CN108736056B - Lithium metal interface protection structure and preparation and application thereof - Google Patents
Lithium metal interface protection structure and preparation and application thereof Download PDFInfo
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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
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a lithium metal interface protection structure and preparation and application thereof. Specifically, the invention discloses an interface protection structure. The invention also discloses a preparation method and application of the interface protection structure. The battery comprising the interface protection structure has excellent cycle performance and service life. The preparation method has the characteristics of simple process, low cost, easily obtained raw materials and the like.
Description
Technical Field
The invention relates to the field of electrochemistry, in particular to a lithium metal interface protection structure and preparation and application thereof.
Background
Owing to the small volume change of 10% of the graphite cathode in the circulation process, the lithium ion battery using the graphite cathode as the cathode material can obtain stable circulation performance and long service life. However, the lithium storage capacity of the graphite negative electrode material is relatively low (339 mAh/g in the case of lithium intercalation and 372mAh/g in the case of lithium deintercalation), and the industrial demand cannot be met in the process that the lithium battery market continuously seeks a higher energy density system.
The application prospect of lithium metal as a high-energy-density negative electrode material (the theoretical capacity of the lithium metal is 3860mAh/g and the lowest electrode potential) in emerging high-energy storage battery systems such as lithium air and lithium sulfur is consistently good, but the problems of low cycle efficiency, poor safety and the like always prevent the further popularization and application of the lithium metal in the battery industry. It has been found through extensive research that non-uniform lithium deposition occurs during battery charging, whether on the surface of a lithium metal or other metal current collector. With a continuous charging process, non-uniform lithium deposition inevitably leads to large volume expansion of the lithium metal surface and local lithium dendrite growth. Volume expansion and dendrite problems can lead to increased electrode interfacial resistance, and loss of battery capacity. The continuous dendritic crystal growth can pierce an electrolyte diaphragm to cause a battery short circuit, so that the lithium metal cathode is always accompanied with huge potential safety hazards in the use process, and the lithium metal cathode is difficult to be applied to working environments with higher requirements on safety coefficients, such as electric vehicles, portable electronic equipment and the like. In recent years, the service life and efficiency of lithium metal anodes have been significantly improved by various solutions proposed in the industry, but it is still difficult to satisfy the demand for large-scale commercialization by improving strength.
The protection effect of the existing protection method on lithium dendrites is too single. Wherein, the use of solid electrolyte can inhibit dendritic growth to a certain extent, but the lower ionic conductivity and the poorer electrode/electrolyte contact surface can cause the internal resistance of the battery to be greatly increased; in addition, the passivation layer with protective effect can be formed at the surface of the electrode in an accelerated manner by adding the film formation promoting additive into the electrolyte, however, the passivation layer does not have the mechanical property of inhibiting the growth of dendrites, uneven dendrite growth still occurs on the surface of the electrode finally, and the overgrowth of dendrites can pierce through the passivation layer, so that the lithium metal part which is not covered by the passivation layer directly contacts with the electrolyte and regenerates a new passivation layer, and the lithium and the electrolyte in the system are continuously consumed by repeatedly breaking and regenerating the passivation layer.
In review, although alternative lithium metal protection methods currently exist in the art, the structural stability and cycling performance of the existing lithium metal negative electrodes are not satisfactory.
Therefore, there is an urgent need in the art to develop a protection method and a preparation process thereof that can effectively achieve high cycle efficiency of lithium metal.
Disclosure of Invention
The invention aims to provide an interface protection structure capable of efficiently protecting lithium metal, and preparation and application thereof.
In a first aspect of the present invention, there is provided an interface protection structure precursor material, which is prepared by:
1) providing a mixed slurry, wherein the mixed slurry comprises: metal fluorides, carbon materials, binders and solvents;
2) coating the mixed slurry on the surface of a metal substrate to obtain the metal substrate containing a first coating;
3) and baking the metal substrate containing the first coating to obtain a metal substrate containing a second coating, wherein the second coating is the precursor material of the interface protection structure.
In another preferred example, the metal substrate is a metal substrate material that does not alloy with lithium metal.
In another preferred embodiment, the metal substrate is selected from the group consisting of: copper foil, nickel foil, stainless steel foil.
In another preferred embodiment, the metal fluoride is selected from the group consisting of: nickel fluoride, manganese fluoride, iron fluoride, titanium fluoride, copper fluoride, tin fluoride, or a combination thereof; and/or
The carbon material is selected from the group consisting of: ultra-dense high-conductivity carbon black, graphene, ketjen black, acetylene black, carbon nanotubes, or a combination thereof; and/or
The binder is selected from the group consisting of: polyvinylidene fluoride, polyimide, t-butyl rubber, polyacrylonitrile, polyacrylate, sodium alginate, or a combination thereof.
In another preferred embodiment, the solvent is selected from the group consisting of: water, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or a combination thereof.
In another preferred example, in the mixed slurry, the mass ratio of the metal fluoride, the carbon material, and the binder is 5 to 12: 1-3: 1-5, preferably 7-10: 1-2: 1-3.
In another preferred embodiment, the thickness of the first coating layer is 10-100 microns, preferably 20-40 microns.
In another preferred embodiment, the temperature of the baking treatment is 60-160 ℃, preferably 100-140 ℃; and/or
The treatment time of the baking treatment at the treatment temperature is 1-20h, preferably 6-16h, more preferably 8-14 h.
In another preferred example, the baking treatment is performed under vacuum or under the protection of inert gas.
In another preferred embodiment, the method further comprises the following step after the step 3): cutting the product obtained in the step 3) to obtain the cathode material containing the interface protection structure precursor material.
In a second aspect of the present invention, an interface protection structure is provided, which is prepared as follows:
i) providing a negative electrode material containing the precursor material of the interface protection structure in the first aspect of the invention, an electrolyte, a diaphragm and a lithium electrode plate;
ii) assembling a battery with the anode material, the electrolyte, the separator, and the lithium electrode sheet;
iii) carrying out electrochemical reduction treatment on the battery obtained in the step ii), and disassembling the battery, thus obtaining the interface protection structure by stripping from the obtained negative electrode.
In another preferred example, the electrolyte, the separator, and the lithium electrode sheet are not particularly limited, and may be prepared using materials conventional in the art, or using methods conventional in the art, or may be commercially available.
In another preferred embodiment, the electrolyte is selected from the group consisting of: 3011R (from Thailand Promega chemical New chemical materials Co., Ltd., Zhanggang), and a self-formulated electrolyte (wherein the lithium salt is selected from the group consisting of lithium hexafluorophosphate, lithium perchlorate, lithium bistrifluoromethanesulfonylimide, or a combination thereof, and the solvent is selected from the group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, ethylene glycol dimethyl ether, 1, 3-dioxolane, or a combination thereof).
In another preferred embodiment, the membrane is selected from the group consisting of: polyethylene membranes, polypropylene membranes, propylene/ethylene copolymer membranes, polyester membranes (PET), cellulose membranes, polyimide membranes (PI), polyamide membranes (PA), spandex or aramid membranes, or combinations thereof.
In another preferred embodiment, the thickness of the lithium electrode plate is 50-200 microns, preferably 100-150 microns.
In another preferred embodiment, the electrochemical reduction treatment is: the cell was discharged to 0V.
In a third aspect of the present invention, there is provided an article comprising an interface protection structure precursor material according to the first aspect of the present invention or an interface protection structure according to the second aspect of the present invention.
In another preferred embodiment, the article is preferably a battery.
In a fourth aspect of the invention, a battery is provided, which comprises the interface protection structure according to the second aspect of the invention.
In another preferred example, the battery is a lithium metal battery, preferably a lithium metal secondary battery.
In another preferred example, the battery further includes a positive electrode material, a negative electrode material, an electrolytic solution, and a separator.
In another preferred embodiment, the interface protection structure of the second aspect of the present invention is disposed adjacent to the membrane.
In another preferred embodiment, the interface protection structure of the second aspect of the present invention is located between the negative electrode material and the separator material.
In another preferred embodiment, the negative electrode material is a support material of the interface protection structure, and preferably, the negative electrode material is selected from the following group: copper foil, copper mesh, lithium foil, nickel mesh, aluminum foil, aluminum mesh, or combinations thereof.
In another preferred embodiment, the battery has a coulombic efficiency of 60% or more, preferably 70% or more, more preferably 80% or more, preferably 90% or more, and most preferably 95% or more, after 100 weeks of the lithium metal deposition/decomposition cycle.
It is to be understood that within the scope of the present invention, the above-described features of the present invention and those specifically described below (e.g., in the examples) may be combined with each other to form new or preferred embodiments. Not to be reiterated herein, but to the extent of space.
Drawings
FIG. 1 illustrates a method of using the interface protection structure of the present invention.
Fig. 2 is a graph showing the change in coulombic efficiency of the lithium copper batteries 1 to 6 obtained in examples 1 to 6 and the lithium copper battery C1 obtained in comparative example 1, which were cycled for 100 weeks under the test conditions of the present invention.
Detailed Description
The present inventors have conducted extensive and intensive studies for a long time and have unexpectedly prepared an interface protection structure capable of efficiently protecting lithium metal, and a battery comprising the interface protection structure can achieve excellent cycle characteristics and service life. The preparation method of the interface protection structure has the characteristics of simple process, low cost, easily obtained raw materials and the like. On this basis, the inventors have completed the present invention.
Interface protection structure and preparation method thereof
In the present invention, it is understood that the interface protection structure obtained by the electrochemical reduction treatment has a lithium fluoride framework.
In the present invention, the interface protection structure precursor material comprises a metal fluoride/carbon material/binder.
Typically, the metal fluorides include (but are not limited to): the conventional metal fluoride such as nickel fluoride, titanium fluoride, copper fluoride, iron fluoride, or manganese fluoride, or a combination thereof, may be selected from materials conventional in the art, or may be prepared by conventional methods, or may be commercially available.
Typically, the particle size of the metal fluoride is 10 to 100 nm.
Typically, the carbon material includes (but is not limited to): ultra-dense high conductivity carbon black (Super-P), Ketjen black, acetylene black, graphene, carbon nanotubes, or combinations thereof.
Typically, the binder includes (but is not limited to): tertiary butyl rubber, polyimide, polyvinylidene fluoride, polyacrylonitrile, polyacrylate, sodium alginate, or a combination thereof.
In a preferred embodiment, the metal fluoride: carbon material: the weight ratio of the binder is 65-89%: 10-30%: 1 to 5 percent.
In the invention, the loading amount of the metal fluoride is 1-5 mg/square centimeter.
Typically, the interface protection structure is prepared as follows:
(1) stirring and pre-dissolving a binder in an organic solvent to obtain a binder solution, wherein the concentration of the binder solution is not more than 30% by mass;
(2) mixing and stirring metal fluoride, a carbon material and a binder solution in an organic solvent to obtain precursor material slurry;
(3) coating the precursor material slurry on one side surface of a current collector, preheating at low temperature to volatilize an organic solvent, and then baking in an inert atmosphere or a vacuum environment;
(4) and (3) putting the baked pole piece into a battery with a counter electrode being a lithium piece, discharging to 0V for reduction, disassembling the battery, and standing the electrochemically reduced pole piece in an air environment to obtain the peelable self-supporting interface protection structure.
Typically, the organic solvent differs depending on the binder, including (but not limited to): water, N-methylpyrrolidone, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, or a combination thereof.
In another preferred embodiment, the solvent is N-methylpyrrolidone.
In another preferred embodiment, the stirring is magnetic stirring.
In another preferred embodiment, the stirring time in step (1) and/or (2) is 1 to 5 hours, preferably 2 to 3 hours.
In another preferred embodiment, the concentration of the binder solution in the step (1) is 5-30%, preferably 10%.
In another preferred embodiment, the low-temperature preheating temperature is 80 to 140 ℃, and more preferably 100 to 120 ℃. In another preferred embodiment, the baking time is 1 to 20 hours, and more preferably 3 to 15 hours.
In another preferred example, the baking is performed under a vacuum environment or under protection of inert gas.
The protective structure according to the present invention mainly constitutes a negative electrode with a support structure for use in a lithium secondary battery. The support structure is selected from the group consisting of: copper foil, copper mesh, lithium foil, nickel mesh.
More specifically, in the present invention, the inventors have found that a self-supporting structure having a lithium fluoride framework can be formed after it is chemically reduced by lithium ion by coating a coating layer consisting of a metal fluoride/carbon material/binder on the surface of a copper foil, a nickel foil or a stainless steel foil and other metal-based current collectors that are not alloyed with lithium metal. The structure is easy to strip from the metal substrate current collector, and after the structure is placed on the surface of lithium metal or other negative electrode current collectors, the lithium metal deposited below the protection structure and on one side close to the current collector can be effectively protected in the battery circulation process, the direct contact between the lithium metal and electrolyte is isolated, side reactions are avoided, dendritic growth and passivation of the lithium metal are prevented, and the like, and the characteristics of optimizing the electrode circulation efficiency and the service life are achieved (the use method of the protection structure is shown in figure 1). Cells containing the interface protection structure can achieve coulombic efficiencies of-98% and cycle lives in excess of 100 weeks at current densities of 0.5 milliamp per square centimeter and operating conditions of 1 milliamp-hour per square centimeter. Meanwhile, the preparation method of the interface protection structure is simple and practical, can be used for large-scale one-time treatment, and has great application potential.
Typically, the interface protection structure directly overlies the copper current collector, protecting the lithium metal deposited between the copper current collector and the protection structure, while characterizing the coulombic efficiency during deposition/decomposition of the lithium metal on the protected copper current collector. Lithium metal placed on the other side of the separator in this system only serves as a lithium source to provide lithium metal deposited on the copper foil side, not the protected object.
It should be understood that in practical applications, the protection structure may also be covered on the lithium metal cathode in the lithium metal battery to protect the lithium metal interface between the lithium metal and the protection structure, as shown in schematic diagram 1.
Applications of
The invention also provides a battery, which comprises the interface protection structure.
In the present invention, the coulombic efficiency of the battery is not less than 60%, preferably not less than 70%, more preferably not less than 80%, preferably not less than 90%, and most preferably not less than 95% after 100 weeks of lithium metal deposition/decomposition cycle.
Compared with the prior art, the invention has the following main advantages:
(1) in the battery comprising the interface protection structure, the interface protection structure can effectively protect lithium metal in a circulating process, so that the lithium metal is isolated from electrolyte in a deposition process, and no side reaction or only trace side reaction occurs;
(2) in the battery comprising the interface protection structure, the interface protection structure can effectively prevent the dendritic crystal growth and passivation of lithium metal;
(3) the battery comprising the interface protection structure has extremely excellent lithium metal negative electrode cycle performance, and can reach-98% of coulombic efficiency and cycle life of more than 100 weeks under the working conditions of current density of 0.5 milliampere/square centimeter and 1 milliampere-hour/square centimeter;
(4) the preparation method of the interface protection structure has the characteristics of simple process, low cost, easily obtained raw materials and the like;
(5) after the protection structure is prepared, the protection structure can be directly stripped from a metal substrate and implanted into other lithium metal batteries to protect the surface of a lithium metal cathode, and the application is strong.
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers. Unless otherwise indicated, percentages and parts are by weight.
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. In addition, any methods and materials similar or equivalent to those described herein can be used in the methods of the present invention. The preferred embodiments and materials described herein are intended to be exemplary only.
Example 1 copper lithium battery 1 with interface protection structure 1
a. Dissolving polyvinylidene fluoride (PVdF) with the mass ratio of 10% in an N-methylpyrrolidone (NMP) solvent in advance, and mixing and stirring for 3 hours in a magnetic stirrer to obtain a uniform solution;
b. according to the mass ratio of 7: 1: 2 stirring nickel fluoride, ultra-dense high-conductivity carbon black (Super-P) and polyvinylidene fluoride, adding a solvent N-methylpyrrolidone (NMP) into the mixture, placing the mixture into a magnetic stirrer, and mixing and stirring for 3 hours to obtain precursor material slurry;
c. coating the precursor material slurry on the surface of a copper foil (the thickness of the coating is about 20-60 mu m), and baking for 12 hours at 120 ℃ in a vacuum environment;
d. c, cutting the baked pole piece in the step c into a wafer with the diameter of 16mm to be used as a negative pole piece of the precursor with the interface protection structure;
e. and (3) dripping the electrolyte 3011R into a polyethylene diaphragm with the thickness of 20 microns according to the volume of 70 mu L, filling the electrolyte, the negative pole piece obtained in the step d and the metal lithium piece for the counter electrode into a CR2032 button battery case, and putting the battery into a glove box containing inert gas for assembly to obtain the battery.
f. Discharging the battery obtained in the step e to 0V for reduction, disassembling the battery, and standing the cathode pole piece subjected to electrochemical reduction in an air environment to obtain the strippable interface protection structure 1.
g. And (3) placing the interface protection structure 1 obtained in the step (f) on the surface of copper foil, dripping the electrolyte 3011R into a polyethylene diaphragm with the thickness of 20 microns according to the volume of 70 mu L, and putting the diaphragm into a CR2032 button battery case together with a metal lithium sheet serving as a counter electrode to obtain the copper lithium battery 1 with the interface protection structure 1.
Example 2 copper lithium battery 2 with interface protection Structure 2
The difference from example 1 is that: in step b the metal fluoride is manganese fluoride.
Example 3 copper lithium battery 3 with interface protection structure 3
The difference from example 1 is that: in step b the metal fluoride is ferric fluoride.
Example 4 copper lithium battery 4 with interface protection structure 4
The difference from example 1 is that: nickel fluoride in step b: ultra-dense high conductivity carbon black (Super-P): the proportion of polyvinylidene fluoride is 8:1: 1.
Example 5 copper lithium battery 5 with interface protection 5
The difference from example 1 is that: in step b the carbon material is graphene.
Example 6 copper lithium battery 6 with interface protection Structure 6
The difference from example 1 is that: in step b the binder is a polyimide.
Comparative example 1 lithium copper battery C1 without interface protection structure
a. And (3) dripping the electrolyte 3011R into a polyethylene diaphragm with the thickness of 20 microns according to the volume of 70 mu L, and filling the diaphragm into a CR2032 button battery case by taking a copper foil as a working electrode and a metal lithium sheet as a counter electrode to obtain the copper lithium battery C1 without an interface protection structure.
Electrochemical performance test
Lithium metal deposition/decomposition cycles were performed at a current density of 0.5 milliamp/square centimeter for lithium copper batteries 1-6 made in examples 1-6 and for lithium copper battery C1 made in comparative example 1, respectively. The cycling conditions were such that 1 mAmph/cm of lithium metal was deposited onto the copper electrode every week and then decomposed to a decomposition cut-off potential of 0.5V. The lithium metal protection effect on the copper electrode side was characterized in terms of coulombic efficiency, i.e., decomposition amount/deposition amount.
The results are shown in table 1 and fig. 2.
TABLE 1 coulombic efficiency results
| Week 10 | At |
|
|
| Example 1 | 97.55％ | 97.60％ | 97.65％ |
| Example 2 | 94.39％ | 97.19％ | 81.95％ |
| Example 3 | 95.75％ | 97.25％ | 68.68％ |
| Example 4 | 92.36％ | 95.25％ | 90.35％ |
| Example 5 | 95.90％ | 97.65％ | 97.15％ |
| Example 6 | 94.4％ | 96.7％ | 90.35％ |
| Comparative example 1 | 55.66％ | 25.22％ | -- |
As can be seen from fig. 2 and table 1: during 100 cycles, the lithium copper batteries 1-6 with the interface protection structure of the invention can maintain the coulombic efficiency of more than 90% in the first 50 cycles, while the lithium copper batteries C1 without the interface protection structure of the invention have the coulombic efficiency of only 55.66% in the 10 th cycle, decay to 25.22% in the 50 th cycle and cannot be cycled to 100 cycles.
All documents referred to herein are incorporated by reference into this application as if each were individually incorporated by reference. Furthermore, it should be understood that various changes and modifications of the present invention can be made by those skilled in the art after reading the above teachings of the present invention, and these equivalents also fall within the scope of the present invention as defined by the appended claims.
Claims (11)
1. A lithium metal battery, wherein the battery comprises an interface protection structure;
the interface protection structure is prepared as follows:
i) providing a negative electrode material, an electrolyte, a diaphragm and a lithium electrode plate of the interface protection structure precursor material;
ii) assembling a battery with the anode material, the electrolyte, the separator, and the lithium electrode sheet;
iii) carrying out electrochemical reduction treatment on the battery obtained in the step ii), and disassembling the battery, so that the interface protection structure can be obtained by stripping from the obtained negative electrode;
the precursor material of the interface protection structure is prepared as follows:
1) providing a mixed slurry, wherein the mixed slurry comprises: metal fluorides, carbon materials, binders and solvents;
2) coating the mixed slurry on the surface of a metal substrate to obtain the metal substrate containing a first coating;
3) baking the metal substrate containing the first coating to obtain a metal substrate containing a second coating, wherein the second coating is the precursor material of the interface protection structure;
the electrochemical reduction treatment is as follows: discharging the battery to 0V;
the interface protection structure obtained by the electrochemical reduction treatment has a lithium fluoride framework;
the battery further comprises a positive electrode material, a negative electrode material, an electrolyte and a separator;
the interface protection structure is located between the anode material and the separator material.
2. The battery of claim 1, wherein the negative electrode material is a support material for the interface protection structure.
3. The battery of claim 1, wherein the negative electrode material is selected from the group consisting of: copper foil, copper mesh, lithium foil, nickel mesh, aluminum foil, aluminum mesh, or combinations thereof.
4. The cell of claim 1, wherein the metal fluoride is selected from the group consisting of: nickel fluoride, manganese fluoride, iron fluoride, titanium fluoride, copper fluoride, tin fluoride, or a combination thereof; and/or
The carbon material is selected from the group consisting of: ultra-dense high-conductivity carbon black, graphene, ketjen black, acetylene black, carbon nanotubes, or a combination thereof; and/or
The binder is selected from the group consisting of: polyvinylidene fluoride, polyimide, t-butyl rubber, polyacrylonitrile, polyacrylate, sodium alginate, or a combination thereof.
5. The battery according to claim 1, wherein a mass ratio of the metal fluoride, the carbon material, and the binder in the mixed slurry is 5 to 12: 1-3: 1-5.
6. The battery of claim 1, wherein the baking process has a process temperature of 60 to 160 ℃; and/or
The treatment time of the baking treatment at the treatment temperature is 1-20 h.
7. The battery of claim 1, wherein the battery has a coulombic efficiency of 60% or more after 100 weeks of lithium metal deposition/decomposition cycles.
8. The battery of claim 1, wherein the battery has a coulombic efficiency of 70% or more after 100 weeks of lithium metal deposition/decomposition cycling.
9. The battery of claim 1, wherein the battery has a coulombic efficiency of 80% or more after 100 weeks of lithium metal deposition/decomposition cycles.
10. The battery of claim 1, wherein the battery has a coulombic efficiency of 90% or more after 100 weeks of lithium metal deposition/decomposition cycling.
11. The battery of claim 1, wherein the battery has a coulombic efficiency of 95% or more after 100 weeks of lithium metal deposition/decomposition cycling.
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| CN110071284B (en) * | 2019-03-01 | 2022-06-14 | 上海大学 | Method for protecting lithium metal electrode |
| CN109950476B (en) * | 2019-04-18 | 2022-10-14 | 电子科技大学 | Metallic lithium negative electrode material and preparation method and application thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070006955A (en) * | 2005-07-07 | 2007-01-12 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| CN103378349A (en) * | 2012-04-30 | 2013-10-30 | 三星Sdi株式会社 | Negative electrode, rechargeable lithium battery including same and method of preparing rechargeable lithium battery |
| CN105280886A (en) * | 2015-09-16 | 2016-01-27 | 中国科学院化学研究所 | Surface in-situ processing method of metal lithium negative electrode and application |
| CN105449156A (en) * | 2015-03-27 | 2016-03-30 | 万向A一二三系统有限公司 | Preparation method of negative electrode of lithium-ion battery |
| CN106207177A (en) * | 2016-09-07 | 2016-12-07 | 天津爱敏特电池材料有限公司 | Containing artificial SEI floor height volume and capacity ratio and the silicon-carbon cathode material of cycle performance |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080026297A1 (en) * | 2005-01-11 | 2008-01-31 | Air Products And Chemicals, Inc. | Electrolytes, cells and methods of forming passivaton layers |
| TWI395359B (en) * | 2005-09-15 | 2013-05-01 | Lg Chemical Ltd | Nonaqueous electrolyte for improving performance and lithium secondary battery comprising the same |
| US10547088B2 (en) * | 2014-09-10 | 2020-01-28 | Battelle Memorial Institute | High Coulombic efficiency cycling of metal batteries |
| US20160172706A1 (en) * | 2014-12-10 | 2016-06-16 | GM Global Technology Operations LLC | Electrolyte and electrode structure |
-
2017
- 2017-04-20 CN CN201710262306.8A patent/CN108736056B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20070006955A (en) * | 2005-07-07 | 2007-01-12 | 삼성에스디아이 주식회사 | Lithium secondary battery |
| CN103378349A (en) * | 2012-04-30 | 2013-10-30 | 三星Sdi株式会社 | Negative electrode, rechargeable lithium battery including same and method of preparing rechargeable lithium battery |
| CN105449156A (en) * | 2015-03-27 | 2016-03-30 | 万向A一二三系统有限公司 | Preparation method of negative electrode of lithium-ion battery |
| CN105280886A (en) * | 2015-09-16 | 2016-01-27 | 中国科学院化学研究所 | Surface in-situ processing method of metal lithium negative electrode and application |
| CN106207177A (en) * | 2016-09-07 | 2016-12-07 | 天津爱敏特电池材料有限公司 | Containing artificial SEI floor height volume and capacity ratio and the silicon-carbon cathode material of cycle performance |
Non-Patent Citations (3)
| Title |
|---|
| Hong Li et al.Reversible formation and decomposition of LiF clusters using transition metal fluorides as precursors and their application in rechargeable Li batteries.《Advanced materials》.Wiley,2003,第15卷(第9期),736-739. * |
| Regulating Li deposition at artificial solid electrolyte interphases;Lei Fan et al;《Journal of Materials Chemistry A》;Royal society of chemistry;20170111;第5卷(第7期);3485、3490 * |
| Reversible formation and decomposition of LiF clusters using transition metal fluorides as precursors and their application in rechargeable Li batteries;Hong Li et al;《Advanced materials》;Wiley;20030502;第15卷(第9期);0736-0738 * |
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