CN112820877A - Anode and preparation method and application thereof - Google Patents

Anode and preparation method and application thereof Download PDF

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Publication number
CN112820877A
CN112820877A CN201911126126.2A CN201911126126A CN112820877A CN 112820877 A CN112820877 A CN 112820877A CN 201911126126 A CN201911126126 A CN 201911126126A CN 112820877 A CN112820877 A CN 112820877A
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Prior art keywords
copper
current collector
anode
lithium
antirust agent
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CN201911126126.2A
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CN112820877B (en
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郑磊
康拓
毛亚云
沈炎宾
陈立桅
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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Suzhou Institute of Nano Tech and Nano Bionics of CAS
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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
    • 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
    • H01M4/134—Electrodes based on metals, Si or alloys
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides an anode and a preparation method and application thereof, and the anode comprises a copper current collector and a copper antirust agent complexed on the surface of the copper current collector. According to the invention, through the property of lithium-philic groups in the copper antirust agent, the copper antirust agent is utilized to modify the surface of the copper current collector, so that the uniform deposition of lithium ions on the surface of copper is guided, and the formation of a dendrite-free anode is facilitated, thereby improving the coulombic efficiency of the lithium metal battery, prolonging the cycle life of the lithium metal battery, and promoting and guiding the development of the lithium metal battery with high energy density and high stability to a certain extent. The anode of the invention has simple preparation process, can be prepared in batches and has lower cost.

Description

Anode and preparation method and application thereof
Technical Field
The invention belongs to the technical field of new energy materials, and particularly relates to an anode and a preparation method and application thereof.
Background
With the wide popularization of lithium battery application, various energy storage systems put higher requirements on the energy density of secondary batteries, and the energy density of the secondary batteries is higherIn the specific energy system, the metal lithium has extremely high theoretical specific capacity (3860 mA.h.g)-1) Low density (0.59g cm)-3) And the lowest electrochemical potential (-3.040V), so that secondary lithium metal batteries in which lithium metal is the negative electrode have attracted attention. However, in the lithium ion plating/stripping process, lithium metal is easy to form dendrites with large surface area, which not only causes internal short circuit, but also causes accumulation of "dead lithium", and the safety problem is serious, and the cycle life is poor, so that the large-scale application thereof is still challenging. In order to solve this problem for over four decades, researchers have also developed various strategies such as electrolyte additives, interfacial protection layers, artificial SEI, polymer coatings, etc. to form high modulus layers on the surface of lithium metal electrodes to inhibit penetration of lithium dendrites. However, the non-uniform deposition of lithium ions still occurs, and dead lithium is formed to cause rapid deterioration of the battery capacity. Therefore, the nucleation is really dispersed in the lithium deposition process, and the strategy for solving the lithium dendrites is very important.
Currently, as a means for suppressing lithium dendrites, it is common to improve the uniformity of a solid electrolyte interface layer (SEI) on the surface of an electrode through a series of electrolyte additives or optimization of an electrolyte system. It is well known that the formation and growth of lithium dendrites cannot be completely eliminated by SEI, which is mechanically weak.
With respect to regulating lithium metal ion deposition, the currently more common technique is to form lithium and metal alloys during electrodeposition by adding an inorganic compound or a second salt to the electrolyte. However, most of these metal cation additives are consumed by the alloy formed during lithium deposition, and thus inhibition of lithium dendrite formation is not sustainable.
In addition, the current lithium dendrite treatment means and method have the defects of high cost, expensive experimental equipment and high requirement on experimental conditions.
Disclosure of Invention
The invention aims to provide an anode capable of guiding lithium ions to be uniformly deposited so as to form a dendrite-free anode, and a preparation method and application thereof.
In order to solve the technical problems, the invention adopts the following technical scheme:
the invention provides an anode which comprises a copper current collector and a copper antirust agent complexed on the surface of the copper current collector.
In the invention, the copper current collector is metal copper with a one-dimensional, and/or two-dimensional, and/or three-dimensional structure.
Preferably, the copper antirust agent is a copper antirust agent containing nitrogen-containing groups or other lithium-philic groups, so that the antirust agent can be complexed on the surface layer of a copper current collector through chemical action, disperse nucleation is performed, lithium ions are guided to be uniformly and orderly deposited, and the stability of SEI (solid electrolyte interphase) on the surface layer is improved, thereby forming a dendrite-free anode.
More preferably, the copper antirust agent is any one or a combination of two or more of benzotriazole, methyl benzotriazole, 1-hydroxy benzotriazole and the like.
The invention also provides a preparation method of the anode, which is prepared by contacting the copper current collector with the copper antirust solution.
In the invention, the copper current collector is metal copper with a one-dimensional, and/or two-dimensional, and/or three-dimensional structure.
Preferably, the copper antirust agent is a copper antirust agent containing a nitrogen-containing group or other lithium-philic groups.
More preferably, the copper antirust agent is any one or a combination of two or more of benzotriazole, methyl benzotriazole, 1-hydroxy benzotriazole and the like.
The solvent in the copper antirust solution can be all liquids capable of dissolving the copper antirust agent, and ethanol and a solvent in an ether electrolyte system are preferably adopted, wherein the solvent in the ether electrolyte system comprises but is not limited to one or more of 1, 3-Dioxolane (DOL), ethylene glycol dimethyl ether (DME) and dimethoxyethane.
Preferably, the mass percentage concentration of the copper antirust agent solution is 0.05-0.2%.
Further preferably, the mass percentage concentration of the copper antirust agent solution is 0.08-0.15%.
The copper antirust agent can be complexed on the surface of the copper current collector by means of spraying, soaking and the like, preferably, the copper antirust agent solution is heated to 40-60 ℃, then the copper current collector is placed into the copper current collector to be soaked for 5-15 min, and the copper current collector is cleaned and dried to obtain the anode.
Further preferably, the copper current collector is cleaned by one or more of ethanol, acetone and the like.
Preferably, the copper current collector is a pretreated copper current collector, and the pretreatment method comprises the following steps: and soaking the copper current collector in dilute hydrochloric acid, and then cleaning and drying.
Further preferably, the copper current collector is soaked in the diluted hydrochloric acid for 20-40 min.
It is further preferred that the copper current collector soaked with the diluted hydrochloric acid is washed with one or more of ethanol, acetone, and the like.
The third aspect of the invention provides an application of the anode or the anode prepared by the preparation method in a lithium metal battery.
The fourth aspect of the invention provides a lithium metal battery, wherein the battery cathode is the anode, or the anode prepared by the preparation method.
The positive electrode is one or more of electrode materials containing lithium sources such as lithium iron phosphate, lithium titanate and lithium cobaltate.
The separator used in the present invention may be a separator commonly used in the art, such as a celgard PP separator, etc.
The lithium metal battery in the present invention may be a button cell, such as 2025 button cell, pouch cell, cylindrical cell, etc.
The negative electrode of the lithium metal battery adopts the copper current collector treated by the copper antirust agent, and lithium is deposited on the surface of the copper current collector from the positive electrode in the first charging cycle to form a lithium metal layer.
According to the invention, the copper antirust agent with the nitrogen-containing group is used, and DFT simulation shows that the affinity of N atoms in the copper antirust agent to lithium ions is higher than that of copper atoms, so that the lithium ions are favorably nucleated on the surface of a copper current collector without dendrites, and the copper antirust agent has high reversible lithium plating/stripping capability. Since only the surface of the copper current collector is subjected to the lithium metal plating and the lithium extraction, the effect of suppressing lithium dendrites can be sustained.
The method selects the copper antirust agent with lower cost, has quite simple and convenient treatment method, and can obtain the dendrite-free anode by simply placing the copper current collector in the copper antirust agent solution for soaking at constant temperature.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
according to the invention, through the property of lithium ion affinity in the copper antirust agent, the copper antirust agent is used for modifying the surface of the copper current collector, so that the lithium ions are guided to be uniformly deposited on the surface of the copper, and the formation of a dendrite-free anode is facilitated, thereby improving the coulomb efficiency of the lithium metal battery, prolonging the cycle life of the lithium metal battery, and promoting and guiding the development of the lithium metal battery with high energy density and high stability to a certain extent.
The anode of the invention has simple preparation process, can be prepared in batches and has lower cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments described in the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a schematic view of a process for preparing an anode of example 1;
FIG. 2 is a charge and discharge curve of example 1;
FIG. 3 is a graph of overpotential of the battery according to example 2 as a function of cycle number;
FIG. 4 is a graph of coulombic efficiency versus cycle number for example 3;
FIG. 5 is an electron micrograph of a lithium-plated and extracted lithium of example 3.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below, and it should be apparent that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The experimental means or test means not shown in the following examples of the present invention are conventional in the art unless otherwise specified.
Example 1
Dissolving commercially available Benzotriazole (BTA) powder in absolute ethyl alcohol to prepare 0.05 wt%, 0.1 wt% and 0.2 wt% BTA solutions respectively, taking the absolute ethyl alcohol as a reference, soaking copper foil stamped sheets into a plurality of wafers with the diameter of 15mm in a dilute hydrochloric acid solution for 30 minutes, then washing the copper foil stamped sheets by the absolute ethyl alcohol, continuously washing the copper foil stamped sheets by the absolute ethyl alcohol in the washing process, washing off redundant dilute hydrochloric acid, then baking the copper foil stamped sheets for 1 hour at the temperature of 40 ℃, then taking out the copper foil stamped sheets to be soaked in the BTA solutions with different concentrations and the absolute ethyl alcohol at the temperature of 50 ℃, taking out the copper foil stamped sheets after ten minutes, and baking the copper foil stamped sheets at the temperature of 40 ℃ overnight. The treated copper foil material and a metal lithium sheet are respectively put in a conventional ether electrolyte system (wherein, the lithium salt is 1M LiTFSI, the solvent is DOL/DME (volume ratio is 1: 1), and the additive is 2 wt% LiNO3) And assembling to obtain the half cell.
The preparation schematic diagram of the negative electrode is shown in fig. 1.
The prepared lithium metal batteries are respectively charged at a rate of 1mA/cm2Current density of 1mAh/cm2The test results are shown in fig. 2, in which 0% of the line is the copper foil treated with the absolute ethanol control group, 0.05% of the line is the copper foil treated with the BTA solution having a BTA concentration of 0.05 wt%, 0.1% of the line is the copper foil treated with the BTA solution having a BTA concentration of 0.1 wt%, and 0.2% of the line is the copper foil treated with the BTA solution having a BTA concentration of 0.2 wt%. As can be seen from FIG. 2, at 0.1 wt% concentration, the half cell overpotential is lowest and the polarization is lowest, so the BTA solution concentrationThe best effect is obtained when the content is 0.1 wt%.
Example 2
0.1g of commercially available Benzotriazole (BTA) powder is dissolved in 100ml of absolute ethyl alcohol to prepare 0.1% BTA solution, a copper foil stamped sheet is a wafer with the diameter of 15mm, the wafer is firstly soaked in a dilute hydrochloric acid solution for 30mins, then is washed by the absolute ethyl alcohol, is continuously washed by the absolute ethyl alcohol in the washing process, eliminates redundant dilute hydrochloric acid, then is baked for 1 hour at the temperature of 40 ℃, part of copper foil is reserved, the other part of copper foil is soaked in the BTA solution at the temperature of 50 ℃, is taken out after ten minutes and is baked at the temperature of 40 ℃ overnight.
The pretreated copper foil and the BTA-soaked copper foil were assembled into half-cells in the manner of example 1, respectively.
The batteries prepared above were charged at 1mA/cm, respectively2Current density of 1mAh/cm2The discharge depth was controlled to 33% (3 mAh/cm lithium was plated on the pretreated copper foil and the copper foil soaked with BTA in advance)2) The curve of the overpotential changing with the cycle number is shown in fig. 3, wherein the line of Cu @ Li | | Cu @ Li is a copper foil which is only subjected to pretreatment and is not soaked in the BTA solution, and the line of BTA-Cu @ Li | | | BTA-Cu @ Li is a copper foil which is soaked in the BTA solution, so that as can be seen from fig. 3, compared with a traditional copper foil current collector, the polarization of the copper foil current collector treated by BTA is smaller, and the electrochemical cycle stability is better.
Example 3
The copper foil pretreated in example 2 and the copper foil soaked with BTA were respectively placed in a conventional ether electrolyte system (lithium salt is 1M LiTFSI, solvent is DOL/DME (volume ratio is 1: 1), and additive is 2 wt% LiNO3) And assembling the button cell to obtain the lithium metal battery.
The batteries prepared by the method are subjected to charge and discharge experiments by 0.5C respectively, and the test results are shown in FIG. 4, wherein Cu < I > LFP is a curve of the capacity retention rate of the battery prepared by the copper foil which is only subjected to pretreatment and is not soaked in the BTA solution along with the change of the cycle number, BTA-Cu < I > LFP is a curve of the capacity retention rate of the battery prepared by the copper foil which is soaked in the BTA solution along with the change of the cycle number, CE of Cu < I > LFP is a curve of the coulombic efficiency of the battery prepared by the copper foil which is only subjected to pretreatment and is not soaked in the BTA solution along with the change of the cycle number, and CE of BTA-Cu < I > LFP is a curve of the coulombic efficiency of the battery prepared by the copper foil which is soaked in the BTA solution along with the change of. As can be seen from fig. 4, the batteries manufactured from the copper foil soaked in the BTA solution have strong coulombic efficiency and capacity retention rate.
Charging the obtained battery until the capacity density of the battery is 3mAh/cm2Respectively observing the appearance of the negative electrode, and then respectively observing the appearance of the negative electrode when the battery is discharged until the voltage of the battery is 1V, wherein an electron microscope picture is shown as figure 5, wherein a is the electron microscope picture after the copper foil soaked in the BTA solution is plated with lithium, and b is the electron microscope picture after the copper foil soaked in the BTA solution is pulled out of the lithium; c is the electron micrograph of the copper foil after lithium plating with only pretreatment without soaking in BTA solution, and d is the electron micrograph of the copper foil after lithium plating with only pretreatment without soaking in BTA solution. As can be seen from FIG. 5, the copper foil soaked in the BTA solution has better restorability in the lithium plating and extraction process, dead lithium is generated little and hardly, and the deposition appearance is more uniform.
Example 4
0.1g of commercially available tolyltriazole (TTA) powder is dissolved in 100ml of absolute ethyl alcohol to prepare 0.1% TTA solution, a copper foil stamping sheet is a wafer with the diameter of 15mm, the wafer is firstly soaked in a dilute hydrochloric acid solution for 30mins, then is washed by the absolute ethyl alcohol, is continuously washed by the absolute ethyl alcohol in the washing process, is washed to remove redundant dilute hydrochloric acid, is baked for 1 hour at the temperature of 40 ℃, is taken out and soaked in the TTA solution at the temperature of 50 ℃, is taken out after ten minutes and is baked at the temperature of 40 ℃ overnight. The treated copper foil material and the lithium iron phosphate positive electrode are assembled into a button cell in a conventional ether electrolyte system to obtain a lithium metal battery without a dendritic anode, and the performance of the battery is similar to that of the battery in example 3.
It should be noted that, the technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.

Claims (17)

1. An anode, characterized by: comprises a copper current collector and a copper antirust agent which is complexed on the surface of the copper current collector.
2. The anode of claim 1, wherein: the copper current collector is metal copper with a one-dimensional, and/or two-dimensional, and/or three-dimensional structure.
3. The anode of claim 1, wherein: the copper antirust agent is a copper antirust agent containing a nitrogen-containing group or other lithium-philic groups.
4. The anode of claim 3, wherein: the copper antirust agent is any one or the combination of two or more of benzotriazole, methyl benzotriazole, 1-hydroxy benzotriazole and the like.
5. A method for preparing an anode is characterized in that: and contacting the copper current collector with a copper antirust solution to obtain the copper-based alloy.
6. The method of claim 5, wherein: the copper antirust agent is a copper antirust agent containing a nitrogen-containing group or other lithium-philic groups.
7. The method of claim 6, wherein: the copper antirust agent is any one or the combination of two or more of benzotriazole, methyl benzotriazole, 1-hydroxy benzotriazole and the like.
8. The method of claim 5, wherein: the solvent in the copper antirust agent solution is one or more of ethanol, 1, 3-dioxolane, ethylene glycol dimethyl ether and dimethoxyethane.
9. The method of claim 5, wherein: the mass percentage concentration of the copper antirust agent solution is 0.05-0.2%.
10. The method of claim 9, wherein: the mass percentage concentration of the copper antirust agent solution is 0.08-0.15%.
11. The method of claim 5, wherein: and heating the copper antirust agent solution to 40-60 ℃, then putting the copper current collector into the copper current collector to be soaked for 5-15 min, and cleaning and drying the copper current collector to obtain the anode.
12. The method of claim 5, wherein: the copper current collector is a pretreated copper current collector, and the pretreatment method comprises the following steps: and soaking the copper current collector in dilute hydrochloric acid, and then cleaning and drying.
13. The method of manufacturing according to claim 12, wherein: and soaking the copper current collector in the dilute hydrochloric acid for 20-40 min.
14. The production method according to claim 11 or 12, characterized in that: and cleaning the copper current collector by adopting one or more of ethanol, acetone and the like.
15. Use of the anode according to any one of claims 1 to 4, or the anode produced by the method according to any one of claims 5 to 14, in a lithium metal battery.
16. A lithium metal battery, characterized in that: the negative electrode of the battery is the anode of any one of claims 1 to 4 or the anode prepared by the preparation method of any one of claims 5 to 14.
17. The lithium metal battery of claim 16, wherein: the anode is one or more of electrode materials containing lithium sources such as lithium iron phosphate, lithium titanate, lithium cobaltate and the like.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113529139A (en) * 2021-06-08 2021-10-22 浙江工业大学 Method for screening electrolytic copper foil additive by using density function theory

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1819324A (en) * 2006-03-03 2006-08-16 浙江阻燃锂电材料有限公司 Cell liquor and lithium ion battery therefor
CN105024081A (en) * 2015-07-07 2015-11-04 安徽铜冠铜箔有限公司 Novel anti-oxidation liquid for copper foil of lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1819324A (en) * 2006-03-03 2006-08-16 浙江阻燃锂电材料有限公司 Cell liquor and lithium ion battery therefor
CN105024081A (en) * 2015-07-07 2015-11-04 安徽铜冠铜箔有限公司 Novel anti-oxidation liquid for copper foil of lithium ion battery

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113529139A (en) * 2021-06-08 2021-10-22 浙江工业大学 Method for screening electrolytic copper foil additive by using density function theory
CN113529139B (en) * 2021-06-08 2022-11-22 浙江工业大学 Method for screening electrolytic copper foil additive by using density function theory

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