CN111710841A - Electro-deposition lithium-carbon-silver composite negative electrode material for lithium battery and preparation method thereof - Google Patents

Electro-deposition lithium-carbon-silver composite negative electrode material for lithium battery and preparation method thereof Download PDF

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Publication number
CN111710841A
CN111710841A CN202010585317.1A CN202010585317A CN111710841A CN 111710841 A CN111710841 A CN 111710841A CN 202010585317 A CN202010585317 A CN 202010585317A CN 111710841 A CN111710841 A CN 111710841A
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lithium
carbon
negative electrode
silver
electrode material
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段华南
田然
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Maanshan Economic And Technological Development Zone Construction Investment Co ltd
Shanghai Jiaotong University
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Maanshan Economic And Technological Development Zone Construction Investment Co ltd
Shanghai Jiaotong 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/381—Alkaline or alkaline earth metals elements
    • H01M4/382—Lithium
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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 relates to an electro-deposition lithium-carbon-silver composite negative electrode material for a lithium battery and a preparation method thereof. Firstly, the metallic silver is evaporated on the surface of the carbon fiber by a thermal evaporation method, and then the metallic lithium-carbon-metallic silver composite cathode is prepared by an electrochemical deposition method. Compared with the prior art, the composite cathode material has the advantages of high coulombic efficiency, high unit area capacity, high electrochemical stability and the like.

Description

Electro-deposition lithium-carbon-silver composite negative electrode material for lithium battery and preparation method thereof
Technical Field
The invention belongs to the field of lithium battery electrode materials, and particularly relates to an electrodeposited lithium-carbon-silver composite negative electrode material for a lithium battery and a preparation method thereof.
Background
Lithium ion batteries have a profound effect on daily life, and the carbon cathode used in commercial lithium batteries is almost close to the theoretical capacity (370mAh g-1) of the carbon cathode, so that the carbon cathode is difficult to meet the increasingly high application requirements in the aspects of portable electronic equipment, electric automobiles, large-scale energy storage and the like. Among the materials that can be used as negative electrodes for lithium batteries, metallic lithium has an extremely large theoretical specific capacity (3860mAh g-1) and the lowest electrochemical potential (-3.04V relative to the standard hydrogen electrode), which is the best choice for the negative electrode material for next generation high energy lithium batteries such as lithium-sulfur and lithium-air batteries. The metal lithium negative electrode has huge volume change before and after circulation, and the SEI film is unstable, so that the service performance of the metal lithium is obviously reduced, and the use of the metal lithium composite electrode is an effective means for improving the negative performance of the metal lithium.
For example, chinese patent ZL201610250626.7 discloses an aggregate of a lithium-carbon composite material formed by a plurality of particles, where the particles include carbon particles, at least part of the surfaces of the carbon particles are attached with lithium metal, and/or at least part of the pores in the aggregate are filled with lithium metal. The lithium-carbon composite material can be directly used as a negative electrode material or can be added into a negative electrode without lithium element as an additive to play a role in compensating lithium, improve the first coulombic efficiency of the negative electrode, reduce the loss of effective lithium and prepare a lithium ion battery with high energy density.
For example, patent application 201910315106.3 discloses a lithium metal negative electrode material, and a preparation method and an application thereof, wherein a metal fluoride is hot-pressed on lithium metal, and a uniform and stable protective layer with excellent electron conductivity and ion conductivity is formed on the surface of the lithium metal by utilizing a displacement reaction between the metal fluoride and the lithium metal, so that a side reaction between the lithium metal and an electrolyte can be prevented, and simultaneously, the high ion mobility and the high electron conductivity on the surface of the lithium metal are beneficial to uniform deposition of lithium ions, the generation of lithium dendrites is effectively inhibited, and the service life of a battery is prolonged. The composite material is obtained by compounding the metal fluoride and the lithium metal, so that the performance of the lithium metal negative electrode is improved to a certain extent, but the lithium metal melting is also needed, the lithium metal melting needs to be carried out in inert gas, and the preparation method is not suitable for large-scale preparation.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide an electrodeposited lithium-carbon-silver composite negative electrode material for a lithium battery and a preparation method thereof, and the electrodeposited lithium-carbon-silver composite negative electrode material has the characteristics of high coulombic efficiency, high unit area capacity, high electrochemical stability and the like.
The purpose of the invention can be realized by the following technical scheme: the composite material is characterized by comprising flexible carbon fibers, metallic lithium and metallic silver, wherein the flexible carbon fibers are used as a substrate, a metallic silver film is arranged on the surface of the flexible carbon fibers, and a layer of metallic lithium is deposited on the surface of the metallic silver film.
Furthermore, the flexible carbon fiber is carbon cloth or carbon paper in a carbon fiber network shape, which is formed by conductive carbon fibers with the diameter of 100 nanometers to 100 micrometers. The preferred is conductive carbon fiber with the diameter of 1-50 microns.
Furthermore, the thickness of the metal silver film is 1 nm-1 μm. Preferably a metallic silver film having a thickness between 5 nm and 500 nm.
Furthermore, the metal silver film is formed by evaporating metal silver on the surface of the flexible carbon fiber in a single direction by a thermal evaporation method.
Furthermore, the metal lithium is formed by adopting an electrodeposition mode, and the capacity of the metal lithium is 1-5mAh cm-2。
A preparation method of an electrodeposited lithium-carbon-silver composite negative electrode material for a lithium battery is characterized by comprising the following steps of: and performing unidirectional evaporation on the metal silver on the flexible carbon fiber by using a thermal evaporation method, and then performing an electrodeposition method to add metal lithium to prepare the lithium-carbon-silver composite negative electrode material.
Further, the thermal evaporation method is vacuum evaporation or electron beam evaporation, and a preferred method is vacuum thermal evaporation.
Furthermore, the electrodeposition method is carried out by using a constant current or a pulse current modeAnd performing lithium metal deposition. The range of current adopted by the electrodeposition method is 0.01-50mA cm-2。
Further, it is preferable to perform electrodeposition by using a constant current method. The preferred current range for constant current electrodeposition is 0.2-5mA cm-2。
The electrolyte adopted by the electrodeposition method is DOL/DME (v/v is 1:1) solution of 1M LiTFSI, and 1w percent of LiNO is added3(ii) a Or 1.0M LiPF6(99.9%) EC/DEC/EMC (v/v/v ═ 1:1:1) solution with 2 w% FEC added. The electrolyte is selected to form a stable negative electrode SEI film.
One of the most effective methods for preparing the metal lithium composite cathode is to grow metal lithium in situ on a three-dimensional conductive and lithium-philic substrate, wherein the common substrate for growing the metal lithium comprises graphene, carbon nanotubes, graphene nanoribbons, a three-dimensional copper mesh, a metal oxide-carbon composite and the like, the substrates can effectively inhibit the growth of metal lithium dendrites and relieve the volume change caused by the metal lithium dendrites, and the electrochemical performance of the metal lithium is improved. The principle of electrodepositing metallic lithium on a substrate mainly comprises two processes, firstly lithium ions are inserted into the substrate to generate common electrochemical reaction, the potential is above 0V vs Li +/Li, and the reaction is changed into the growth of the metallic lithium because the substrate is saturated after the lithium ions are inserted, and the potential is below 0V vs Li +/Li.
Compared with the prior art, the invention has the following advantages:
1. the composite cathode material is formed by three parts of metal lithium, metal silver and carbon, wherein the carbon is carbon cloth or carbon paper with a network structure, the carbon substrates have good conductivity and mechanical property and can be tightly combined with a metal silver film, the metal silver and the metal lithium can form LiAg alloy, nucleation and growth of the metal lithium on the surface of the carbon can be changed, and the finally obtained composite material has the advantages of large capacity, high circulating coulombic efficiency (up to more than 97 percent), and good safety and circulating life.
2. The application range of the metal lithium negative electrode can be further expanded, and a new metal lithium composite negative electrode structure is formed.
Drawings
FIG. 1 is a coulombic efficiency cycle test chart of the composite material obtained in example 1;
FIG. 2 is a coulombic efficiency cycle test chart of the composite material obtained in example 2;
FIG. 3 is a coulombic efficiency cycle test chart of the composite material obtained in example 3.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
Carbon cloth composed of carbon fibers with the diameter of 10 microns is subjected to silver plating under the condition of vacuum evaporation, the silver plating thickness is 20nm, the carbon cloth is cut into electrode plates, then the electrode plates and metal lithium form two electrodes of a battery, the battery is assembled in a glove box, the electrolyte is DOL/DME (v/v is 1:1) solution of 1M LiTFSI, and 1 w% of LiNO is added3. At 5mAh cm-2At 1mA cm for over-intercalation of lithium-2The coulomb efficiency of 97.1% can still be maintained when the current density of (1) is cycled for 50 cycles, as shown in fig. 1.
Example 2
Silver plating is carried out on carbon cloth composed of carbon fibers with the diameter of 10 microns under the condition of vacuum evaporation, the silver plating thickness is 20nm, the carbon cloth is cut into electrode plates, then the electrode plates and metal lithium form two poles of a battery, the battery is assembled in a glove box, and the electrolyte is 1.0M LiPF6(99.9%) EC/DEC/EMC (v/v/v ═ 1:1:1) solution with 2 w% FEC added. At 5mAhcm-2At 1mA cm for over-intercalation of lithium-2The coulomb efficiency of 97.1% can still be maintained when the current density of the current transformer is cycled for 30 circles. As shown in fig. 2.
Example 3
Silver plating is carried out on carbon cloth composed of carbon fibers with the diameter of 10 microns under the condition of vacuum evaporation, the thickness of the silver plating is 20nm, the carbon cloth is cut into electrode plates, then the electrode plates and lithium metal form two poles of a battery, and 2mAhcm is carried out-2The lithium pre-intercalation is assembled into a battery in a glove box, and the electrolyte is 1.0M LiPF6(99.9%) EC/DEC/EMC (v/v/v ═ 1:1:1) solution with 2 w% FEC added. Then the electrode was removed and the areal density was about 14.7mg cm-2Of LiCoO (R) in a gas phase2The positive electrode is assembled into a full cell, the electrolyte is unchanged, and the current density of the first circle of the test is 0.2mA cm-2Subsequent current density of 1mAh cm-2The voltage range of the battery test is 4.25-2.7V. After 100 cycles, the cell still maintained 155mAh g-1. As shown in fig. 3.
Example 4
Carbon paper composed of carbon fibers with the diameter of 100 microns is subjected to silver plating under the condition of vacuum evaporation (a conventional vacuum evaporation method), the thickness of the silver plating is 1 micron, the carbon paper is cut into electrode plates, then the electrode plates and metal lithium are combined to form two electrodes of a battery, the battery is assembled in a glove box, the electrolyte is DOL/DME (v/v is 1:1) solution of 1M LiTFSI, and 1 w% of LiNO is added3. Performing electrodeposition at 0.2mAcm by constant current-2Under the current condition of (3), the metallic lithium is electrodeposited, and the capacity of the metallic lithium is 1mAh cm-2Obtaining the composite cathode material of the lithium battery, wherein the obtained material is 1mA cm-2The coulomb efficiency of 96.8% can still be maintained when the current density of the current sensor is cycled for 100 circles.
Example 5
Carbon paper composed of carbon fibers with the diameter of 100 nanometers is subjected to silver plating under the condition of electron beam evaporation (a conventional electron beam evaporation method), the silver plating thickness is 1 nanometer, the carbon paper is cut into electrode plates, then the electrode plates and metal lithium form two poles of a battery, the battery is assembled in a glove box, and the electrolyte is 1.0M LiPF6(99.9%) EC/DEC/EMC (v/v/v ═ 1:1:1) solution with 2 w% FEC added. Performing electrodeposition at 5mA cm by using a constant current mode-2Under the current condition of (3), the metallic lithium is electrodeposited, and the capacity of the metallic lithium is 5mAh cm-2To obtain a lithium batteryComposite negative electrode material, the obtained material is 1mA cm-2The coulomb efficiency of 98.2% can still be maintained when the current density of the current transformer is cycled for 100 circles.

Claims (10)

1. The composite material is characterized by comprising flexible carbon fibers, metallic lithium and metallic silver, wherein the flexible carbon fibers are used as a substrate, a metallic silver film is arranged on the surface of the flexible carbon fibers, and a layer of metallic lithium is deposited on the surface of the metallic silver film.
2. The electrodeposited lithium-carbon-silver composite negative electrode material for a lithium battery as claimed in claim 1, wherein the flexible carbon fiber is carbon cloth or paper in a carbon fiber network form composed of conductive carbon fibers having a diameter of 100 nm to 100 μm.
3. The electrodeposited lithium-carbon-silver composite negative electrode material for a lithium battery as claimed in claim 1, wherein the metallic silver thin film has a thickness of 1nm to 1 μm.
4. The electrodeposited lithium-carbon-silver composite negative electrode material for a lithium battery as claimed in claim 1, wherein the metallic silver thin film is formed by depositing metallic silver on the surface of the flexible carbon fiber in one direction by thermal evaporation.
5. The electrodeposited lithium-carbon-silver composite negative electrode material for lithium battery as claimed in claim 1, wherein the metallic lithium is formed by electrodeposition and has a capacity of 1 to 5mAh cm-2。
6. A method for preparing an electrodeposited lithium-carbon-silver composite negative electrode material for a lithium battery as claimed in claim 1, comprising the steps of: and performing unidirectional evaporation on the metal silver on the flexible carbon fiber by using a thermal evaporation method, and then performing an electrodeposition method to add metal lithium to prepare the lithium-carbon-silver composite negative electrode material.
7. The method of claim 6, wherein the thermal evaporation method is vacuum evaporation or electron beam evaporation.
8. The method for preparing an electrodeposited lithium-carbon-silver composite negative electrode material for a lithium battery as claimed in claim 6, wherein the electrodeposition method is a method of depositing metallic lithium by using a constant current or a pulse current.
9. The method for preparing an electrodeposited lithium-carbon-silver composite negative electrode material for a lithium battery as claimed in claim 8, wherein the electrodeposition method uses a current ranging from 0.01 to 50mA cm-2。
10. The method for preparing an electrodeposited lithium-carbon-silver composite negative electrode material for a lithium battery as claimed in claim 8, wherein the electrolyte used in the electrodeposition method is 1M DOL/DME (v/v ═ 1:1) solution of LiTFSI, to which 1 w% of LiNO is added3(ii) a Or 1.0M LiPF6(99.9%) EC/DEC/EMC (v/v/v ═ 1:1:1) solution with 2 w% FEC added.
CN202010585317.1A 2020-06-24 2020-06-24 Electro-deposition lithium-carbon-silver composite negative electrode material for lithium battery and preparation method thereof Pending CN111710841A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112331825A (en) * 2020-10-19 2021-02-05 中国电子科技集团公司第十八研究所 Preparation method of silicon-carbon-silver composite cathode of lithium ion battery
CN112736251A (en) * 2020-12-30 2021-04-30 电子科技大学 Three-dimensional porous material containing lithium alloy skeleton network, composite lithium negative electrode material and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107910496A (en) * 2017-10-09 2018-04-13 中南大学 A kind of secondary cell lithium anode, preparation method and applications
CN110854380A (en) * 2019-11-27 2020-02-28 电子科技大学 Lithium-carbon composite material, lithium battery and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107910496A (en) * 2017-10-09 2018-04-13 中南大学 A kind of secondary cell lithium anode, preparation method and applications
CN110854380A (en) * 2019-11-27 2020-02-28 电子科技大学 Lithium-carbon composite material, lithium battery and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
RAN TIAN等: "Electrodeposition behavior of lithium metal on carbon substrates with surface silvering", 《CARBON》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112331825A (en) * 2020-10-19 2021-02-05 中国电子科技集团公司第十八研究所 Preparation method of silicon-carbon-silver composite cathode of lithium ion battery
CN112736251A (en) * 2020-12-30 2021-04-30 电子科技大学 Three-dimensional porous material containing lithium alloy skeleton network, composite lithium negative electrode material and preparation method thereof
CN112736251B (en) * 2020-12-30 2022-06-03 电子科技大学 Three-dimensional porous material containing lithium alloy skeleton network, composite lithium negative electrode material and preparation method thereof

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