CN111755699A - High-stability long-life metal lithium negative electrode material and preparation method and application thereof - Google Patents
High-stability long-life metal lithium negative electrode material and preparation method and application thereof Download PDFInfo
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- CN111755699A CN111755699A CN202010651940.2A CN202010651940A CN111755699A CN 111755699 A CN111755699 A CN 111755699A CN 202010651940 A CN202010651940 A CN 202010651940A CN 111755699 A CN111755699 A CN 111755699A
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
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Abstract
The invention relates to the technical field of lithium ion batteries, in particular to a high-stability long-life metal lithium negative electrode material and a preparation method thereof, and more particularly relates to a method for passivating the surface of metal lithium by using low-temperature gallium-based liquid metal, reducing the reaction activity of the metal lithium and stabilizing a metal lithium negative electrode; the high-stability long-life lithium metal negative electrode material is lithium metal optimized by a lithium-based alloy passivation layer; the method comprises the following steps: coating a layer of low-temperature gallium-based liquid metal on the surface of the metal lithium, and then carrying out alloying reaction in an inert atmosphere to obtain the alloy. The invention uses low-temperature gallium-based liquid metal with low melting point, good fluidity, good conductivity, lithium affinity and innocuity to coat the surface of the metal lithium with high reaction activity, and forms a lithium-based alloy passivation layer with good lithium affinity, corrosion resistance and high ion diffusion coefficient on the surface of the metal lithium, thereby reducing the nucleation barrier of lithium, accelerating the electrochemical dynamics of an electrode interface, and improving the cycling stability and the service life of the metal lithium.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, particularly relates to a high-stability long-life metal lithium negative electrode material and a preparation method thereof, and more particularly relates to a method for passivating the surface of metal lithium, reducing the reaction activity of the metal lithium and stabilizing a metal lithium negative electrode by using low-temperature gallium-based liquid metal.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
The rapid development of electric vehicles and power grids puts higher demands on battery systems. Conventional electrode materials need to be innovated. The lithium metal has high theoretical specific capacity (3860mAh/g), low standard electrode potential (-3.040V) and light weight (0.534 g/cm)3) And the conductive performance is good, and the like, and the lithium ion battery is an ideal candidate negative electrode material for constructing next-generation high-energy-density lithium ion batteries. However, corrosion of the electrolyte, uneven lithium deposition, large volume expansion effects, and unstable Solid Electrolyte Interface (SEI) can cause instability of the lithium metal negative electrode during operation, resulting in a reduction in cycle life.
The high reactivity of metallic lithium is one of the main causes of instability of metallic lithium negative electrodes. In a lithium metal battery, the lithium metal is always in a liquid electrolyte. Thermodynamically, lithium metal cannot stably coexist with all organic solvents. Corrosion of the liquid electrolyte to the metallic lithium is inevitable due to the high reactivity of the metallic lithium. This corrosion not only results in the constant consumption of electrolyte and active lithium, but also results in unstable interfaces and increased growth of lithium dendrites, which greatly reduces the stability and cycle life of the lithium metal battery.
Passivating the high-reactivity interface of the metallic lithium is an important method for preparing the high-stability long-life metallic lithium negative electrode material. At present, methods for passivating the surface of metallic lithium include designing artificial SEI, designing a host material for the metallic lithium, improving electrolyte components, covering a protective film and the like. However, the inventors found that: these methods tend to have problems of complexity, high pollution, and the like.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing a high-stability long-life metal lithium negative electrode material by passivating the surface of metal lithium by using low-temperature gallium-based liquid metal. The method for passivating the metal lithium, which is green, environment-friendly, simple and easy to operate, is developed, the high-stability and long-life metal lithium cathode material is prepared, and the material is applied to the high-energy-density and high-safety metal lithium battery, has an important promotion effect on the development of a new energy industry, and is significant.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a high-stability long-life lithium metal negative electrode material, comprising:
metallic lithium;
and a lithium-based alloy passivation layer loaded on the surface of the metal lithium.
One of the characteristics of the method of the invention is as follows: the surface of the metal lithium with high reaction activity is coated by the low-temperature gallium-based liquid metal with low melting point, good fluidity, good conductivity, lithium affinity and no toxicity, and a lithium-based alloy passivation layer with good lithium affinity, corrosion resistance and high ion diffusion coefficient is formed on the surface of the metal lithium, so that the nucleation barrier of lithium is reduced, the electrochemical dynamics of an electrode interface is accelerated, and the cycling stability and the service life of the metal lithium are improved.
In a second aspect of the present invention, a method for preparing a high-stability long-life lithium metal negative electrode material is provided, which comprises:
coating a layer of gallium-based liquid metal on the surface of the metal lithium;
and carrying out alloying reaction on the lithium sheet coated with the gallium-based liquid metal to form a lithium-based alloy passivation layer.
The invention adopts simple liquid metal coating, has simple operation and is very beneficial to large-scale application. The invention adopts environment-friendly low-temperature gallium-based liquid metal as a coating agent, thereby avoiding the problem of environmental pollution.
In a third aspect of the invention, there is provided a use of any one of the above metallic lithium negative electrode materials in the manufacture of lithium batteries, electric vehicles and power grids.
The invention effectively improves the cycling stability and the service life of the metal lithium, and is expected to be widely applied to the manufacture of electric automobiles and power grids, thereby promoting the development of new energy industries.
The invention has the beneficial effects that:
(1) the invention adopts environment-friendly low-temperature gallium-based liquid metal as a coating agent, thereby avoiding the problem of environmental pollution.
(2) The invention adopts simple liquid metal coating, has simple operation and is very beneficial to large-scale application.
(3) The method provided by the invention can reduce the nucleation barrier of lithium, improve the corrosion resistance of the metal lithium, accelerate the electrochemical dynamics of an electrode interface, and improve the cycle stability and the service life of the metal lithium.
(4) The method is simple, low in cost, strong in practicability and easy to popularize.
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 preparation of a high-stability long-life metallic lithium negative electrode material by using liquid metal coated metallic lithium in examples 1 to 10 of the present invention.
FIG. 2 is a scanning electron micrograph of a lithium sheet according to comparative example and example of the present invention.
FIG. 3 is a scanning electron microscope image of a GaInSn-Zn liquid metal coated lithium plate in example 1 of the present invention.
Fig. 4 is an X-ray diffraction pattern of a lithium sheet optimized for a lithium-based alloy passivation layer in example 1 of the present invention.
Fig. 5 is a scanning electron micrograph of a lithium sheet optimized for a lithium-based alloy passivation layer according to example 1 of the present invention.
Fig. 6 is a voltage-capacity curve of lithium on a lithium sheet and a lithium-based alloy passivation layer optimized lithium sheet according to comparative example and example 1 of the present invention.
Fig. 7 is a voltage-time plot of a symmetric cell for a lithium sheet and a symmetric cell for a lithium-based alloy passivation layer optimized lithium sheet in comparative example and example 1 of the present invention.
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 previously described, highly reactive metallic lithium is easily corroded by the liquid electrolyte, which not only results in continuous consumption of electrolyte and active lithium, but also results in unstable interface and increased growth of lithium dendrites, reducing the cycle stability and life of the metallic lithium negative electrode. Surface passivation is an effective modification scheme, but the current method has the problems of complexity, high pollution and the like. Therefore, the invention provides a green, environment-friendly, simple and easy-to-operate surface passivation method, namely a high-stability and long-life metal lithium cathode material is prepared by coating the surface of metal lithium with low-temperature gallium-based liquid metal (the melting point is more than 0 ℃ and less than 30 ℃).
This technical solution will now be further explained.
In some exemplary embodiments, the lithium metal includes, but is not limited to: any one of a lithium sheet, a lithium tape, a lithium foil, a lithium block, a lithium wire, and the like. According to the invention, the simple liquid metal is adopted to coat the metal lithium, so that the cycling stability and the service life of the metal lithium cathode are improved, the operation is simple, and the large-scale application is facilitated.
In some exemplary embodiments, the low temperature gallium-based liquid metal includes any one of gallium, gallium-zinc alloy, gallium-indium-tin-zinc alloy, and the like. The invention adopts environment-friendly low-temperature gallium-based liquid metal as a coating agent, thereby avoiding the problem of environmental pollution.
In some exemplary embodiments, the low temperature gallium-based liquid metal is coated on the lithium metal in an amount of 0.5 to 5.0mg/cm2. As the amount of coating is increased in the coating amount,the thickness of the surface passivation layer is increased, but when the low-temperature gallium-based liquid metal is coated on the lithium metal, the coating amount reaches 5.0mg/cm2The performance of metallic lithium is not greatly improved by continuing to increase the coating amount.
In some exemplary embodiments, the alloying reaction temperature is in the range of 25 ℃ to 45 ℃ to improve the alloying efficiency.
In some exemplary embodiments, the alloying reaction time is 5-30h to form a lithium-based alloy passivation layer with good lithium affinity, corrosion resistance and high ion diffusion coefficient on the surface.
The specific type of button cell is not particularly limited in this application and in some exemplary embodiments the button cell is a lithium-copper half cell or a lithium-lithium symmetric cell.
The specific type of the electrolyte is not particularly limited, and in some exemplary embodiments, the electrolyte of the battery is an ether or ester electrolyte.
In some exemplary embodiments, the inert atmosphere is helium, argon, a hydrogen-argon mixture, a vacuum atmosphere, or the like, and has an oxygen content of less than 1ppm and a moisture content of less than 1 ppm.
The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.
Example 1
The preparation method of the high-stability long-life lithium metal negative electrode material comprises the following steps:
(1) the fresh lithium pieces were removed from the inert atmosphere of argon and placed in a dry ambient (about 25 ℃) air atmosphere.
(2) And (3) cleaning oil stains and impurities on the surface of the lithium sheet in the step (1) by using a dry paper towel.
(3) Rapidly and uniformly coating a layer of gallium indium tin zinc liquid metal (melting point 3 ℃) on the upper surface and the lower surface of the cleaned lithium sheet by using a clean small hairbrush, wherein the loading capacity is 1mg/cm2As shown in fig. 1-3.
(4) And (4) rapidly putting the liquid metal coated lithium sheet in the step (3) into an argon inert atmosphere, and carrying out alloying reaction at the reaction temperature of 25 ℃ for 24 hours to obtain the high-stability long-life lithium metal cathode material, as shown in fig. 4 and 5.
(5) Using CR2032 button cell in 1M LiPF6Evaluating the electrochemical performance of the lithium metal anode material in the step (4) in an EC/EMC (volume ratio 1:1) liquid electrolyte. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Example 2
The preparation method of the high-stability long-life lithium metal negative electrode material comprises the following steps:
(1) the fresh lithium pieces were removed from the inert atmosphere of argon and placed in a dry ambient (about 25 ℃) air atmosphere.
(2) And (3) cleaning oil stains and impurities on the surface of the lithium sheet in the step (1) by using a dry paper towel.
(3) Rapidly and uniformly coating a layer of gallium indium tin liquid metal (melting point 5 ℃) on the upper surface and the lower surface of the cleaned lithium sheet by using a clean small brush, wherein the loading capacity is 1mg/cm2。
(4) And (4) rapidly putting the liquid metal coated lithium sheet in the step (3) into an argon inert atmosphere, and carrying out alloying reaction at the reaction temperature of 25 ℃ for 24 hours to obtain the high-stability long-life metal lithium cathode material.
(5) Using CR2032 button cell in 1M LiPF6Evaluating the electrochemical performance of the lithium metal anode material in the step (4) in an EC/EMC (volume ratio 1:1) liquid electrolyte. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Example 3
The preparation method of the high-stability long-life lithium metal negative electrode material comprises the following steps:
(1) the fresh lithium pieces were removed from the inert atmosphere of argon and placed in a dry ambient (about 25 ℃) air atmosphere.
(2) And (3) cleaning oil stains and impurities on the surface of the lithium sheet in the step (1) by using a dry paper towel.
(3) Rapidly and uniformly coating a layer of gallium-zinc liquid metal (melting point 25 ℃) on the upper surface and the lower surface of the cleaned lithium sheet by using a clean small hairbrush, wherein the loading capacity of the gallium-zinc liquid metal is 1mg/cm2。
(4) And (4) rapidly putting the liquid metal coated lithium sheet in the step (3) into an argon inert atmosphere, and carrying out alloying reaction at the reaction temperature of 25 ℃ for 24 hours to obtain the high-stability long-life metal lithium cathode material.
(5) Using CR2032 button cell in 1M LiPF6Evaluating the electrochemical performance of the lithium metal anode material in the step (4) in an EC/EMC (volume ratio 1:1) liquid electrolyte. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Example 4
The preparation method of the high-stability long-life lithium metal negative electrode material comprises the following steps:
(1) the fresh lithium pieces were removed from the inert atmosphere of argon and placed in a dry ambient (about 25 ℃) air atmosphere.
(2) And (3) cleaning oil stains and impurities on the surface of the lithium sheet in the step (1) by using a dry paper towel.
(3) Rapidly and uniformly coating a layer of gallium indium tin zinc liquid metal (melting point 3 ℃) on the upper surface and the lower surface of the cleaned lithium sheet by using a clean small hairbrush, wherein the loading capacity is 0.5mg/cm2。
(4) And (4) rapidly putting the liquid metal coated lithium sheet in the step (3) into an argon inert atmosphere, and carrying out alloying reaction at the reaction temperature of 25 ℃ for 24 hours to obtain the high-stability long-life metal lithium cathode material.
(5) Using CR2032 button cell in 1M LiPF6Evaluating the electrochemical performance of the lithium metal anode material in the step (4) in an EC/EMC (volume ratio 1:1) liquid electrolyte. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Example 5
The preparation method of the high-stability long-life lithium metal negative electrode material comprises the following steps:
(1) the fresh lithium pieces were removed from the inert atmosphere of argon and placed in a dry ambient (about 25 ℃) air atmosphere.
(2) And (3) cleaning oil stains and impurities on the surface of the lithium sheet in the step (1) by using a dry paper towel.
(3) Rapidly and uniformly coating a layer of gallium indium tin zinc liquid metal (melting point 3 ℃) on the upper surface and the lower surface of the cleaned lithium sheet by using a clean small hairbrush, wherein the loading capacity is 2mg/cm2。
(4) And (4) rapidly putting the liquid metal coated lithium sheet in the step (3) into an argon inert atmosphere, and carrying out alloying reaction at the reaction temperature of 25 ℃ for 24 hours to obtain the high-stability long-life metal lithium cathode material.
(5) Using CR2032 button cell in 1M LiPF6Evaluating the electrochemical performance of the lithium metal anode material in the step (4) in an EC/EMC (volume ratio 1:1) liquid electrolyte. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Example 6
The preparation method of the high-stability long-life lithium metal negative electrode material comprises the following steps:
(1) the fresh lithium pieces were removed from the inert atmosphere of argon and placed in a dry ambient (about 25 ℃) air atmosphere.
(2) And (3) cleaning oil stains and impurities on the surface of the lithium sheet in the step (1) by using a dry paper towel.
(3) Rapidly and uniformly coating a layer of gallium indium tin zinc liquid metal (melting point 3 ℃) on the upper surface and the lower surface of the cleaned lithium sheet by using a clean small hairbrush, wherein the loading capacity is 1mg/cm2。
(4) And (4) rapidly putting the liquid metal coated lithium sheet in the step (3) into an argon inert atmosphere, and carrying out alloying reaction at the reaction temperature of 15 ℃ for 24 hours to obtain the high-stability long-life metal lithium cathode material.
(5) Using CR2032 button cell in 1M LiPF6Evaluating the electrochemical performance of the lithium metal anode material in the step (4) in an EC/EMC (volume ratio 1:1) liquid electrolyte. BuckleThe structure of the battery comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Example 7
The preparation method of the high-stability long-life lithium metal negative electrode material comprises the following steps:
(1) the fresh lithium pieces were removed from the inert atmosphere of argon and placed in a dry ambient (about 25 ℃) air atmosphere.
(2) And (3) cleaning oil stains and impurities on the surface of the lithium sheet in the step (1) by using a dry paper towel.
(3) Rapidly and uniformly coating a layer of gallium indium tin zinc liquid metal (melting point 3 ℃) on the upper surface and the lower surface of the cleaned lithium sheet by using a clean small hairbrush, wherein the loading capacity is 1mg/cm2。
(4) And (4) rapidly putting the liquid metal coated lithium sheet in the step (3) into an argon inert atmosphere, and carrying out alloying reaction at the reaction temperature of 35 ℃ for 24 hours to obtain the high-stability long-life metal lithium cathode material.
(5) Using CR2032 button cell in 1M LiPF6Evaluating the electrochemical performance of the lithium metal anode material in the step (4) in an EC/EMC (volume ratio 1:1) liquid electrolyte. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Example 8
The preparation method of the high-stability long-life lithium metal negative electrode material comprises the following steps:
(1) the fresh lithium pieces were removed from the inert atmosphere of argon and placed in a dry ambient (about 25 ℃) air atmosphere.
(2) And (3) cleaning oil stains and impurities on the surface of the lithium sheet in the step (1) by using a dry paper towel.
(3) Rapidly and uniformly coating a layer of gallium indium tin zinc liquid metal (melting point 3 ℃) on the upper surface and the lower surface of the cleaned lithium sheet by using a clean small hairbrush, wherein the loading capacity is 1mg/cm2。
(4) And (4) rapidly putting the liquid metal coated lithium sheet in the step (3) into an argon inert atmosphere, and carrying out alloying reaction at the reaction temperature of 25 ℃ for 12 hours to obtain the high-stability long-life metal lithium cathode material.
(5) Using CR2032 button cell in 1M LiPF6Evaluating the electrochemical performance of the lithium metal anode material in the step (4) in an EC/EMC (volume ratio 1:1) liquid electrolyte. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Example 9
The preparation method of the high-stability long-life lithium metal negative electrode material comprises the following steps:
(1) the fresh lithium pieces were removed from the inert atmosphere of argon and placed in a dry ambient (about 25 ℃) air atmosphere.
(2) And (3) cleaning oil stains and impurities on the surface of the lithium sheet in the step (1) by using a dry paper towel.
(3) Rapidly and uniformly coating a layer of gallium indium tin zinc liquid metal (melting point 3 ℃) on the upper surface and the lower surface of the cleaned lithium sheet by using a clean small hairbrush, wherein the loading capacity is 1mg/cm2。
(4) And (4) rapidly putting the liquid metal coated lithium sheet in the step (3) into an argon inert atmosphere, and carrying out alloying reaction at the reaction temperature of 25 ℃ for 48 hours to obtain the high-stability long-life metal lithium cathode material.
(5) Using CR2032 button cell in 1M LiPF6Evaluating the electrochemical performance of the lithium metal anode material in the step (4) in an EC/EMC (volume ratio 1:1) liquid electrolyte. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Example 10
The preparation method of the high-stability long-life lithium metal negative electrode material comprises the following steps:
(1) the fresh lithium pieces were removed from the inert atmosphere of argon and placed in a dry ambient (about 25 ℃) air atmosphere.
(2) And (3) cleaning oil stains and impurities on the surface of the lithium sheet in the step (1) by using a dry paper towel.
(3) With clean hairThe upper surface and the lower surface of the cleaned lithium sheet are quickly and uniformly coated with a layer of gallium indium tin zinc liquid metal (melting point is 3 ℃) by a brush, and the loading capacity of the liquid metal is 1mg/cm2。
(4) And (4) rapidly putting the liquid metal coated lithium sheet in the step (3) into an argon inert atmosphere, and carrying out alloying reaction at the reaction temperature of 25 ℃ for 24 hours to obtain the high-stability long-life metal lithium cathode material.
(5) Using CR2032 button cell in 1M LiTFSI-DOL/DME (volume ratio 1:1, 1 wt% LiNO)3) And (4) evaluating the electrochemical performance of the lithium metal negative electrode material in the step (4) in the liquid electrolyte. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Comparative example
The implementation of the comparative example mainly comprises the following steps:
(1) and cleaning oil stains and impurities on the surface of the fresh lithium sheet by using a dry paper towel.
(2) Using CR2032 button cell in 1M LiPF6Evaluating the electrochemical performance of the lithium metal anode material in step (1) in an EC/EMC (volume ratio 1:1) liquid electrolyte. The button cell structure comprises a positive electrode shell (stainless steel), a negative electrode shell (stainless steel), a gasket (stainless steel), a current collector, a lithium negative electrode, electrolyte and a diaphragm (PP).
Performance testing
(1) The nucleation barrier and cycling stability of lithium-based alloy passivation layer optimized lithium sheets were evaluated using a charge and discharge device (nover CT-4008) using the button cell assembled in example 1 as an example. Meanwhile, as a comparison, the above-described performance of a battery (comparative example) assembled with a lithium sheet not coated with a liquid metal was also tested, and the results are shown in fig. 6 and 7, in which,
first, at a current density of 0.5mA/cm2Test of lithium nucleation barriers (nucleation overpotentials) on lithium sheets and lithium-based alloy passivation layer optimized lithium sheets are shown in fig. 6. Fig. 6 is a graph of lithium deposition voltage versus capacity on a lithium sheet and a lithium-based alloy passivation layer optimized lithium sheet. The nucleation barrier of lithium on the lithium sheet was 0.476V, lithium on lithiumThe nucleation barrier on the lithium sheet optimized for the base alloy passivation layer was 0.081V. The results show that the lithium-based alloy passivation layer formed after coating of the liquid metal has good lithium affinity and can reduce the nucleation barrier of lithium.
Next, at a current density of 1.0mA/cm2The capacity is 1.0mAh/cm2The cycling stability of the symmetric cells of the lithium sheet and the symmetric cells of the lithium-based alloy passivation layer optimized lithium sheet were tested under the conditions and the results are shown in fig. 7. Fig. 7 is a voltage-time curve for a symmetric cell for a lithium sheet and a symmetric cell for a lithium sheet optimized for a lithium-based alloy passivation layer. It can be seen that the voltage of the symmetric cell of the lithium plate is unstable and fluctuates severely up and down due to the instability of the electrode interface structure induced by corrosion. And the symmetrical battery voltage of the lithium sheet optimized by the lithium-based alloy passivation layer is stable and can last for 400 h. The results show that the lithium-based alloy passivation layer formed after the liquid metal is coated can resist the corrosion of electrolyte to the electrode, the interface structure stability of the electrode is improved, and the cycle stability and the service life of the electrode are improved.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. 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. Although the present invention has been described with reference to the specific embodiments, it should be understood by those skilled in the art that various changes and modifications may be made without departing from the spirit and scope of the invention.
Claims (10)
1. A high-stability long-life lithium metal negative electrode material is characterized by comprising:
metallic lithium;
and a lithium-based alloy passivation layer loaded on the surface of the metal lithium.
2. The highly stable long-life lithium metal negative electrode material of claim 1, wherein said lithium-based alloy passivation layer is alloyed with a gallium-based liquid metal coated on the surface of lithium metal.
3. The highly stable long-life metallic lithium negative electrode material of claim 2, wherein said gallium-based liquid metal comprises: gallium, gallium-zinc alloy, gallium-indium-tin alloy or gallium-indium-tin-zinc alloy.
4. The highly stable long life lithium metal anode material of claim 1, wherein said lithium metal comprises: any one of a lithium sheet, a lithium tape, a lithium foil, a lithium block, or a lithium wire.
5. The highly stable long life lithium metal anode material of claim 2, wherein said gallium based liquid metal is coated in an amount of 0.5 to 5.0mg/cm2。
6. The highly stable long life lithium metal anode material of claim 2, wherein said coating method comprises: any one of manual coating, spray coating and spin coating.
7. The highly stable long life lithium metal anode material of claim 2, wherein the alloying reaction is carried out under the following conditions: reacting for 5-30h at 25-45 ℃ under the protection of inert gas.
8. The highly stable long life lithium metal anode material of claim 7, wherein said inert atmosphere comprises: one of helium, argon, hydrogen-argon mixed gas and vacuum atmosphere, its oxygen content is less than 1ppm, and its water content is less than 1 ppm.
9. A preparation method of a high-stability long-life metal lithium negative electrode material is characterized in that,
coating a layer of gallium-based liquid metal on the surface of the metal lithium;
and carrying out alloying reaction on the lithium sheet coated with the gallium-based liquid metal to form a lithium-based alloy passivation layer.
10. Use of the lithium metal negative electrode material of any one of claims 1 to 8 in the manufacture of lithium batteries, electric vehicles and power grids.
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