CN108346778A - A kind of electrochemical method preparing ultra-thin lithium an- ode - Google Patents
A kind of electrochemical method preparing ultra-thin lithium an- ode Download PDFInfo
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- CN108346778A CN108346778A CN201810122459.7A CN201810122459A CN108346778A CN 108346778 A CN108346778 A CN 108346778A CN 201810122459 A CN201810122459 A CN 201810122459A CN 108346778 A CN108346778 A CN 108346778A
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- lithium
- ode
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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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- 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
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Abstract
The invention discloses a kind of method preparing ultra-thin lithium an- ode, belong to can charge and discharge high specific energy secondary battery technology.The processing step of this method is:The electrolyte aqueous solution that molar concentration is 0.01 5.0mol/L is prepared first, and copper electrode is immersed into aqueous solution later;Copper electrode after cleaning and dipping and drying;Using copper electrode and lithium foil as electrode, electro-deposition is carried out in non-aqueous liquid electrolyte to get the ultra-thin lithium an- ode for being 0.1~10 micron to thickness.Operating method of the present invention is simple, convenient for large-scale production and quantitative control;The thickness of prepared ultra-thin cathode of lithium breaks through the thickness of the lithium foil obtained by existing machinery roll-in, can meet the needs of lithium metal battery development;The thickness of ultra-thin lithium can be adjusted by the method for adjusting electrodeposition time and current density, have prodigious flexibility.
Description
Technical field
The present invention relates to a kind of electrochemical method preparing ultra-thin lithium an- ode, belong to can charge and discharge the secondary electricity of high specific energy
Pool technology field.
Background technology
During the production of the energy and effective use, energy storage technology plays extremely important role, wherein can fill
The secondary cell put is one of most important energy storage technology.With the fast developments of portable consumer electronics, new-energy automobile
It widelys popularize and the construction of intelligent grid, existing lithium ion battery cannot meet the needs of state and society.Have
More high specific energy, safe secondary cell becomes whole society's focus of attention.New breakthrough needs are innovated from material system, because
This, science researcher again focuses on sight in the lithium metal battery field using lithium metal as cathode.Lithium metal is used as negative
It is great to have natural advantage, such as most negative electrode potential (- 3.040V), high theoretical capacity (3860mAh g-1).These
Special property makes lithium metal battery have higher volume energy density, to meet growing social demand.
It in lithium battery, is limited by the internal confined space, battery needs store more energy in limited volume.
Therefore, the volume shared by the electrode in battery, diaphragm, collector and various accessories is smaller, is more conducive to the volume for improving battery
And mass energy density.And in lithium metal battery, the theoretical specific capacity of cathode lithium is 3860mAh g-1, it is far longer than anode
Specific capacity (generally 200-400mAh g-1).Even if in the case where considering that cathode is slightly excessive, the volume of cathode lithium, again smaller than
The quality of positive active material.Therefore, positive active material can be increased by minimizing volume shared by cathode lithium to promote electricity
The volume and mass energy density in pond.But it is limited by mechanical rolling equipment, the thickness of existing lithium foil is difficult to be less than 20 microns.
So exploitation prepares technology of the lithium foil thickness less than 20 microns and has important meaning for the energy density for promoting lithium metal battery
Justice.
Invention content
The object of the present invention is to provide a kind of electrochemical methods preparing ultra-thin lithium an- ode, to meet lithium metal battery
In for ultra-thin lithium an- ode demand.
Technical scheme is as follows:
A kind of electrochemical method preparing ultra-thin lithium an- ode, it is characterised in that this method comprises the following steps:
1) it prepares electrolyte molar concentration and is the aqueous solution of 0.01-5.0mol/L, and copper electrode is immersed into aqueous solution;
2) copper electrode after cleaning and dipping and drying;
3) using copper electrode and lithium foil as electrode, electro-deposition is carried out in non-aqueous liquid electrolyte, it is 0.1- that thickness, which can be obtained,
10 microns of ultra-thin lithium an- ode.
Preferably, the electrolyte in aqueous solution be lithium nitrate, it is LiBF4, lithium hexafluoro phosphate, dioxalic acid lithium borate, double
One or more of trifluoromethanesulfonimide lithium and double fluorine sulfimide lithiums.
Preferably, used copper electrode is copper foil, copper mesh or foam copper.
Preferably, the non-aqueous liquid electrolyte is made of lithium hexafluoro phosphate and esters solvent, wherein hexafluorophosphoric acid
Lithium molar concentration is 0.1-5.0mol/L, and esters solvent is the mixture of ethylene carbonate and diethyl carbonate.
The present invention compared with prior art, has the following advantages that and high-lighting effect:Operating method of the present invention is simple, convenient for big
The production of scale and quantitative control;The thickness of prepared ultra-thin cathode of lithium breaks through the thickness of the lithium foil obtained by existing machinery roll-in
Degree can meet the needs of lithium metal battery development;The thickness of ultra-thin lithium can pass through the side of adjusting electrodeposition time and current density
Method adjusts, and has prodigious flexibility.
Specific implementation mode
The present invention provides a kind of electrochemical method preparing ultra-thin lithium an- ode, is as follows:
1) it prepares electrolyte molar concentration and is the aqueous solution of 0.01-5.0mol/L, and copper electrode is immersed into aqueous solution;
2) copper electrode after cleaning and dipping and drying;
3) using copper electrode and lithium foil as electrode, electro-deposition is carried out in non-aqueous liquid electrolyte, it is 0.1- that thickness, which can be obtained,
10 microns of ultra-thin lithium an- ode.
Electrolyte in the present invention in aqueous solution be lithium nitrate, LiBF4, lithium hexafluoro phosphate, dioxalic acid lithium borate,
One or more of double trifluoromethanesulfonimide lithiums and double fluorine sulfimide lithiums.
Copper electrode used in the present invention is copper foil, copper mesh or foam copper.
The electro-deposition electrolyte group used in the present invention becomes lithium hexafluoro phosphate and esters solvent, wherein lithium hexafluoro phosphate
Molar concentration is 0.1-5.0mol/L, and esters solvent is the mixture of ethylene carbonate and diethyl carbonate.
With reference to example, the present invention will be further described, but protection scope of the present invention is not limited to reality below
Apply example.
Embodiment 1:It prepares molar concentration and is the lithium nitrate aqueous solution of 1.0mol/L, and copper foil is immersed.Cleaning leaching
Copper foil after bubble and drying.Using copper foil and lithium foil as electrode, carried out in the esters solvent containing 1.0mol/L lithium hexafluoro phosphates
Electro-deposition, current density 0.5mAcm-2, sedimentation time is 1 hour.The thickness of gained lithium metal sedimentary is 2.5 microns.
Embodiment 2:It prepares molar concentration and is the LiBF4 aqueous solution of 0.5mol/L, and foam copper is immersed.
Foam copper after cleaning and dipping and drying.Using foam copper and lithium foil as electrode, in the esters containing 2.0mol/L lithium hexafluoro phosphates
Electro-deposition, current density 0.5mAcm are carried out in solvent-2, sedimentation time is 2 hours.The thickness of gained lithium metal sedimentary is 5
Micron.
Embodiment 3:It prepares molar concentration and is the lithium hexafluoro phosphate aqueous solution of 2.0mol/L, and copper foil is immersed.Clearly
Wash the copper foil after impregnating and drying.Using copper foil and lithium foil as electrode, in the esters solvent containing 3.0mol/L lithium hexafluoro phosphates
Carry out electro-deposition, current density 1mAcm-2, sedimentation time is 2 hours.The thickness of gained lithium metal sedimentary is 10 microns.
Embodiment 4:It prepares molar concentration and is double fluorine sulfimide lithium aqueous solutions of 5.0mol/L, and foam copper is immersed it
In.Foam copper after cleaning and dipping and drying.Using foam copper and lithium foil as electrode, in the ester containing 0.5mol/L lithium hexafluoro phosphates
Electro-deposition, current density 2.0mAcm are carried out in class solvent-2, sedimentation time is 1 hour.The thickness of gained lithium metal sedimentary
It is 10 microns.
Embodiment 5:Double trifluoromethanesulfonimide lithium aqueous solutions that molar concentration is 0.01mol/L are prepared, and by 200 mesh
Copper mesh be immersed.Copper mesh after cleaning and dipping and drying.Using copper mesh and lithium foil as electrode, containing 0.1mol/L hexafluoro phosphorus
Electro-deposition, current density 0.1mAcm are carried out in the esters solvent of sour lithium-2, sedimentation time is 0.2 hour.Gained lithium metal is heavy
The thickness of lamination is 0.1 micron.
Embodiment 6:The lithium hexafluoro phosphate aqueous solution that molar concentration is 0.1mol/L is prepared, and the copper mesh of 400 mesh is immersed
Wherein.Copper mesh after cleaning and dipping and drying.Using copper mesh and lithium foil as electrode, in the esters containing 4.0mol/L lithium hexafluoro phosphates
Electro-deposition, current density 2mAcm are carried out in solvent-2, sedimentation time is 1 hour.The thickness of gained lithium metal sedimentary is 10
Micron.
Embodiment 7:Prepare the lithium hexafluoro phosphate water of double trifluoromethanesulfonimide lithiums and 1.0mol/L containing 1.0mol/L
Solution, and copper foil is immersed.Copper foil after cleaning and dipping and drying.Using copper foil and lithium foil as electrode, containing 1.5mol/
Electro-deposition, current density 5mAcm are carried out in the esters solvent of L lithium hexafluoro phosphates-2, sedimentation time is 0.2 hour.Gained lithium gold
The thickness for belonging to sedimentary is 5 microns.
Embodiment 8:Prepare double fluoroform sulphurs of double trifluoromethanesulfonimide lithiums and 2.0mol/L containing 2.0mol/L
Imide li aqueous solution, and copper foil is immersed.Copper foil after cleaning and dipping and drying.Using copper foil and lithium foil as electrode,
Electro-deposition, current density 10mAcm are carried out in esters solvent containing 1.0mol/L lithium hexafluoro phosphates-2, sedimentation time 0.2
Hour.The thickness of gained lithium metal sedimentary is 10 microns.
Embodiment 9:Prepare double trifluoromethanesulfonimide lithiums containing 2.0mol/L, double fluoroform sulphonyl of 2.0mol/L
The lithium hexafluoro phosphate aqueous solution of imine lithium and 1.0mol/L, and foam copper is immersed.Foam copper after cleaning and dipping and baking
It is dry.Using foam copper and lithium foil as electrode, electro-deposition is carried out in the esters solvent containing 1.0mol/L lithium hexafluoro phosphates, electric current is close
Degree is 20mAcm-2, sedimentation time is 0.1 hour.The thickness of gained lithium metal sedimentary is 10 microns.
Embodiment 10:The lithium hexafluoro phosphate aqueous solution containing 0.05mol/L is prepared, and foam copper is immersed.Cleaning leaching
Foam copper after bubble and drying.Using foam copper and lithium foil as electrode, in the esters solvent containing 2.0mol/L lithium hexafluoro phosphates
Carry out electro-deposition, current density 0.2mAcm-2, sedimentation time is 10 hours.The thickness of gained lithium metal sedimentary is 10 micro-
Rice.
Embodiment 11:The lithium hexafluoro phosphate aqueous solution containing 0.025mol/L is prepared, and 300 mesh copper mesh are immersed.Clearly
Wash the copper mesh after impregnating and drying.Using copper mesh and lithium foil as electrode, containing 2.0mol/L lithium hexafluoro phosphates, 1.0mol/L nitric acid
Electro-deposition, current density 0.1mAcm are carried out in the esters solvent of lithium-2, sedimentation time is 0.50 hour.Gained lithium metal deposits
The thickness of layer is 0.3 micron.
Embodiment 12:The lithium hexafluoro phosphate aqueous solution containing 0.025mol/L is prepared, and copper mesh is immersed.Cleaning and dipping
Copper mesh afterwards and drying.Using copper mesh and lithium foil as electrode, containing the bis- trifluoromethanesulfonimide lithiums of 1.0mol/L, 0.5mol/L
Electro-deposition, current density 0.05mAcm are carried out in the esters solvent of lithium nitrate-2, sedimentation time is 0.30 hour.Gained lithium gold
The thickness for belonging to sedimentary is 0.12 micron.
Claims (4)
1. a kind of electrochemical method preparing ultra-thin lithium an- ode, it is characterised in that this method comprises the following steps:
1) electrolyte aqueous solution that molar concentration is 0.01-5.0mol/L is prepared, copper electrode is then immersed into aqueous solution;
2) copper electrode after cleaning and dipping and drying;
3) using copper electrode and lithium foil as electrode, electro-deposition is carried out in non-aqueous liquid electrolyte to get being 0.1~10 micro- to thickness
The ultra-thin lithium an- ode of rice.
2. a kind of electrochemical method preparing ultra-thin lithium an- ode described in accordance with the claim 1, which is characterized in that described
Electrolyte is lithium nitrate, lithium hexafluoro phosphate, LiBF4, dioxalic acid lithium borate, double trifluoromethanesulfonimide lithiums and double fluorine
One or more of sulfimide lithium.
3. a kind of electrochemical method preparing ultra-thin lithium an- ode described in accordance with the claim 1, which is characterized in that the copper
Electrode is copper foil, copper mesh or foam copper.
4. a kind of electrochemical method preparing ultra-thin lithium an- ode described in accordance with the claim 1, which is characterized in that described
Non-aqueous liquid electrolyte is made of lithium hexafluoro phosphate and esters solvent, wherein lithium hexafluoro phosphate molar concentration is 0.1-
5.0mol/L, esters solvent are the mixture of ethylene carbonate and diethyl carbonate.
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Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109273664A (en) * | 2018-09-13 | 2019-01-25 | 中国电子科技集团公司第十八研究所 | Electrochemical preparation method of ultrathin lithium foil |
CN109524708A (en) * | 2018-09-11 | 2019-03-26 | 湖南立方新能源科技有限责任公司 | High-energy-density flexible-package metal lithium battery |
CN110504451A (en) * | 2019-08-09 | 2019-11-26 | 电子科技大学 | A kind of preparation method of ultra-thin lithium an- ode |
CN111081968A (en) * | 2018-10-19 | 2020-04-28 | 通用汽车环球科技运作有限责任公司 | Negative electrode for lithium secondary battery and method for manufacturing same |
CN112216819A (en) * | 2019-07-10 | 2021-01-12 | 上海展枭新能源科技有限公司 | Large-scale production method of copper-lithium composite electrode |
CN116598617A (en) * | 2023-07-18 | 2023-08-15 | 帕瓦(长沙)新能源科技有限公司 | Lithium metal composite negative electrode, preparation method thereof and battery |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101162772A (en) * | 2007-10-12 | 2008-04-16 | 哈尔滨工业大学 | Spume lithium cathode of lithium metal secondary batteries and method for producing the same |
CN105655649A (en) * | 2016-03-30 | 2016-06-08 | 武汉大学 | Incombustible electro-deposition lithium battery and application thereof |
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 |
CN106784635A (en) * | 2017-01-13 | 2017-05-31 | 北京科技大学 | A kind of solid state battery preparation method for being combined cathode of lithium |
CN107093705A (en) * | 2017-03-22 | 2017-08-25 | 清华大学 | A kind of cathode of lithium surface treatment method of lithium metal battery |
-
2018
- 2018-02-07 CN CN201810122459.7A patent/CN108346778A/en active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101162772A (en) * | 2007-10-12 | 2008-04-16 | 哈尔滨工业大学 | Spume lithium cathode of lithium metal secondary batteries and method for producing the same |
CN105655649A (en) * | 2016-03-30 | 2016-06-08 | 武汉大学 | Incombustible electro-deposition lithium battery and application thereof |
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 |
CN106784635A (en) * | 2017-01-13 | 2017-05-31 | 北京科技大学 | A kind of solid state battery preparation method for being combined cathode of lithium |
CN107093705A (en) * | 2017-03-22 | 2017-08-25 | 清华大学 | A kind of cathode of lithium surface treatment method of lithium metal battery |
Non-Patent Citations (1)
Title |
---|
XIN-BING CHENG 等: "《Dendrite-Free Lithium Deposition Induced by Uniformly Distributed Lithium Ions for Efficient Lithium Metal Batteries》", 《ADV. MATER.》 * |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109524708A (en) * | 2018-09-11 | 2019-03-26 | 湖南立方新能源科技有限责任公司 | High-energy-density flexible-package metal lithium battery |
CN109273664A (en) * | 2018-09-13 | 2019-01-25 | 中国电子科技集团公司第十八研究所 | Electrochemical preparation method of ultrathin lithium foil |
CN111081968A (en) * | 2018-10-19 | 2020-04-28 | 通用汽车环球科技运作有限责任公司 | Negative electrode for lithium secondary battery and method for manufacturing same |
CN111081968B (en) * | 2018-10-19 | 2023-08-29 | 通用汽车环球科技运作有限责任公司 | Negative electrode for lithium secondary battery and method for manufacturing same |
CN112216819A (en) * | 2019-07-10 | 2021-01-12 | 上海展枭新能源科技有限公司 | Large-scale production method of copper-lithium composite electrode |
CN112216819B (en) * | 2019-07-10 | 2021-10-15 | 上海展枭新能源科技有限公司 | Large-scale production method of copper-lithium composite electrode |
CN110504451A (en) * | 2019-08-09 | 2019-11-26 | 电子科技大学 | A kind of preparation method of ultra-thin lithium an- ode |
CN110504451B (en) * | 2019-08-09 | 2022-03-15 | 电子科技大学 | Preparation method of ultrathin lithium metal cathode |
CN116598617A (en) * | 2023-07-18 | 2023-08-15 | 帕瓦(长沙)新能源科技有限公司 | Lithium metal composite negative electrode, preparation method thereof and battery |
CN116598617B (en) * | 2023-07-18 | 2023-09-12 | 帕瓦(长沙)新能源科技有限公司 | Lithium metal composite negative electrode, preparation method thereof and battery |
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