CN110752375A - Lithium battery for inhibiting growth of lithium dendrite by using liquid metal and preparation method and application thereof - Google Patents
Lithium battery for inhibiting growth of lithium dendrite by using liquid metal and preparation method and application thereof Download PDFInfo
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M4/667—Composites in the form of layers, e.g. coatings
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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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- 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 the technical field of lithium ion batteries, in particular to a lithium battery for inhibiting the growth of lithium dendrites by utilizing liquid metal and a preparation method and application thereof; the method comprises the following steps: and coating a gallium-based liquid metal layer on a current collector, taking the current collector as a positive electrode, and assembling the current collector and parts required by the lithium battery together into a liquid battery in an inert atmosphere to obtain the lithium ion battery. The invention utilizes the low-temperature gallium-based liquid metal coating to improve the lithium affinity of the current collector, further reduces the initial nucleation barrier of lithium, finally eliminates the growth of lithium dendrites, realizes uniform metal lithium deposition, obviously improves the coulombic efficiency of the battery, stabilizes the SEI film, prolongs the cycle life of the battery, and reduces the occurrence of the safety problem induced by the lithium dendrites. The method can complete the preparation of the current collector through simple liquid metal coating, and is very beneficial to large-scale production.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium battery for inhibiting growth of lithium dendrites by utilizing liquid metal and a preparation method and application thereof.
Background
The information disclosed in this background of the invention is only for enhancement of understanding of the general background of the invention and is not necessarily to be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person skilled in the art.
With the rapid development of new energy industries such as electric vehicles and the like, people have more and more urgent requirements on energy storage devices with high safety and high energy density. Lithium ion batteries are the most rapidly developed new energy storage devices at present. However, the energy density of currently used lithium ion batteries is generally low, which limits their further development. Metallic lithium is the most promising negative electrode for lithium ion batteries, and has a light weight (0.534 g/cm)3) The electrochemical potential is low (-3.040V/vs. standard hydrogen electrode). More importantly, the lithium metal cathode can be matched with a lithium-free high-capacity anode such as sulfur, selenium, vanadium pentoxide, oxygen and the like to form a high-energy-density battery system. However, non-uniform deposition of lithium can produce lithium dendrites, which in turn can lead to safety problems, lower coulombic efficiency, and lower cycle life of the battery. The lithium affinity of the current collector has an important influence on the deposition morphology of lithium, and the current collector with general lithium affinity (such as copper foil, copper foam, nickel foam) has a large nucleation barrier (or nucleation overpotential) at the initial nucleation of lithium, thereby causing subsequent non-uniform lithium deposition and generation of lithium dendrites. In order to improve the lithium affinity of the current collector and reduce the initial nucleation barrier of lithium, researchers have conducted related research works to improve the lithium affinity of the current collector, such as in-situ formation of an oxide layer, magnetron sputtering of nucleation seeds (e.g., gold, zinc, silver, etc.), doping of heterogeneous non-metal atoms (e.g., nitrogen, sulfur, phosphorus), and the like. However, these studies are still far from adequate, and some methods are complicated, costly and difficult to implement on a large scale.
Disclosure of Invention
The method which is low in cost and capable of realizing large-scale production is developed to improve the lithium affinity of the current collector, and the method is applied to the lithium metal negative electrode, and has important significance for further development of high-safety and high-energy-density lithium metal batteries. In view of the above problems, the present invention provides a lithium battery using a liquid metal coating to inhibit the growth of lithium dendrites, and a method and application thereof.
In order to achieve the purpose, the invention adopts the following technical means:
the invention discloses a lithium battery for inhibiting growth of lithium dendrite by utilizing liquid metal, which comprises a current collector, a lithium negative electrode, electrolyte and a diaphragm, wherein the diaphragm is positioned between the lithium negative electrode and the current collector, the electrolyte is filled in the battery, and a gallium-based liquid metal layer is coated on one surface of the current collector, which is close to the diaphragm.
Secondly, the invention discloses a preparation method of a lithium battery for inhibiting the growth of lithium dendrites by utilizing liquid metal, which comprises the following steps: and coating a gallium-based liquid metal layer on a current collector, taking the current collector as a positive electrode, and assembling the current collector and parts required by the lithium battery together into a liquid battery in an inert atmosphere to obtain the lithium ion battery.
Finally, the invention discloses the application of the lithium battery for inhibiting the growth of the lithium dendrite by utilizing the liquid metal and the method thereof in the field of new energy industry, such as electric vehicles, energy storage devices and the like.
The method provided by the invention is characterized in that: the lithium affinity of the current collector is improved by using the low-temperature gallium-based liquid metal coating, so that the initial nucleation barrier of lithium is reduced, the growth of lithium dendrites is finally eliminated, and uniform metal lithium deposition is realized. This is because: (1) the gallium-based liquid metal has low melting point, fluidity and easy film formation, and is easy to coat. (2) The gallium-based liquid metal can perform an alloying reaction with lithium, so that the liquid metal has lithium affinity, the coating can reduce the initial nucleation barrier of the lithium, the growth of lithium dendrites is finally eliminated, and uniform lithium deposition is realized. However, a general current collector (e.g., copper foil) cannot undergo an alloying reaction with lithium, and thus has lithium-phobicity. Nucleation of lithium on these lithium-phobic current collectors requires overcoming large interfacial energies and nucleation barriers, resulting in non-uniform lithium nucleation, which is the source of the formation of non-uniform lithium deposits. The lithium-philic liquid metal is coated on the surface of the lithium-phobic current collector to form a thin layer, so that the lithium-philic property of the surface of the current collector can be improved, the interface energy and nucleation potential barrier of lithium in the deposition process are further reduced, and uniform lithium nucleation and deposition are induced.
Compared with the prior art, the invention has the following beneficial effects:
(1) the method provided by the invention can complete the preparation of the current collector through simple liquid metal coating, and is very beneficial to large-scale production.
(2) The method provided by the invention can effectively improve the lithium affinity of the current collector, reduce the initial nucleation barrier of lithium and realize uniform dendrite-free lithium deposition.
(3) The method provided by the invention obviously improves the coulombic efficiency of the battery, stabilizes the SEI film, prolongs the cycle life of the battery and reduces the safety problem of lithium dendrite induction.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a schematic flow chart of the current collector preparation in examples 1 to 15 of the present invention.
Fig. 2 is a voltage-capacity diagram of a battery in a comparative example of the present invention.
Fig. 3 is a voltage-capacity diagram of the battery in example 1 of the present invention.
Fig. 4 is a graph of coulombic efficiencies for cells of example 1 of the present invention and comparative example.
FIG. 5 shows the deposition of 0.2mAh/cm in the comparative example of the present invention2Scanning electron microscopy images of lithium onto current collectors.
FIG. 6 shows the deposition of 0.2mAh/cm in example 1 of the present invention2Scanning electron microscopy of lithium on copper foil coated with gallium-based liquid metal.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As mentioned above, the uneven deposition of lithium can generate lithium dendrites, which can cause safety problems, lower coulombic efficiency and lower cycle life of the battery, but the current solutions to overcome the problems have the problems of complex process, high cost and difficulty in mass production. Therefore, the technical scheme of the lithium battery for inhibiting the growth of the lithium dendrite by using the liquid metal and the preparation method thereof are further explained.
In some exemplary embodiments, the lithium metal includes, but is not limited to: any one of lithium foil, lithium sheet, lithium ribbon, lithium block, lithium powder, lithium alloy, and the like.
In some exemplary embodiments, the current collector includes, but is not limited to: any one of copper foil, bronze foil, brass foil, copper mesh, stainless steel mesh, copper foam, nickel foam, carbon paper, carbon cloth, and the like.
In some exemplary embodiments, the gallium-based liquid metal includes any one of gallium, gallium-zinc alloy, gallium-indium-tin-zinc alloy, and the like.
In some exemplary embodiments, the gallium-based liquid metal is supported on the current collector at a loading of 0.1 to 2.0mg/cm2。
In some exemplary embodiments, the electrolyte of the liquid battery is an ester electrolyte or an ether electrolyte.
In some exemplary embodiments, the inert atmosphere comprises any one of argon, helium, hydrogen argon, etc., having a moisture content of less than 1ppm and an oxygen content of less than 1 ppm.
In some exemplary embodiments, the liquid battery is of a symmetrical battery or a full battery type.
The invention is further described below with reference to fig. 1-3.
Example 1
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the copper foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin gallium indium tin zinc liquid metal layer (melting point is 3 ℃) on the copper foil obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The 2032 type button cell is assembled under argon atmosphere and comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium sheet, electrolyte and a diaphragm (PP).
Example 2
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the copper foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a layer of gallium indium tin liquid metal thin layer (melting point 5 ℃) on the copper foil obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 3
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the copper foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating the copper foil obtained in the step (1) with a small brushA thin liquid metal layer (melting point 25 ℃) of gallium zinc is formed, and the loading capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 4
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the copper foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a layer of gallium liquid metal thin layer (melting point is 30 ℃) on the copper foil obtained in the step (1) by using a small brush, wherein the loading capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 5
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the bronze foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a gallium indium tin zinc liquid metal thin layer (melting point is 3 ℃) on the bronze foil obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 6
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) the surface of the yellow copper foil (current collector) is cleaned by absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin layer of gallium indium tin zinc liquid metal (melting point 3 ℃) on the yellow copper foil obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 7
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the foam copper foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin layer of gallium indium tin zinc liquid metal (melting point 3 ℃) on the foamed copper foil obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 8
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the foamed nickel foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin gallium indium tin zinc liquid metal layer (melting point 3 ℃) on the foamed nickel foil obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 9
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the copper mesh (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin gallium indium tin zinc liquid metal layer (melting point 3 ℃) on the copper mesh obtained in the step (1) by using a small brush, wherein the loading capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 10
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the stainless steel mesh (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin layer of gallium indium tin zinc liquid metal (melting point 3 ℃) on the stainless steel mesh in the step (1) by using a small brush, wherein the loading capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 11
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the carbon paper (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin gallium indium tin zinc liquid metal layer (melting point 3 ℃) on the carbon paper obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 0.5mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 12
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the carbon cloth (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin gallium indium tin zinc liquid metal layer (melting point 3 ℃) on the carbon cloth obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 0.1mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 13
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the copper foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin gallium indium tin zinc liquid metal layer (melting point is 3 ℃) on the copper foil obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 1.0mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, and then taking a lithium wafer with the diameter of 1cm as a counter electrodeEther liquid electrolyte 1MLiTFSiDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 14
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the copper foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin gallium indium tin zinc liquid metal layer (melting point is 3 ℃) on the copper foil obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 2.0mg/cm2As shown in fig. 1.
(3) Cutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Example 15
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the copper foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Coating a thin gallium indium tin zinc liquid metal layer (melting point 3 ℃) on the copper foil obtained in the step (1) by using a small brush, wherein the capacity of the liquid metal is 0.1mg/cm2As shown in fig. 1.
(3) The obtained current collector was cut into a circular piece with a diameter of 1cm, and then a lithium piece with a diameter of 1cm was used as a counter electrode, and the current collector of this example was assembled into a 2032 type button cell shown in example 1 under an argon atmosphere using an ester liquid electrolyte 1MLiPF6EC/DEC (1: 1).
Comparative example
A method for preparing a lithium battery for inhibiting the growth of lithium dendrites using a liquid metal, comprising the steps of:
(1) and (3) cleaning the surface of the copper foil (current collector) by using absolute ethyl alcohol to remove impurities and oil stains.
(2) Will be provided withCutting the obtained current collector into a wafer with the diameter of 1cm, then taking a lithium wafer with the diameter of 1cm as a counter electrode, and adopting an ether liquid electrolyte 1MLiTFSIDOL/DME (1: 11% LiNO)3) The current collector of this example was assembled into a 2032 type button cell as shown in example 1 under an argon atmosphere.
Performance testing
(1) Taking the button cell prepared in example 1 as an example, the nucleation barrier and coulombic efficiency of the cell were evaluated by using a charge and discharge device (novyi CT-4008). Meanwhile, as a comparison, the above-described performance of the battery (comparative example 1) assembled with the current collector without the gallium-based liquid metal layer coated thereon was also tested, and the results are shown in fig. 2 to 4.
First, at a current density of 1.0mA/cm2Lithium was deposited under the conditions of (1), and the nucleation barrier of lithium was measured, and the results are shown in fig. 2 and 3, which are voltage-capacity graphs of the battery in comparative example and example 1, respectively. As can be seen in fig. 2, the nucleation barrier for lithium on the copper foil is approximately 256.1 mV. As can be seen in fig. 3, the nucleation overpotential for lithium was reduced to 23.1mV after coating with the gallium-based liquid metal. The results show that the liquid metal coating can obviously improve the lithium affinity of the current collector and reduce the initial nucleation barrier of lithium.
Next, at a current density of 1.0mA/cm2The capacity is 1.0mAh/cm2The coulombic efficiencies of the two batteries are tested under the conditions, and the results are shown in fig. 4, and it can be seen that the average coulombic efficiency is improved from 94.1% to 96.9% after the liquid metal is coated, so that the coulombic efficiency is obviously improved.
(2) And (3) characterizing the lithium deposition morphology:
the batteries prepared according to the method of example 1 and comparative example were used at a current density of 0.2mA/cm2Under the condition of (1), 0.2mA/cm is deposited2To the current collector. And then disassembling the battery under the argon atmosphere to obtain a current collector after lithium deposition, and observing the lithium growth morphology on the surface of the pole piece by using a scanning electron microscope. The results are shown in FIG. 5 (comparative example) and FIG. 6 (example 1). As can be seen in fig. 5, the copper foil (current collector) that was not coated with the gallium-based liquid metal had many dendritic lithium dendrites thereon. As can be seen in FIG. 6, the gallium-based coatingNo dendritic lithium dendrites were found on the copper foil of the liquid metal. The above results indicate that the liquid metal coating can inhibit the generation of lithium dendrites and induce uniform lithium deposition, which helps to improve the coulombic efficiency of the battery, stabilize the SEI film, prolong the cycle life of the battery, and reduce the occurrence of lithium dendrite-induced safety problems.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The lithium battery is characterized by comprising a current collector, a lithium negative electrode, electrolyte and a diaphragm, wherein one surface of the current collector, which is close to the diaphragm, is coated with a gallium-based liquid metal layer.
2. The lithium battery of claim 1, wherein the lithium negative electrode comprises: any one of lithium foil, lithium sheet, lithium ribbon, lithium block, lithium powder and lithium alloy.
3. The lithium battery of claim 1, wherein the current collector comprises: any one of copper foil, bronze foil, brass foil, copper mesh, stainless steel mesh, foam copper, foam nickel, carbon paper and carbon cloth; preferably, the electrolyte of the liquid battery is an ester electrolyte or an ether electrolyte.
4. A lithium battery as in any of claims 1-3, wherein the gallium-based liquid metal comprises: gallium, gallium-zinc alloy, gallium-indium-tin-zinc alloy.
5. The lithium battery of any of claims 1-4, wherein the gallium-based liquid metal is present on the current collector in an amount of from 0.1 to 2.0mg/cm2(ii) a Preferably, theThe liquid battery is of a symmetrical or full type.
6. A method for preparing a lithium battery by utilizing liquid metal to inhibit the growth of lithium dendrites is characterized by comprising the following steps: and coating a gallium-based liquid metal layer on a current collector, taking the current collector as a positive electrode, and assembling the current collector and parts required by the lithium battery together into a liquid battery in an inert atmosphere to obtain the lithium ion battery.
7. The preparation method according to claim 6, wherein the electrolyte of the liquid battery is an ester electrolyte or an ether electrolyte;
preferably, the current collector includes: any one of copper foil, bronze foil, brass foil, copper mesh, stainless steel mesh, foam copper, foam nickel, carbon paper and carbon cloth.
8. The method of claim 6, wherein the gallium-based liquid metal comprises: any one of gallium, gallium-zinc alloy, gallium-indium-tin alloy and gallium-indium-tin-zinc alloy; preferably; the load capacity of the gallium-based liquid metal on the current collector is 0.1-2.0mg/cm2。
9. The method according to any one of claims 6 to 8, wherein the inert gas atmosphere comprises any one of argon gas, helium gas, and a hydrogen-argon gas mixture, and has a moisture content of less than 1ppm and an oxygen content of less than 1 ppm; preferably, the type of the liquid battery is a symmetrical battery or a full battery.
10. Use of a lithium battery utilizing a liquid metal to inhibit lithium dendrite growth according to any one of claims 1-5 and/or a battery prepared by the method according to any one of claims 6-9 in the new energy industry field.
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