613A (en) * | 2022-03-03 | 2022-05-31 | 电子科技大学 | High-stability composite lithium negative electrode |
| CN115020657A (en) * | 2022-07-27 | 2022-09-06 | 西安交通大学 | Alkali metal composite cathode and integrated preparation method thereof |
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| CN102694158A (en) * | 2012-06-13 | 2012-09-26 | 上海空间电源研究所 | Silicon-containing lithium cathode, preparation method thereof and lithium sulfur battery with silicon-containing lithium cathode |
| CN103682368A (en) * | 2012-09-20 | 2014-03-26 | 中国科学院金属研究所 | Rapidly charged flexible lithium ion battery and preparation method of electrodes of rapidly charged flexible lithium ion battery |
| CN105098143A (en) * | 2014-05-16 | 2015-11-25 | 中国科学院金属研究所 | Flexible high-sulfur load self-repairing cathode structure for lithium-sulfur battery and preparation method of flexible high-sulfur load self-repairing cathode structure |
| CN106702441A (en) * | 2016-12-19 | 2017-05-24 | 天齐锂业股份有限公司 | Method for preparing lithium strip by means of continuous electrodeposition |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109671902A (en) * | 2018-11-28 | 2019-04-23 | 上海空间电源研究所 | A kind of long-life lithium metal battery cathode preparation method and lithium battery |
| CN112117437A (en) * | 2019-06-20 | 2020-12-22 | 北京航空航天大学 | Lithium metal composite electrode capable of controlling nucleation and growth of lithium metal and preparation method thereof |
| CN111416156A (en) * | 2020-03-30 | 2020-07-14 | 武汉中原长江科技发展有限公司 | Non-lithium substrate ASEI for negative electrode of lithium metal secondary battery and preparation method thereof |
| CN114566616A (en) * | 2022-03-03 | 2022-05-31 | 广州鹏辉能源科技股份有限公司 | Lithium ion battery and method for supplementing lithium by graphite material |
| CN114566613A (en) * | 2022-03-03 | 2022-05-31 | 电子科技大学 | High-stability composite lithium negative electrode |
| CN114566616B (en) * | 2022-03-03 | 2022-11-15 | 广州鹏辉能源科技股份有限公司 | Lithium ion battery and method for supplementing lithium by using graphite material |
| CN115020657A (en) * | 2022-07-27 | 2022-09-06 | 西安交通大学 | Alkali metal composite cathode and integrated preparation method thereof |
| CN115020657B (en) * | 2022-07-27 | 2024-01-30 | 西安交通大学 | Alkali metal composite negative electrode and integrated preparation method thereof |
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Application publication date: 20180522 |