CN110911689A - Current collector and preparation method thereof, electrode plate and secondary battery - Google Patents
Current collector and preparation method thereof, electrode plate and secondary battery Download PDFInfo
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- CN110911689A CN110911689A CN201911063329.1A CN201911063329A CN110911689A CN 110911689 A CN110911689 A CN 110911689A CN 201911063329 A CN201911063329 A CN 201911063329A CN 110911689 A CN110911689 A CN 110911689A
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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
- H01M4/662—Alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C28/00—Alloys based on a metal not provided for in groups C22C5/00 - C22C27/00
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
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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
- H01M4/665—Composites
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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
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- 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 the technical field of batteries, and particularly relates to a current collector, a preparation method of the current collector, an electrode plate and a secondary battery. The preparation method provided by the invention comprises the following steps: obtaining a copper metal substrate and gallium-based liquid metal; and coating the gallium-based liquid metal on the surface of the copper metal substrate, so that the gallium-based liquid metal and the copper on the surface of the copper metal substrate are subjected to alloying reaction to prepare the copper metal substrate with an alloy layer formed on the surface, wherein the alloy layer is made of copper-gallium-based alloy. Simple process, low energy consumption, green and pollution-free, and is suitable for large-scale production. The surface of the obtained current collector is formed with the copper-gallium-based alloy, so that the surface of the current collector is provided with uniformly distributed gallium active sites, alkali metal ions can be induced to be uniformly deposited on the surface of the current collector in the subsequent battery charging and discharging processes, and the formation and growth of dendritic crystals can be effectively inhibited.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a current collector, a preparation method of the current collector, an electrode plate and a secondary battery.
Background
Due to the characteristics of low de-intercalation ion potential, high utilization rate and the like, the construction of the secondary energy storage battery based on the metal lithium cathode and the metal sodium cathode is the ultimate target of the alkali metal ion battery and is one of the focus points of the current alkali metal ion battery research. However, in the process of charging and discharging the alkali metal negative electrode, needle-like or dendritic dendrites such as lithium dendrites or sodium dendrites are easily formed on the surface of the alkali metal negative electrode due to the reduction of alkali metal ions. The existence of the dendrite may puncture the diaphragm and contact with the positive electrode, so that the internal short circuit of the battery is caused, thermal failure is generated, and risks such as spontaneous combustion or explosion are caused; on the other hand, the dendrite structure is loose and porous, such as lithium dendrites, and easily fall off to form "dead lithium" without electrochemical activity, and the capacity is lost. In addition, the specific surface area of the negative electrode is increased due to the growth of dendrites, and a large amount of electrolyte is consumed to form a solid electrolyte membrane, resulting in the degradation of the capacity and the reduction of the cycle life of the battery. Therefore, the dendrite growth problem has severely hindered the commercial application of the new generation of high energy density secondary alkali metal batteries.
Disclosure of Invention
The invention mainly aims to provide a current collector and a preparation method thereof, and also aims to provide an electrode plate and a secondary battery, aiming at improving the electrochemical performance of the battery by effectively inhibiting dendritic crystal growth.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method of making a current collector, comprising the steps of:
obtaining a copper metal substrate and gallium-based liquid metal;
and coating the gallium-based liquid metal on the surface of the copper metal substrate, so that the gallium-based liquid metal and the copper on the surface of the copper metal substrate are subjected to an alloying reaction to prepare the copper metal substrate with an alloy layer formed on the surface, wherein the alloy layer is made of a copper-gallium-based alloy.
According to the preparation method of the current collector, the copper-gallium-based alloy is formed on the surface of the copper metal substrate by utilizing the alloying reaction between the gallium-based liquid metal and the copper, the process is simple, the energy consumption is low, the method is green and pollution-free, and the method is suitable for large-scale production. The surface of the obtained current collector is formed with the copper-gallium-based alloy, so that the surface of the current collector has gallium active sites which are uniformly distributed, and alkali metal ions can be induced to be uniformly deposited on the surface of the current collector in the subsequent battery charging and discharging processes, thereby effectively inhibiting the formation and growth of dendrites and improving the electrochemical performance of the alkali metal battery.
Accordingly, a current collector, comprising: the device comprises a copper metal substrate and an alloy layer arranged on the copper metal substrate, wherein the alloy layer is made of copper-gallium-based alloy.
The surface of the current collector provided by the invention is formed with the copper-gallium-based alloy, has the gallium-based active sites which are uniformly distributed, and can induce alkali metal ions to be uniformly deposited on the surface of the current collector in the charging and discharging processes of a battery, so that the formation and growth of dendritic crystals are effectively inhibited, and the electrochemical performance of the battery is improved.
Correspondingly, an electrode slice includes: the current collector prepared by the preparation method or the current collector, and a metal layer deposited on the current collector; the metal layer is arranged on the surface of the alloy layer far away from the copper metal substrate.
The electrode plate provided by the invention adopts the current collector, so that the formation and growth of dendritic crystals in the charging and discharging processes of the battery can be effectively inhibited, and the electrochemical performance of the battery is improved.
Correspondingly, a secondary battery comprises the electrode plate.
The secondary battery provided by the invention has good electrochemical performance by adopting the electrode plate.
Drawings
FIG. 1 is a schematic view of the liquid metal of indium gallium tin prepared in example 1 at room temperature;
FIG. 2 is a surface morphology of a copper foil having a copper indium gallium tin alloy layer formed on the surface thereof in example 1;
FIG. 3 is a 20k SEM image of the surface of the Cu-in-Ga-Sn alloy layer in example 1;
FIG. 4 is a graph showing the cycle profiles of the copper lithium half-cells obtained in example 4 and comparative example 4;
fig. 5 is a graph showing the cycle profiles of the copper-lithium half cells obtained in example 5 and comparative example 5.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail below with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A method of making a current collector, comprising the steps of:
s01, obtaining a copper metal substrate and gallium-based liquid metal;
and S02, coating the gallium-based liquid metal on the surface of the copper metal substrate, so that the gallium-based liquid metal and the copper on the surface of the copper metal substrate are subjected to alloying reaction to prepare the copper metal substrate with an alloy layer formed on the surface, wherein the alloy layer is made of a copper-gallium-based alloy.
According to the preparation method of the current collector provided by the embodiment of the invention, the copper-gallium-based alloy is formed on the surface of the copper metal substrate by utilizing the alloying reaction between the gallium-based liquid metal and the copper, the process is simple, the energy consumption is low, the method is green and pollution-free, and the method is suitable for large-scale production. The surface of the obtained current collector is formed with the copper-gallium-based alloy, so that the surface of the current collector has gallium active sites which are uniformly distributed, and alkali metal ions can be induced to be uniformly deposited on the surface of the current collector in the subsequent battery charging and discharging processes, thereby effectively inhibiting the formation and growth of dendrites and improving the electrochemical performance of the alkali metal battery.
Specifically, in step S01, the copper metal substrate is used as the main body of the current collector, and can spontaneously perform an alloying reaction with gallium-based liquid metal, such as indium-gallium-tin liquid metal, and the like, and due to the characteristics of high melting point, good conductivity, relatively stable chemical properties, and the like, the copper metal substrate is not only beneficial to the subsequent deposition of a metal layer on the current collector, but also can perform good conduction and current collection functions when a layer battery is assembled by using the copper metal substrate.
The gallium-based liquid metal takes gallium as a main component, and the general formula of the gallium-based liquid metal is Ga-X, wherein X is In, Sn or In-Sn. In one embodiment, the gallium-based liquid metal is indium gallium tin liquid metal and/or gallium tin liquid metal. On one hand, the liquid metal of indium gallium tin and/or gallium tin is contacted with the copper metal to spontaneously generate alloying reaction to form copper indium gallium tin alloy and/or copper gallium tin alloy, so that the surface of the current collector is provided with uniformly distributed active sites of indium gallium tin and/or gallium tin, and alkali metal ions are further promoted to be uniformly deposited on the surface of the current collector; on the other hand, the reaction degree between the indium gallium tin liquid metal and/or the gallium tin liquid metal and the copper metal is moderate, so that the current collector can be prevented from being corroded and damaged by the liquid metal, and the structural integrity of the current collector is ensured; on the other hand, the indium gallium tin alloy and/or the copper gallium tin alloy have high ionic conductivity, and can play a role of a fast ion migration conductor when the battery is charged and discharged, so that the conductivity of the battery is ensured to meet the battery requirement.
In the gallium-based liquid metal, based on 100 percent of the total weight of the gallium-based liquid metal, 30 to 100 percent of gallium, 0 to 50 percent of indium and 0 to 20 percent of tin are contained; or, based on 100 percent of the total weight of the gallium-based liquid metal, 60 to 100 percent of gallium and 0 to 40 percent of tin.
In some embodiments, the gallium-based liquid metal is indium-gallium-tin liquid metal, and is prepared by alloying indium, gallium and tin. In a further embodiment, the weight ratio of the gallium atoms, the indium atoms and the tin atoms in the indium gallium tin liquid metal is 7: 2: 1, mixing indium, gallium and tin according to a proportion, and quickly heating to 400 ℃ for alloying.
In some embodiments, the gallium-based liquid metal is gallium-tin liquid metal, and is prepared by alloying gallium and tin. In a further embodiment, the weight ratio of gallium atoms to tin atoms in the gallium-tin liquid metal is 92: and 8, mixing gallium and tin according to a proportion, and quickly heating to 400 ℃ for alloying to obtain the alloy.
Specifically, in step S02, the liquid metal is coated on the surface of the copper metal substrate, so that the liquid metal and the copper on the surface of the copper metal substrate are subjected to an alloying reaction to form an alloy layer on the surface of the copper metal substrate, where the alloy layer is made of a copper-gallium-based alloy, so that the surface of the current collector has gallium-based active sites uniformly distributed, so as to induce alkali metal ions to uniformly deposit on the surface of the current collector, thereby effectively inhibiting the formation and growth of dendrites. In some embodiments, the liquid metal is coated on the surface of the copper metal substrate by a blade coating method, the process is simple, expensive equipment is not needed, the cost is low, and the method is suitable for large-scale production.
As one embodiment, in the step of coating the liquid metal on the surface of the copper metal substrate, the liquid metal is coated on the surface of the copper metal substrate at 23 to 30 ℃. The alloy layer can be prepared by reaction at room temperature, the energy consumption is low, the steps are simple, and the large-scale mass production of the current collector is easy to realize.
As an embodiment, after the step of coating the liquid metal on the surface of the copper metal substrate, the liquid metal on the surface of the copper metal substrate is removed to obtain the current collector. In some embodiments, the liquid metal is removed from the copper metal substrate surface using an alcohol. In other embodiments, the alloy layer has a thickness of 0.5 to 4 μm.
Correspondingly, the current collector prepared by the preparation method comprises the following steps: the device comprises a copper metal substrate and an alloy layer arranged on the copper metal substrate, wherein the alloy layer is made of copper-gallium-based alloy.
The current collector provided by the embodiment of the invention is prepared by the preparation method, the copper-gallium-based alloy is formed on the surface of the current collector, the gallium-based alloy has uniformly distributed gallium-based active sites, and alkali metal ions can be induced to be uniformly deposited on the surface of the current collector in the charging and discharging processes of a battery, so that the formation and growth of dendrites are effectively inhibited, and the electrochemical performance of the battery is improved.
Specifically, the general formula of the copper-gallium-based alloy is Cu-Ga-X, wherein X is In, Sn or In-Sn. In one embodiment, the copper-gallium-based alloy is a copper-indium-gallium-tin alloy and/or a copper-gallium-tin alloy.
In the gallium-based liquid metal, based on 100 percent of the total weight of the copper-gallium-based alloy, 10 to 50 percent of copper, 20 to 90 percent of gallium, 0 to 50 percent of indium and 0 to 20 percent of tin are contained; or, based on the total weight of the copper-gallium-based alloy as 100%, the copper accounts for 10% -40%, the gallium accounts for 60% -90%, and the tin accounts for 0% -40%. In some embodiments, the copper gallium based alloy is a copper indium gallium tin alloy. In other embodiments, the copper gallium based alloy is a copper gallium tin alloy.
In one embodiment, the alloy layer has a thickness of 0.5 to 4 μm.
Correspondingly, an electrode slice includes: the current collector prepared by the preparation method or the current collector, and a metal layer deposited on the current collector; the metal layer is arranged on the surface of the alloy layer far away from the copper metal substrate.
According to the electrode plate provided by the embodiment of the invention, the current collector is adopted, so that the formation and growth of dendritic crystals in the charging and discharging processes of the battery can be effectively inhibited, and the electrochemical performance of the battery is improved.
In one embodiment, the material of the metal layer is lithium or sodium. When the metal layer is made of lithium, the electrode plate obtained by the method is a lithium metal negative electrode which has a sandwich structure of a lithium metal layer-alloy layer-copper metal substrate and can be applied to the preparation of lithium ion batteries, particularly lithium sulfur batteries. When the metal layer is made of sodium, the electrode plate obtained by the method is a sodium metal negative electrode, has a sandwich structure of a sodium metal layer-alloy layer-copper metal substrate, and can be applied to preparation of sodium ion batteries, especially sodium-sulfur batteries.
During preparation, a metal layer can be deposited on the surface of the alloy layer of the current collector by adopting the conventional technical means in the field. In some embodiments, the electrode sheet is a lithium metal negative electrode, and the discharge current and the discharge time may be determined according to a required negative electrode capacity by depositing a lithium metal layer on the surface of the alloy layer of the current collector by using an electrochemical deposition process.
Correspondingly, a secondary battery comprises the electrode plate.
The secondary battery provided by the embodiment of the invention has good electrochemical performance by adopting the electrode plate.
In one embodiment, the secondary battery is a lithium ion battery or a sodium ion battery, preferably a lithium sulfur battery or a sodium sulfur battery.
In order that the above implementation details and operations of the present invention will be clearly understood by those skilled in the art, and the advanced performance of a current collector, a method of manufacturing the same, an electrode sheet, and a secondary battery according to an embodiment of the present invention will be remarkably embodied, the implementation of the present invention will be exemplified by the following embodiments.
Example 1
The embodiment provides a lithium-sulfur battery, and a specific preparation method comprises the following steps:
1. preparation of current collectors
The method comprises the following steps of (1) mixing gallium, indium and tin according to a mass ratio of 7: 2: 1, rapidly heating to 400 ℃ for alloying, and allowing the formed indium gallium tin liquid metal to exist in a liquid state at normal temperature, as shown in figure 1.
And (3) dropwise adding the indium-gallium-tin liquid metal prepared in the steps to the surface of the copper foil, blade-coating by using a scraper to enable the indium-gallium-tin liquid metal to be uniformly coated on the surface of the copper foil to be subjected to alloying reaction with copper, removing the residual unreacted indium-gallium-tin liquid metal by using alcohol, and exposing the surface of the copper-indium-gallium-tin alloy to obtain the copper foil with the copper-indium-gallium-tin alloy layer formed on the surface as shown in the figures 2 and 3 as a current collector. The surface of the collector has indium gallium tin sites which are uniformly distributed, so that lithium ions in the subsequent charging and discharging process can be induced to be uniformly deposited on the surface of the collector, and the formation of lithium dendrites is inhibited.
2. Preparation of negative plate
Cutting the current collector prepared in the step into a pole piece with the diameter of 16mm, and taking the pole piece as a positive pole; obtaining a lithium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a negative electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; preparation of LS-09 model lithium Sulfur ElectrolysisThe liquid (the solvent is a mixed solvent of ethylene glycol dimethyl ether (DME) and 1, 3-Dioxolane (DOL) with the volume ratio of 1:1, and the solutes are 1M LiTFSI and 2 wt% LiNO3)。
And assembling the positive electrode, the negative electrode, the diaphragm and the lithium-sulfur electrolyte into a 2025 type button cell, then placing the obtained 2025 type button cell in a novyi cell charge-discharge testing system, and discharging for 2 hours according to a constant current discharge process with the current of 2mA so that a lithium metal layer is deposited on the surface of a current collector to obtain the lithium metal electrode plate.
3. Battery assembly
Assembling a sulfur-carbon composite positive plate (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400-type polypropylene diaphragm, LS-09 type lithium-sulfur electrolyte and the lithium metal electrode plate prepared in the steps to form the lithium-sulfur battery, wherein the surface density of an active substance of the lithium-sulfur battery is 2.6mg/cm2。
After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test under the test condition of 2mA/cm2The voltage interval is 1.7-2.8V.
Comparative example 1
The present comparative example provides a lithium sulfur battery, the specific method of manufacture comprising the steps of:
1. preparation of negative plate
Cutting the copper foil into pole pieces with the diameter of 16mm, and taking the pole pieces as positive electrodes; obtaining a lithium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a negative electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; preparing LS-09 type lithium sulfur electrolyte (a mixed solvent of ethylene glycol dimethyl ether (DME) and 1,3 Dioxolane (DOL) as a solvent, wherein the volume ratio of the two is 1:1, and solutes of 1M LiTFSI and 2 wt% LiNO3)。
And assembling the anode, the cathode, the diaphragm and the lithium-sulfur electrolyte into a 2025 type button cell, then placing the obtained 2025 type button cell in a novyi cell charge-discharge testing system, and discharging for 3 hours according to a constant current discharge process with the current of 4mA so that a lithium metal layer is deposited on the surface of the copper foil to obtain the lithium metal electrode plate.
3. Battery assembly
Assembling a sulfur-carbon composite positive plate (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400-type polypropylene diaphragm, LS-09 type lithium-sulfur electrolyte and the lithium metal electrode plate prepared in the steps to form the lithium-sulfur battery, wherein the surface density of an active substance of the lithium-sulfur battery is 2.38mg/cm2。
After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test under the test condition of 2mA/cm2The voltage interval is 1.7-2.8V.
The lithium sulfur batteries prepared in example 1 and comparative example 1 were used to perform electrochemical performance tests, respectively. Under the test condition that the charge-discharge rate is 0.5C, the initial specific Capacity of the lithium-sulfur battery of example 1 is 810mAh/g, the specific Capacity (Capacity) of the battery for 250 cycles is 630mAh/g, and the Coulombic Efficiency (CE) is more than 99%. However, the initial specific Capacity of the lithium-sulfur battery of comparative example 1 was 800mAh/g, the specific Capacity (Capacity) of the battery after 60 cycles (Cycle Number) was 80mAh/g, and the Coulombic Efficiency (CE) was < 95%.
Example 2
The embodiment provides a lithium-sulfur battery, and a specific preparation method comprises the following steps:
1. preparation of current collectors
The method comprises the following steps of (1) mixing gallium and tin according to a mass ratio of 92: 8, quickly heating to 400 ℃ for alloying, and allowing the formed gallium-tin liquid metal to exist in a liquid state at normal temperature.
And (3) dropwise adding the gallium-tin liquid metal prepared in the step to the surface of the copper foil, blade-coating by a scraper to enable the gallium-tin liquid metal to be uniformly coated on the surface of the copper foil to perform alloying reaction with copper, removing the residual unreacted gallium-tin liquid metal by using alcohol, and exposing the surface of the copper-indium-gallium-tin alloy to obtain the copper foil with the copper-gallium-tin alloy layer formed on the surface as a current collector. The surface of the collector has uniformly distributed gallium and tin sites, which can induce lithium ions to uniformly deposit on the surface of the collector in the subsequent charging and discharging process and inhibit the formation of lithium dendrites.
2. Preparation of negative plate
Cutting the current collector prepared in the step into a pole piece with the diameter of 16mm, and taking the pole piece as a positive pole; obtaining a lithium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a negative electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; preparing LS-09 type lithium sulfur electrolyte (a mixed solvent of ethylene glycol dimethyl ether (DME) and 1,3 Dioxolane (DOL) as a solvent, wherein the volume ratio of the two is 1:1, and solutes of 1M LiTFSI and 2 wt% LiNO3)。
And assembling the positive electrode, the negative electrode, the diaphragm and the lithium-sulfur electrolyte into a 2025 type button cell, then placing the obtained 2025 type button cell in a novyi cell charge-discharge testing system, and discharging for 2 hours according to a constant current discharge process with the current of 2mA so that a lithium metal layer is deposited on the surface of a current collector to obtain the lithium metal electrode plate.
3. Battery assembly
Assembling a sulfur-carbon composite positive plate (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400-type polypropylene diaphragm, LS-09 type lithium-sulfur electrolyte and the lithium metal electrode plate prepared in the steps to form the lithium-sulfur battery, wherein the surface density of an active substance of the lithium-sulfur battery is 2.6mg/cm2。
After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test under the test condition of 2mA/cm2The voltage interval is 1.7-2.8V.
Comparative example 2
The present comparative example provides a lithium sulfur battery, the specific method of manufacture comprising the steps of:
1. preparation of negative plate
Cutting the copper foil into pole pieces with the diameter of 16mm, and taking the pole pieces as positive electrodes; obtaining a lithium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a negative electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; preparing LS-09 type lithium sulfur electrolyte (a mixed solvent of ethylene glycol dimethyl ether (DME) and 1,3 Dioxolane (DOL) as a solvent, wherein the volume ratio of the two is 1:1, and solutes of 1M LiTFSI and 2 wt% LiNO3)。
And assembling the anode, the cathode, the diaphragm and the lithium-sulfur electrolyte into a 2025 type button cell, then placing the obtained 2025 type button cell in a novyi cell charge-discharge testing system, and discharging for 3 hours according to a constant current discharge process with the current of 4mA so that a lithium metal layer is deposited on the surface of the copper foil to obtain the lithium metal electrode plate.
3. Battery assembly
Assembling a sulfur-carbon composite positive plate (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400-type polypropylene diaphragm, LS-09 type lithium-sulfur electrolyte and the lithium metal electrode plate prepared in the steps to form the lithium-sulfur battery, wherein the surface density of an active substance of the lithium-sulfur battery is 2.38mg/cm2。
After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test under the test condition of 2mA/cm2The voltage interval is 1.7-2.8V.
The lithium sulfur batteries prepared in example 2 and comparative example 2 were used to perform electrochemical performance tests, respectively. Under the test condition that the charge-discharge rate is 0.5C, the initial specific Capacity of the lithium-sulfur battery of the example 2 is 810mAh/g, the specific Capacity (Capacity) of the battery for 250 cycles is 630mAh/g, and the Coulombic Efficiency (CE) is more than 99%. However, the initial specific Capacity of the lithium-sulfur battery of comparative example 2 was 800mAh/g, the specific Capacity (Capacity) of the battery after 60 cycles (Cycle Number) was 80mAh/g, and the Coulombic Efficiency (CE) was < 95%.
Example 3
The embodiment provides a sodium-sulfur battery, and a specific preparation method comprises the following steps:
1. preparation of current collectors
The method comprises the following steps of (1) mixing gallium and tin according to a mass ratio of 92: 8, quickly heating to 400 ℃ for alloying, and allowing the formed gallium-tin liquid metal to exist in a liquid state at normal temperature.
And (3) dropwise adding the gallium-tin liquid metal prepared in the step to the surface of the copper foil, blade-coating by a scraper to enable the gallium-tin liquid metal to be uniformly coated on the surface of the copper foil to perform alloying reaction with copper, removing the residual unreacted gallium-tin liquid metal by using alcohol, and exposing the surface of the copper-indium-gallium-tin alloy to obtain the copper foil with the copper-gallium-tin alloy layer formed on the surface as a current collector.
2. Preparation of negative plate
Cutting the current collector prepared in the step into a pole piece with the diameter of 16mm, and taking the pole piece as a positive pole; obtaining a sodium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a negative electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; NS-08 type sodium-sulfur electrolyte (the solvent is a mixed solvent of ethylene glycol dimethyl ether (DME) and 1,3 Dioxolane (DOL), the volume ratio of the two is 1:1, and the solute is 1M LiTFSI) is prepared.
And assembling the positive electrode, the negative electrode, the diaphragm and the sodium-sulfur electrolyte into a 2025 type button cell, then placing the obtained 2025 type button cell in a novyi cell charge-discharge testing system, and discharging for 2 hours according to a constant current discharge process with the current of 2mA so that a sodium metal layer is deposited on the surface of a current collector to obtain a sodium metal electrode plate.
3. Battery assembly
Assembling a sulfur-carbon composite positive plate (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400-type polypropylene diaphragm, an NS-08 type sodium-sulfur electrolyte and the sodium metal electrode plate prepared in the steps to form a sodium-sulfur battery, wherein the surface density of an active substance of the sodium-sulfur battery is 2.6mg/cm2。
After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test under the test condition of 2mA/cm2The voltage interval is 1.7-2.8V.
Comparative example 3
The comparative example provides a sodium-sulfur battery, and the specific preparation method comprises the following steps:
1. preparation of negative plate
Cutting the copper foil into pole pieces with the diameter of 16mm, and taking the pole pieces as positive electrodes; obtaining a sodium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a negative electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; NS-08 type sodium-sulfur electrolyte is prepared.
And assembling the anode, the cathode, the diaphragm and the sodium-sulfur electrolyte into a 2025 type button cell, then placing the obtained 2025 type button cell in a novyi cell charge-discharge testing system, and discharging for 3 hours according to a constant current discharge process with the current of 4mA so that a sodium metal layer is deposited on the surface of the copper foil to obtain a sodium metal electrode plate.
3. Battery assembly
Assembling a sulfur-carbon composite positive plate (carbon fiber is a carrier of the sulfur-carbon composite, the mass ratio of sulfur to carbon is 3:1), a 2400-type polypropylene diaphragm, an NS-08 type sodium-sulfur electrolyte and the sodium metal electrode plate prepared in the steps to form a sodium-sulfur battery, wherein the surface density of an active substance of the sodium-sulfur battery is 2.38mg/cm2。
After the detected voltage is normal, the battery is placed in a new power battery charge-discharge tester for charge-discharge test under the test condition of 2mA/cm2The voltage interval is 1.7-2.8V.
The sodium-sulfur batteries prepared in example 3 and comparative example 3 were respectively subjected to electrochemical performance tests. Under the test condition that the charge-discharge rate is 0.5C, the initial specific Capacity of the sodium-sulfur battery of the example 3 is 810mAh/g, the specific Capacity (Capacity) of the battery after 250 cycles is 630mAh/g, and the Coulombic Efficiency (CE) is more than 99%. However, the initial specific Capacity of the sodium-sulfur battery of comparative example 3 was 800mAh/g, the specific Capacity (Capacity) of the battery after 60 cycles (Cycle Number) was 80mAh/g, and the Coulombic Efficiency (CE) was < 95%.
Example 4
The embodiment provides a copper-lithium half cell, and the specific preparation method comprises the following steps:
1. the method comprises the following steps of (1) mixing gallium and tin according to a mass ratio of 92: 8, quickly heating to 400 ℃ for alloying, and allowing the formed gallium-tin liquid metal to exist in a liquid state at normal temperature.
And (3) dropwise adding the gallium-tin liquid metal prepared in the step to the surface of the copper foil, blade-coating by using a scraper to enable the gallium-tin liquid metal to be uniformly coated on the surface of the copper foil to be subjected to an alloying reaction with copper, removing the residual unreacted gallium-tin liquid metal by using alcohol, and exposing the surface of the copper-gallium-tin alloy to obtain the copper foil with the surface formed with the copper-gallium-tin alloy layer as a current collector.
2. Cutting the current collector prepared in the step into pole pieces with the diameter of 16mm, and taking the pole pieces as a negative pole; obtaining a lithium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a positive electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; preparing LS-09 type lithium-sulfur electrolyte; and assembling the positive electrode, the negative electrode, the diaphragm and the lithium-sulfur electrolyte into the 2025 type button cell.
Placing the obtained 2025 button cell in a New Wien cell charging and discharging test system, testing voltage, and placing in a New Wien cell charging and discharging tester to perform charging and discharging test on lithium half cell with charging voltage of 0.3V and discharging current of 1mA/cm2Discharging for 1 h.
Comparative example 4
The comparative example provides a copper-lithium half cell, and the specific preparation method comprises the following steps:
1. cutting the copper foil into pole pieces with the diameter of 16mm, and taking the pole pieces as a negative pole; obtaining a lithium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a positive electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; LS-09 type lithium-sulfur electrolyte is prepared. And assembling the positive electrode, the negative electrode, the diaphragm and the lithium-sulfur electrolyte into the 2025 type button cell.
2. Placing the obtained 2025 button cell in a New Wien cell charging and discharging test system, testing voltage, and placing in a New Wien cell charging and discharging tester to perform charging and discharging test on lithium half cell with charging voltage of 0.3V and discharging current of 1mA/cm2Discharging for 1 h.
The electrochemical performance of the copper lithium half-cells prepared in example 4 and comparative example 4 was measured. As shown in FIG. 4, the current density was 1mA/cm2The initial specific Capacity of the half-cell of copper-lithium of example 4 was 1100mAh/g, the specific Capacity (Capacity) of the cell after 600 cycles was 1000mAh/g, and the Coulombic Efficiency (CE)>99 percent. However, the initial specific Capacity of the copper-lithium half cell of comparative example 4 was 1100mAh/g, and the specific Capacity (Capacity) of the cell was 800mAh/g over 150 cycles (cycleNumber).
Example 5
The embodiment provides a copper-lithium half cell, and the specific preparation method comprises the following steps:
1. the method comprises the following steps of (1) mixing gallium and tin according to a mass ratio of 92: 8, quickly heating to 400 ℃ for alloying, and allowing the formed gallium-tin liquid metal to exist in a liquid state at normal temperature.
And (3) dropwise adding the gallium-tin liquid metal prepared in the step to the surface of the copper foil, blade-coating by using a scraper to enable the gallium-tin liquid metal to be uniformly coated on the surface of the copper foil to be subjected to an alloying reaction with copper, removing the residual unreacted gallium-tin liquid metal by using alcohol, and exposing the surface of the copper-gallium-tin alloy to obtain the copper foil with the surface formed with the copper-gallium-tin alloy layer as a current collector.
2. Cutting the current collector prepared in the step into pole pieces with the diameter of 16mm, and taking the pole pieces as a negative pole; obtaining a lithium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a positive electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; preparing LS-09 type lithium-sulfur electrolyte; and assembling the positive electrode, the negative electrode, the diaphragm and the lithium-sulfur electrolyte into the 2025 type button cell.
Placing the obtained 2025 button cell in a New Wien cell charging and discharging test system, testing voltage, and placing in a New Wien cell charging and discharging tester to perform charging and discharging test on lithium half cell with charging voltage of 0.3V and discharging current of 0.5mA/cm2Discharging for 1 h.
Comparative example 5
The comparative example provides a copper-lithium half cell, and the specific preparation method comprises the following steps:
1. cutting the copper foil into pole pieces with the diameter of 16mm, and taking the pole pieces as a negative pole; obtaining a lithium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a positive electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; LS-09 type lithium-sulfur electrolyte is prepared. And assembling the positive electrode, the negative electrode, the diaphragm and the lithium-sulfur electrolyte into the 2025 type button cell.
2. Placing the obtained 2025 button cell in a New Wien cell charging and discharging test system, testing voltage, and placing in a New Wien cell charging and discharging tester to perform charging and discharging test on lithium half cell with charging voltage of 0.3V and discharging current of 0.5mA/cm2Discharging for 1 h.
The electrochemical performance of the copper lithium half-cells prepared in example 5 and comparative example 5 were respectively tested. As shown in FIG. 5, the current density was 0.5mA/cm2Test strip ofAs a result, the initial specific Capacity of the half-cell of copper lithium of example 5 was 550mAh/g, the specific Capacity (Capacity) of the cell after 600 cycles was 530mAh/g, and the Coulombic Efficiency (CE)>99 percent. However, the initial specific Capacity of the copper-lithium half cell of comparative example 5 was 560mAh/g, and the specific Capacity (Capacity) of the cell was 400mAh/g over 140 cycles (Cycle Number).
Example 6
The embodiment provides a copper-lithium half cell, and the specific preparation method comprises the following steps:
1. the method comprises the following steps of (1) mixing gallium and tin according to a mass ratio of 92: 8, quickly heating to 400 ℃ for alloying, and allowing the formed gallium-tin liquid metal to exist in a liquid state at normal temperature.
And (3) dropwise adding the gallium-tin liquid metal prepared in the step to the surface of the copper foil, blade-coating by using a scraper to enable the gallium-tin liquid metal to be uniformly coated on the surface of the copper foil to be subjected to an alloying reaction with copper, removing the residual unreacted gallium-tin liquid metal by using alcohol, and exposing the surface of the copper-gallium-tin alloy to obtain the copper foil with the surface formed with the copper-gallium-tin alloy layer as a current collector.
2. Cutting the current collector prepared in the step into pole pieces with the diameter of 16mm, and taking the pole pieces as a negative pole; obtaining a sodium metal sheet with the diameter of 16mm and the thickness of 0.6mm as a positive electrode; obtaining a 2400 type polyethylene diaphragm as a diaphragm; preparing NS-08 type sodium-sulfur electrolyte; and assembling the positive electrode, the negative electrode, the diaphragm and the sodium-sulfur electrolyte into the 2025 type button cell.
Placing the obtained 2025 button cell in a New Wien cell charging and discharging test system, testing voltage, and placing in a New Wien cell charging and discharging tester to perform charging and discharging test on lithium half cell with charging voltage of 0.3V and discharging current of 0.5mA/cm2Discharging for 1 h.
The electrochemical performance of the copper-lithium half cell prepared in example 6 was tested. At a current density of 0.5mA/cm2The initial specific Capacity of the half-cell of example 6 was 600mAh/g, the specific Capacity (Capacity) of the cell over 80 cycles (cyclePower) was 530mAh/g, and the Coulombic Efficiency (CE)>99％。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A preparation method of a current collector is characterized by comprising the following steps:
obtaining a copper metal substrate and gallium-based liquid metal;
and coating the gallium-based liquid metal on the surface of the copper metal substrate, so that the gallium-based liquid metal and the copper on the surface of the copper metal substrate are subjected to an alloying reaction to prepare the copper metal substrate with an alloy layer formed on the surface, wherein the alloy layer is made of a copper-gallium-based alloy.
2. The method of claim 1, wherein the gallium-based liquid metal has a general formula Ga-X, wherein X is In, Sn, or In-Sn.
3. The method according to claim 1, wherein the gallium-based liquid metal is an indium-gallium-tin liquid metal and/or a gallium-tin liquid metal.
4. The production method according to any one of claims 1 to 3, wherein in the step of coating the liquid metal on the surface of the copper metal substrate, the liquid metal is coated on the surface of the copper metal substrate at 23 to 30 ℃.
5. A current collector, comprising: the device comprises a copper metal substrate and an alloy layer arranged on the copper metal substrate, wherein the alloy layer is made of copper-gallium-based alloy.
6. The current collector of claim 5, wherein the copper gallium-based alloy has a general formula of Cu-Ga-X, wherein X is In, Sn, or In-Sn.
7. The current collector of claim 5, wherein the copper gallium based alloy is a copper indium gallium tin alloy and/or a copper gallium tin alloy.
8. An electrode sheet, comprising: a current collector produced by the production method according to any one of claims 1 to 4 or the current collector according to any one of claims 5 to 7, and a metal layer deposited on the current collector; the metal layer is arranged on the surface of the alloy layer far away from the copper metal substrate.
9. The electrode sheet according to claim 8, wherein the material of the metal layer is lithium or sodium.
10. A secondary battery comprising the electrode sheet according to claim 8 or 9.
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| CN114094114A (en) * | 2021-11-23 | 2022-02-25 | 山东大学 | Sodium battery current collector and preparation method and application thereof |
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