CN111430663A - Lithium negative pole piece, preparation method thereof and lithium battery - Google Patents
Lithium negative pole piece, preparation method thereof and lithium battery 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
- 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
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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
- H01M4/139—Processes of manufacture
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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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- 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
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Abstract
The invention provides a lithium negative pole piece, a preparation method thereof and a lithium battery. The lithium negative electrode sheet includes: a lithium negative electrode; a protective layer including a lithium carbide layer disposed on one surface of the lithium negative electrode. Therefore, the lithium carbide is arranged on the surface of the lithium cathode as the protective layer, so that the problems of falling, breaking and the like of the protective layer can be effectively prevented, the long-term effectiveness of the protective layer is further ensured, and the coulombic efficiency of the battery and the capacity retention rate of the battery in long-term circulation are effectively improved; the lithium carbide layer can also inhibit the growth of lithium dendrites, effectively preventing the short circuit of the battery due to the generation of lithium dendrites.
Description
Technical Field
The invention relates to the technical field of batteries, in particular to a lithium negative pole piece, a preparation method thereof and a lithium battery.
Background
At present, lithium metal is taken as a negative electrode material, which is a hot spot of solid-state battery research, on one hand, the lithium metal is one of the negative electrode materials with the largest theoretical energy density, meanwhile, the lithium metal has lower electrochemical potential, and the larger the voltage difference between the positive electrode and the negative electrode is, the higher the specific energy of the battery is. However, when lithium metal is used as a negative electrode material, the deposition is uneven due to the difference of the electrodeposition rate in the use process, so that lithium dendrites are generated, the lithium dendrites are easy to pierce through a solid electrolyte to cause short circuit, and simultaneously, waste lithium is generated, so that the cycle capacity is reduced; and the lithium metal cathode has high requirements on solid electrolyte, and has high ionic conductivity, good electronic blocking capability and the like. In order to effectively protect the lithium metal of the negative electrode, a protection layer is coated on the surface of the lithium negative electrode, but the protection layer coated on the surface of the lithium metal has the problems of fracture, breakage, falling and the like of the protection layer caused by severe volume change of the lithium metal negative electrode in the battery circulation process, and finally the protection layer fails.
Therefore, research on the lithium negative electrode tab is awaited.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, an object of the present invention is to provide a lithium negative electrode sheet, in which a protective layer is not easy to fall off or break, or effectively inhibits a battery short circuit caused by lithium dendrite, or improves the coulombic efficiency or the battery capacity retention rate of the battery.
In one aspect of the invention, a lithium negative electrode tab is provided. According to an embodiment of the present invention, the lithium negative electrode tab includes: a lithium negative electrode; a protective layer including a lithium carbide layer disposed on one surface of the lithium negative electrode. Therefore, the lithium carbide is arranged on the surface of the lithium cathode as the protective layer, so that the problems of falling, breaking and the like of the protective layer can be effectively prevented, the long-term effectiveness of the protective layer is further ensured, and the coulombic efficiency of the battery and the capacity retention rate of the battery in long-term circulation are effectively improved; the lithium carbide layer can also inhibit the growth of lithium dendrites, effectively preventing the short circuit of the battery due to the generation of lithium dendrites.
According to an embodiment of the invention, the protective layer further comprises: a graphite layer disposed on a surface of the lithium carbide layer distal from the lithium negative electrode.
According to an embodiment of the present invention, the graphite layer is at least one of natural graphite, artificial graphite, bulk graphite, flake graphite, and graphene.
According to an embodiment of the invention, the thickness of the protective layer is 5 nanometers to 50 micrometers.
In another aspect of the invention, the invention provides a method for preparing the lithium negative electrode plate. According to the embodiment of the invention, the method for preparing the lithium negative pole piece comprises the following steps: a layer of graphite is formed on one surface of a lithium foil and reacted at a predetermined temperature for a predetermined time to form a lithium carbide layer on the surface of the lithium foil, resulting in a protective layer. Therefore, graphite reacts with lithium, and a layer of lithium carbide is generated on the surface of the lithium foil and serves as a protective layer arranged on the surface of the lithium cathode, so that the problems of falling, breaking and the like of the protective layer can be effectively prevented, the long-term effectiveness of the protective layer is further ensured, and the coulombic efficiency of the battery and the capacity retention rate of the battery in long-term circulation are effectively improved; the lithium carbide layer can also inhibit the growth of lithium dendrites, and effectively prevent the short circuit of the battery caused by the generation of the lithium dendrites; in addition, the preparation method has the advantages of simple process, easy operation and low cost, and can obviously improve the production efficiency.
According to the embodiment of the invention, the preset temperature is 20-80 ℃, and the preset time is 1-24 hours.
According to an embodiment of the invention, the reaction satisfies at least one of the following conditions: under dry conditions; the method is carried out under the protection of inert gas.
According to an embodiment of the present invention, the graphite is adsorbed on the surface of the lithium carbide layer.
According to an embodiment of the present invention, the graphite is at least one of natural graphite, artificial graphite, bulk graphite, and flake graphite, and preferably, the graphite is flake graphite.
In yet another aspect of the present invention, a lithium battery is provided. According to an embodiment of the invention, the lithium battery comprises the lithium negative electrode plate. Therefore, the battery has high coulombic efficiency, good capacity retention rate in long-term circulation and long service life. As will be understood by those skilled in the art, the lithium battery has all the features and advantages of the negative electrode plate of the lithium battery, and the details are not repeated herein.
Drawings
Fig. 1 is a schematic structural diagram of a lithium negative electrode tab according to an embodiment of the present invention.
Fig. 2 is a schematic structural diagram of a lithium negative electrode tab according to another embodiment of the present invention.
Fig. 3 is a schematic structural diagram of a lithium battery according to still another embodiment of the present invention.
Fig. 4 is a graph comparing test data of discharge capacities of the lithium batteries in example 1 and comparative example 1.
Fig. 5 is a graph comparing test data of discharge capacities of lithium batteries in example 2 and comparative example 1.
Detailed Description
The following describes embodiments of the present invention in detail. The following examples are illustrative only and are not to be construed as limiting the invention. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
In one aspect of the invention, a lithium negative electrode tab is provided. According to an embodiment of the present invention, referring to fig. 1, a lithium negative electrode tab 10 includes: a lithium negative electrode 11; a protective layer 12, the protective layer 12 including a lithium carbide layer 121, the lithium carbide layer 121 being disposed on one surface of the lithium negative electrode 11. Therefore, the lithium carbide is arranged on the surface of the lithium cathode as the protective layer, so that the problems of falling, breaking and the like of the protective layer can be effectively prevented, the long-term effectiveness of the protective layer is further ensured, and the coulombic efficiency of the battery and the capacity retention rate of the battery in long-term circulation are effectively improved; the lithium carbide layer can also inhibit the growth of lithium dendrites, effectively preventing the short circuit of the battery due to the generation of lithium dendrites.
According to the embodiment of the invention, the lithium negative electrode can adopt the lithium foil, so that the cutting of the lithium negative electrode is convenient, and the manufacturing of the battery is convenient.
According to an embodiment of the present invention, referring to fig. 2, the protective layer further includes: and a graphite layer 122, wherein the graphite layer 122 is arranged on the surface of the lithium carbide layer 121 far away from the lithium negative electrode 11. Therefore, the graphite layer can act together with the lithium carbide layer to inhibit the growth of lithium dendrites and further prevent the short circuit of the battery caused by the lithium dendrites; moreover, the existence of the graphite layer can improve the compactness of the protective layer, increase the specific surface area in the lithium deposition process and have small influence on the internal resistance of the lithium battery using the lithium negative pole piece; in addition, the existence of the graphite layer can also improve the structural stability of the lithium carbide layer, and further improve the coulombic efficiency of the battery and the capacity retention rate of the battery; in addition, the graphite has certain flexibility, so that the solid-solid interface impedance of the solid-state lithium battery using the lithium negative electrode pole piece can be obviously reduced, and the service performance of the solid-state lithium battery is further improved.
According to an embodiment of the present invention, the graphite layer may be at least one of natural graphite, artificial graphite, bulk graphite, flake graphite, and graphene. Therefore, the graphite is widely selected, the growth of lithium dendrites can be well inhibited, and the solid-solid interface impedance of the solid lithium battery using the lithium negative pole piece is reduced. The graphene layer is graphene when the graphene layer is of a single-layer structure, and can also be formed by multilayer laminated graphene, so that the graphene of a laminated structure can better increase the specific surface area in the lithium deposition process.
According to an embodiment of the invention, the thickness of the protective layer is 5 nanometers to 50 micrometers, such as 5 nanometers, 10 nanometers, 20 nanometers, 50 nanometers, 80 nanometers, 100 nanometers, 300 nanometers, 500 nanometers, 700 nanometers, 900 nanometers, 1 micrometer, 5 micrometers, 10 micrometers, 20 micrometers, 30 micrometers, 40 micrometers or 50 micrometers. Therefore, the protective layer with the thickness can well inhibit the growth of lithium dendrites and prevent the short circuit of the battery, and the thinner protective layer has less influence on the internal resistance of the lithium battery using the lithium negative pole piece; if the thickness is less than 5 nanometers, the thickness of the protective layer is too thin, the protective effect on the lithium cathode is relatively poor, and the growth of lithium dendrites cannot be well inhibited; if the thickness is larger than 1 micrometer, the internal resistance inside the battery is relatively large, and the deposition of lithium in the use process of the lithium battery is further influenced.
In another aspect of the invention, the invention provides a method for preparing the lithium negative electrode plate. According to the embodiment of the invention, the method for preparing the lithium negative pole piece comprises the following steps: a layer of graphite is formed on one surface of a lithium foil and reacted at a predetermined temperature for a predetermined time to form a lithium carbide layer on the surface of the lithium foil, resulting in a protective layer. Therefore, graphite reacts with lithium, and a layer of lithium carbide is generated on the surface of the lithium foil and serves as a protective layer arranged on the surface of the lithium cathode, so that the problems of falling, breaking and the like of the protective layer can be effectively prevented, the long-term effectiveness of the protective layer is further ensured, and the coulombic efficiency of the battery and the capacity retention rate of the battery in long-term circulation are effectively improved; the lithium carbide layer can also inhibit the growth of lithium dendrites, and effectively prevent the short circuit of the battery caused by the generation of the lithium dendrites; in addition, the preparation method has the advantages of simple process, easy operation and low cost, and can obviously improve the production efficiency.
According to the embodiment of the present invention, the reaction between graphite and lithium occurs only on the surface of the lithium foil, and after lithium carbide is formed on the surface of the lithium foil, the lithium carbide separates the graphite from the lithium foil, thereby preventing the reaction from further extending into the lithium foil, so that the reaction between lithium and graphite does not affect the function of the lithium foil as a battery negative electrode.
The particular method of forming a layer of graphite on one surface of a lithium foil according to embodiments of the present invention is not particularly required, and those skilled in the art can flexibly select the method according to the actual situation. In some embodiments, a layer of graphite may be formed on the surface of the lithium foil by at least one of spraying, manual coating, mechanical coating, wet coating, and inkjet coating, all of which may form a layer of graphite powder uniformly on the surface of the lithium foil. Wherein the spray may be sieved through a screen and uniformly sprinkled on the surface of the lithium foil.
According to an embodiment of the present invention, the predetermined temperature is 20 to 80 ℃ (such as 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃) and the predetermined time is 1 to 24 hours (such as 1 hour, 1.2 hours, 1.5 hours, 2 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours or 24 hours). Therefore, a uniform lithium carbide layer can be quickly and effectively obtained on the surface of the lithium foil under the conditions, and the lithium foil is ensured not to generate side reaction; if the temperature is lower than 20 ℃, the reaction rate of lithium and graphite is slow, so that the reaction time is long, and the production efficiency is influenced; if the temperature is higher than 80 ℃, lithium may generate a side reaction with oxygen, which affects the service performance of the lithium negative electrode, and further affects the battery performance of the lithium battery using the lithium negative electrode sheet.
According to an embodiment of the invention, the reaction satisfies at least one of the following conditions: under dry conditions; the method is carried out under the protection of inert gas. Therefore, the side reaction between water and the lithium foil can be avoided under the dry condition, and the side reaction between the lithium foil and oxygen can be avoided under the protective atmosphere (such as nitrogen atmosphere, argon atmosphere and helium atmosphere) condition. In some embodiments, the reaction of graphite and lithium foil may be performed in dry air; in other embodiments, the reaction of the graphite and lithium foil is performed in a glove box, which may better prevent the lithium foil from side reactions.
According to an embodiment of the present invention, after the lithium carbide layer is generated on the surface of the lithium foil, graphite that does not participate in the reaction is adsorbed on the surface of the lithium carbide layer, i.e., the surface of the lithium carbide layer is adsorbed with graphite. Thus, the adsorbed graphite can act together with the lithium carbide layer to inhibit the growth of lithium dendrites and further prevent the short circuit of the battery caused by the lithium dendrites; moreover, the graphite adsorbed on the surface (namely, the graphite layer) can improve the compactness of the protective layer, can increase the specific surface area in the lithium deposition process, and has small influence on the internal resistance of the battery using the lithium negative pole piece; in addition, the existence of the graphite layer can also improve the structural stability of the lithium carbide layer, and further improve the coulombic efficiency of the battery and the capacity retention rate of the battery; in addition, the graphite has certain flexibility, so that the solid-solid interface impedance of the solid battery using the lithium negative pole piece can be obviously reduced, and the service performance of the solid battery is further improved.
According to the embodiment of the invention, if the graphite powder coated at the beginning is relatively more and the graphite layer on the surface of the lithium carbide layer is thicker, a certain measure can be taken to thin the graphite layer, for example, a certain amount of graphite can be lightly blown off by using an aurilave, so that the thickness of the protective layer is 5 nanometers to 50 micrometers.
Further, in order to prevent the graphite layer adsorbed on the surface of the lithium carbide layer from falling off, the graphite layer may be further pressed so that the graphite layer is more strongly adhered to the surface of the lithium carbide layer. In some specific manufacturing processes, the graphite layer may be lightly pressed by a finger, or a pressing plate (a plate structure with a flat surface) may be used for lightly pressing.
According to an embodiment of the present invention, the graphite is at least one of natural graphite, artificial graphite, bulk graphite, and flake graphite. Therefore, the graphite is widely selected, the growth of lithium dendrites can be well inhibited, and the solid-solid interface impedance of the solid lithium battery using the lithium negative pole piece is reduced. In some preferred embodiments, the graphite is flake graphite (flake graphite), which can more uniformly and sufficiently react with the lithium foil and strongly adsorb on the surface of the lithium carbide layer to form a graphite layer, thereby more effectively improving the capacity retention rate and coulomb efficiency of the lithium battery.
According to an embodiment of the present invention, the particle size of the graphite is 5 μm or less. Therefore, the graphite with smaller particle size can react with the lithium foil more uniformly to obtain a lithium carbide layer with more uniform distribution; and the graphite layer that adsorbs in the lithium carbide layer also distributes comparatively evenly, and the adsorption affinity on lithium carbide layer surface is great to prevent that graphite from taking place to drop in the use of lithium negative pole piece.
According to the embodiment of the invention, the lithium negative electrode plate can be applied to various types of lithium batteries, such as solid lithium batteries, liquid lithium batteries, lithium sulfur batteries or lithium air batteries, and the like, and the lithium negative electrode plate with the structure has good stability for the structures such as electrolytes in the various lithium batteries.
In yet another aspect of the present invention, a lithium battery is provided. According to an embodiment of the invention, the lithium battery comprises the lithium negative electrode plate. Therefore, the lithium battery has high coulombic efficiency, good capacity retention rate of the battery in long-term circulation and long service life. As will be understood by those skilled in the art, the lithium battery has all the features and advantages of the negative electrode plate of the lithium battery, and the details are not repeated herein.
According to an embodiment of the present invention, referring to fig. 3, the lithium battery further includes: the positive pole piece 20 is arranged opposite to the lithium negative pole piece 10, and the positive pole piece 20 is arranged close to the protective layer 12 in the lithium negative pole piece 10; an electrolyte membrane 30, wherein the electrolyte membrane 30 is arranged between the positive pole piece 20 and the lithium negative pole piece 10. Therefore, the protective layer in the battery can well inhibit lithium dendrites and prevent short circuit of the battery, thereby improving the coulombic efficiency of the lithium battery and the capacity retention rate of the battery in long-term circulation and prolonging the service life of the battery.
According to the embodiment of the invention, the size and the shape of the positive pole piece and the lithium negative pole piece have no special requirements, and a person skilled in the art can flexibly select the size and the shape of the required battery according to the practical situation such as the size and the shape of the required battery. In some embodiments, the lithium negative electrode sheet can be a disk with a diameter of 10mm, and the positive electrode sheet can be a disk with a diameter of 8 mm. The specific method for assembling the positive pole piece, the lithium negative pole piece and the electrolyte membrane into the full cell also has no special requirements, and a person skilled in the art can flexibly select a conventional assembling mode according to the actual situation, for example, a 2032 button cell can be adopted for assembling.
According to an embodiment of the present invention, the positive electrode sheet includes a positive electrode sheet current collector and a positive active material disposed on a surface of the positive electrode sheet current collector, and the positive active material is disposed adjacent to the electrolyte membrane. The material of the current collector of the positive electrode plate includes, but is not limited to, copper and aluminum, and the specific material of the positive active material includes, but is not limited to, lithium cobaltate, lithium manganate, lithium iron phosphate, and ternary material (such as NCM 811).
In some embodiments, the material of the electrolyte membrane includes, but is not limited to, one or more of a sulfide electrolyte, an oxide electrolyte, a polymer electrolyte, an organic-inorganic composite electrolyte, and the like, wherein the specific material of the sulfide electrolyte includes, but is not limited to, x L i2S·(1-x)P2S5(L PS for short) and derivatives thereof, e.g. L i10GeP2S12(L GPS for short), L i6PS5Cl (L PSCl) L i10SnP2S12(L SPS), and further, the sulfide electrolyte may be further doped with Si, Ta, Hf, Sc, L iI, ZnO and P2O5Specific materials of the oxide electrolyte include, but are not limited TO, LL ZO (lithium lanthanum zirconium oxygen), LL TO (lithium lanthanum titanium oxygen), LL ZTO (lithium lanthanum zirconium titanium oxygen), L ATP (lithium aluminum titanium phosphorus), L AGP (lithium aluminum germanium phosphorus) and other derivative oxides thereof.
Further, the specific type of the lithium battery is not particularly required, and those skilled in the art can flexibly select the lithium battery according to practical situations, for example, the specific type of the lithium battery includes but is not limited to at least one of an all-solid battery, a gel battery, a liquid lithium battery, a lithium sulfur battery, and a lithium air battery.
Examples
Example 1
In a glove box, 0.1g of natural graphite is uniformly sprayed on a metal lithium foil cathode, then manual coating and pressing are slightly performed, reaction is performed for 6 hours at 60 ℃, after the reaction is completed, extra graphite powder on the surface is slightly blown off by an ear washing ball, a metal lithium cathode pole piece with a protective layer of 10nm thickness is obtained, wherein the protective layer comprises a lithium carbide layer and a graphite layer adsorbed on the surface of the lithium carbide layer, the lithium cathode pole piece is cut for standby, NCM811 is used as a positive pole material, sulfide electrolyte (L PSCl) is used as an electrolyte membrane, an assembly cycle test of an all-solid-state battery is performed, the battery capacity retention rate is 96.3% after 27 cycles, and the specific test result is shown in FIG. 4.
Example 2
0.05g of scaly graphite is uniformly sprayed on a metal lithium foil cathode in a glove box, then manual coating and pressing are slightly carried out, reaction is carried out for 6 hours at the temperature of 60 ℃, after the reaction is finished, extra graphite powder on the surface is slightly blown off by an ear washing ball, a metal lithium cathode pole piece with a protective layer of 10nm thickness is obtained, wherein the protective layer comprises a lithium carbide layer and a graphite layer adsorbed on the surface of the lithium carbide layer, the lithium cathode pole piece is cut for standby, NCM811 is used as a positive pole material, sulfide electrolyte (L PSCl) is used as an electrolyte membrane, an assembly cycle test of an all-solid-state battery is carried out, the battery capacity retention rate is 82.6% after 27 cycles, and the specific test result is shown in figure 5.
Comparative example 1
An assembly cycle test of an all-solid battery was performed using a lithium foil as a negative electrode and a sheet (without a protective layer on the surface), NCM811 as a positive electrode material, a sulfide electrolyte (L PSCl) as an electrolyte membrane, and the battery size was the same as in examples 1 and 2, and the battery capacity retention rate was 17.1% after 27 cycles, and the specific test results are shown in fig. 4 and 5.
Comparative example 2
And arranging a protective layer on the surface of the lithium foil negative electrode to obtain a lithium negative electrode piece, wherein the protective layer is made of a mixture of PEO (polyethylene oxide) and silicon dioxide, the thickness of the protective layer is 30 micrometers, the lithium negative electrode piece is cut for standby, the size of the battery is consistent with that of the battery in examples 1 and 2, NCM811 is used as a positive electrode material, sulfide electrolyte (L PSCl) is used as an electrolyte membrane, and an assembly cycle test of the all-solid-state battery is carried out, and the capacity retention rate of the battery after 27 cycles is 23.2%.
As can be seen from examples 1 and 2 and comparative examples 1 and 2, the lithium negative electrode in the lithium battery of the present application uses lithium carbide and graphite as a protective layer, and the battery capacity retention rate of the lithium battery is very high, which indicates that the protective layer significantly inhibits the growth of lithium dendrites and significantly improves the battery capacity retention rate; also, the protective layer did not crack or fall off during 480 hours of use in the batteries of examples 1 and 2, while the protective layer of comparative example 2 cracked during the same period of use.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A lithium negative electrode sheet, comprising:
a lithium negative electrode;
a protective layer including a lithium carbide layer disposed on one surface of the lithium negative electrode.
2. The lithium negative electrode sheet according to claim 1, wherein the protective layer further comprises:
a graphite layer disposed on a surface of the lithium carbide layer distal from the lithium negative electrode.
3. The lithium negative electrode tab of claim 2, wherein the graphite layer is at least one of natural graphite, artificial graphite, bulk graphite, flake graphite, and graphene.
4. The lithium negative electrode plate according to claim 1 or 2, wherein the thickness of the protective layer is 5 nm to 50 μm.
5. A method for preparing the lithium negative electrode plate of any one of claims 1 to 4, which is characterized by comprising the following steps:
a layer of graphite is formed on one surface of a lithium foil and reacted at a predetermined temperature for a predetermined time to form a lithium carbide layer on the surface of the lithium foil, resulting in a protective layer.
6. The method according to claim 5, wherein the predetermined temperature is 20 to 80 ℃ and the predetermined time is 1 to 24 hours.
7. The method according to claim 5 or 6, wherein the reaction satisfies at least one of the following conditions:
under dry conditions;
the method is carried out under the protection of inert gas.
8. The method of claim 5, wherein the graphite is adsorbed on a surface of the lithium carbide layer.
9. The method according to claim 5 or 8, wherein the graphite is at least one of natural graphite, artificial graphite, bulk graphite, and flake graphite,
preferably, the graphite is flake graphite.
10. A lithium battery comprising the lithium negative electrode sheet according to any one of claims 1 to 4.
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Cited By (3)
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| TWI750103B (en) * | 2021-07-16 | 2021-12-11 | 明志科技大學 | Preparation method of lithium foil anode of all solid-state lithium battery |
| CN114256441A (en) * | 2021-11-16 | 2022-03-29 | 东莞市加伏新材料研究院有限公司 | Lithium-carbon composite negative electrode, preparation method thereof and lithium battery |
| CN114335429A (en) * | 2021-12-31 | 2022-04-12 | 柯良节 | Lithium battery cathode, preparation method thereof and lithium battery |
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| 博克: "《分析化学中试样分解方法手册》", 31 March 1987 * |
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| TWI750103B (en) * | 2021-07-16 | 2021-12-11 | 明志科技大學 | Preparation method of lithium foil anode of all solid-state lithium battery |
| CN114256441A (en) * | 2021-11-16 | 2022-03-29 | 东莞市加伏新材料研究院有限公司 | Lithium-carbon composite negative electrode, preparation method thereof and lithium battery |
| CN114335429A (en) * | 2021-12-31 | 2022-04-12 | 柯良节 | Lithium battery cathode, preparation method thereof and lithium battery |
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