CN111613771A - Battery cathode and preparation method and application thereof - Google Patents
Battery cathode and preparation method and application thereof Download PDFInfo
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- CN111613771A CN111613771A CN202010607076.6A CN202010607076A CN111613771A CN 111613771 A CN111613771 A CN 111613771A CN 202010607076 A CN202010607076 A CN 202010607076A CN 111613771 A CN111613771 A CN 111613771A
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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- H01M2220/00—Batteries for particular applications
- H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
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Abstract
The invention discloses a battery cathode and a preparation method and application thereof, wherein the battery cathode comprises: the lithium ion battery comprises a negative electrode substrate and a coating, wherein the negative electrode substrate comprises at least one of a carbon-based material, a silicon-based material and a silicon-oxygen-based material, the coating is arranged on at least one part of the surface of the negative electrode substrate, and the coating comprises metal lithium, a fast ion conductor and a binder. Thus, the lithium battery loaded with the battery negative electrode has excellent first efficiency, energy density and cycle life.
Description
Technical Field
The invention belongs to the field of lithium batteries, and particularly relates to a battery cathode and a preparation method and application thereof.
Background
With the rapid development of new energy vehicles, the requirements on the energy density and the safety performance of the power battery for vehicles are continuously improved. It is expected that the energy density of the power battery will reach over 500Wh/kg by 2025. With the increasing demand for energy density of power batteries, the gram capacity and the compaction density of the existing graphite cathode material reach limit values, and the silicon carbon material has excellent gram capacity and compaction density, so that the use of the silicon carbon material as the cathode material is a hot spot for a period of time in the future. However, the silicon-carbon material has low first charge-discharge efficiency, large expansion ratio, material pulverization problem caused by long-time circulation and matching problem with related electrolyte and glue always puzzles related researchers.
The prior research shows that the first effect and the cycle performance of the silicon-carbon negative electrode can be improved by lithium supplement and pre-lithiation technologies. In the current lithium supplement technology, lithium powder and an ultrathin lithium belt are taken as main research trends, but in the preparation process of the ultrathin lithium belt, the requirements on the process and equipment are high, and high-precision roll squeezer equipment, certain specific protective films and lubricating oil are required for assistance. Lithium is supplemented by lithium powder, in order to prevent the dispersion of the lighter lithium powder, wet lithium supplementation is mostly adopted, the lithium powder, a solvent and a binder are well dispersed in advance, and then the lithium powder is dispersed on a negative electrode plate in a blade coating, dropping coating or gravure printing mode, but the prior disclosed wet lithium supplementation technology does not solve the problem of controlling lithium dendrites after lithium pre-preparation, because a layer of lithium powder is paved on the surface of the negative electrode in advance for lithium pre-preparation, lithium precipitation and lithium dendrites are easy to generate in the charging and discharging process, the lithium pre-preparation mode is improved to a certain extent in the first effect, but the cycle life is also damaged due to the rapid growth of the lithium precipitation and the lithium dendrites.
Thus, the existing battery negative electrode is in need of improvement.
Disclosure of Invention
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. To this end, an object of the present invention is to provide a battery negative electrode, a method of manufacturing the same, and a use thereof, in which a lithium battery loaded with the battery negative electrode has excellent first efficiency, energy density, and cycle life.
In one aspect of the invention, a battery anode is provided. According to an embodiment of the invention, the battery negative electrode comprises:
a negative electrode substrate including at least one of a carbon-based material, a silicon-based material, and a silicon-oxygen-based material;
a coating disposed on at least a portion of a surface of the negative electrode substrate, and the coating comprising metallic lithium, a fast ion conductor, and a binder.
According to the battery negative electrode of the embodiment of the invention, by adopting the material comprising at least one of the carbon-based material, the silicon-based material and the silicon-oxygen-based material as the negative electrode substrate, the composed negative electrode substrate has excellent gram capacity and compaction density relative to the traditional graphite negative electrode material, and the coating comprising the metallic lithium, the fast ion conductor and the binder is formed on the surface of the negative electrode substrate of the application, and the fast ion conductor in the coating can not only guide the ordered deposition of the lithium ions on the surface of the negative electrode substrate, but also can effectively inhibit the growth of lithium dendrites in the charging and discharging processes, so that the lithium battery loaded with the battery negative electrode has excellent first effect, energy density and cycle life.
In addition, the battery negative electrode according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the present invention, the mass ratio of the lithium metal, the fast ion conductor and the binder is (1-80): (1-80): (1-10). Therefore, the lithium battery loaded with the battery negative electrode has excellent first efficiency, energy density and cycle life.
In some embodiments of the present invention, the lithium metal has a particle size of 5 to 100 μm.
In some embodiments of the present invention, the outer surface of the lithium metal has a protective layer comprising at least one of lithium carbonate, lithium fluoride, lithium iodide, lithium oxide, lithium hydroxide, and an organic lithium salt. Thus, the activity of the metallic lithium can be reduced, thereby avoiding harsh drying conditions of the preparation process.
In some embodiments of the invention, the fast ion conductor comprises at least one of an oxide electrolyte and a ceramic, preferably an oxide electrolyte.
In some embodiments of the present invention, the oxide electrolyte comprises at least one of LLZO, LLZTO and LATP. Therefore, the lithium battery loaded with the battery negative electrode has excellent first efficiency, energy density and cycle life.
In some embodiments of the invention, the binder comprises at least one of polyvinylidene fluoride, styrene butadiene rubber, polytetrafluoroethylene, polyacrylic acid, carboxymethyl cellulose, and polyimide.
In yet another aspect of the invention, a method of making the above battery negative electrode is provided. According to an embodiment of the invention, the method comprises:
mixing metal lithium, a fast ion conductor, a binder and a solvent to obtain a mixed solution;
the mixed solution is applied on the surface of a negative electrode substrate and dried and rolled so as to form the coating on the surface of the negative electrode substrate.
According to the method for preparing the battery negative electrode, the mixed solution obtained by mixing the metal lithium, the fast ion conductor, the binder, the organic solvent and the water is applied to the surface of the negative electrode substrate and dried, the fast ion conductor in the mixed solution can guide the ordered deposition of lithium ions on the surface of the negative electrode substrate and can effectively inhibit the growth of lithium dendrites in the charging and discharging processes, and therefore the lithium battery loaded with the battery negative electrode has excellent first effect, energy density and cycle life.
In addition, the method for preparing the battery anode according to the above embodiment of the present invention may further have the following additional technical features:
in some embodiments of the invention, the mass concentration of the mixed solution is 1-10%.
In some embodiments of the invention, the solvent comprises at least one of n-hexane, toluene, xylene, ethylene carbonate, and dimethyl carbonate.
In a third aspect of the present invention, a lithium battery is provided. According to an embodiment of the invention, the lithium battery has the battery negative electrode or the battery negative electrode prepared by the method. Thus, the lithium battery has excellent first efficiency, energy density, and cycle life.
In a fourth aspect of the present invention, a vehicle is presented. According to an embodiment of the present invention, the vehicle has the lithium battery described above. Therefore, the endurance mileage of the automobile can be improved by loading the lithium battery having excellent first efficiency, energy density and cycle life.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
fig. 1 is a schematic flow diagram of a method of making a battery anode according to one embodiment of the invention;
FIG. 2 is a graph showing charge and discharge curves of lithium batteries corresponding to example 1, comparative example 1 and comparative example 2;
FIG. 3 is a comparison graph of the first effect of lithium batteries corresponding to example 1, comparative example 1 and comparative example 2;
fig. 4 is a graph of charge and discharge efficiency after 55 charge and discharge cycles of lithium batteries corresponding to example 1, comparative example 1, and comparative example 2.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings, wherein like or similar reference numerals refer to the same or similar elements or elements having the same or similar function throughout. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
In the description of the present invention, it is to be understood that the terms "central," "longitudinal," "lateral," "length," "width," "thickness," "upper," "lower," "front," "rear," "left," "right," "vertical," "horizontal," "top," "bottom," "inner," "outer," "clockwise," "counterclockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings for convenience in describing the invention and to simplify the description, and are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include at least one such feature. In the description of the present invention, "a plurality" means at least two, e.g., two, three, etc., unless specifically limited otherwise.
In one aspect of the invention, a battery anode is provided. According to an embodiment of the present invention, the battery negative electrode includes a negative electrode substrate including at least one of a carbon-based material, a silicon-based material, and a silicon-oxygen-based material, and a coating layer provided on at least a part of a surface of the negative electrode substrate, and the coating layer includes metallic lithium, a fast ion conductor, and a binder. The inventors found that by using a material including at least one of a carbon-based material, a silicon-based material, and a silicon-oxygen-based material as an anode substrate, the anode substrate of the composition has excellent gram capacity and compacted density relative to conventional graphite anode materials, and a coating including metallic lithium, a fast ion conductor, and a binder is formed on the surface of the anode substrate of the present application, and the fast ion conductor in the coating can not only guide the ordered deposition of lithium ions on the surface of the anode substrate, but also effectively suppress the growth of lithium dendrites during charge and discharge, thereby enabling a lithium battery loaded with the battery anode to have excellent first efficiency, energy density, and cycle life. Preferably, the coating layer is formed on the entire surface of the anode base. When the negative electrode base includes at least two of the carbon-based material, the silicon-based material, and the silicon-oxygen-based material, the respective materials constituting the negative electrode base may be mixed in an arbitrary ratio.
Further, the mixing ratio of the metallic lithium, the fast ion conductor and the binder in the coating layer is not particularly limited as long as the above effects can be achieved, and it is preferable that the mass ratio of the metallic lithium, the fast ion conductor and the binder in the coating layer is (1 to 80): (1-80): (1-10). The inventor finds that the content of metal lithium needs to be controlled according to the lithium supplementing amount required by the design of a corresponding battery cell, if the lithium supplementing amount is too small, the effect of supplementing lithium cannot be achieved, if the lithium supplementing amount is too much, not only can lithium be separated out, but also material waste can be caused, meanwhile, if the fast ion conductor is too little, the effect of inhibiting lithium dendrite and guiding lithium ions to be uniformly deposited can not be achieved, and if the fast ion conductor is too much, the overall ion conductivity of a coating can be reduced, the interface impedance is increased, and the polarization voltage is increased, so that the first effect and the circulation are influenced; in addition, if the content of the binder is too low, the mixed solution cannot be uniformly dispersed, so that the lithium powder floats on the surface of the solution and cannot be uniformly coated, and if the content of the binder is too much, the internal resistance of the battery is increased, and the electrochemical performance of the pole piece is influenced. According to an embodiment of the present invention, the particle size of the lithium metal in the coating is 5 to 100 μm, and the inventors found that the control of the pre-lithium amount is affected by the excessive particle size of the lithium powder. Preferably, in order to reduce the activity of the above-mentioned metal lithium, a protective layer is provided on the outer surface of the metal lithium, wherein the protective layer includes at least one of lithium carbonate, lithium fluoride, lithium iodide, lithium oxide, lithium hydroxide, and an organic lithium salt. Therefore, the protective layer is formed on the surface of the metal lithium, so that the activity of the metal lithium can be reduced, and harsh drying conditions are avoided in the preparation process. The thickness of the coating on the battery negative electrode is determined according to the lithium amount required by the battery negative electrode during charging and discharging.
Further, the fast ion conductor used in the coating layer includes at least one of an oxide electrolyte and a ceramic, wherein the oxide electrolyte includes at least one of LLZO, LLZTO and LATP, and the ceramic includes at least one of lithium nitride and lithium iodide, and preferably, the fast ion conductor is an oxide electrolyte. The inventors found that the oxide electrolyte as a fast ion conductor has excellent ion conductivity and can significantly better inhibit the growth of lithium dendrites than other types. Meanwhile, the binder in the coating comprises at least one of polyvinylidene fluoride, styrene butadiene rubber, polytetrafluoroethylene, polyacrylic acid, carboxymethyl cellulose and polyimide.
In yet another aspect of the invention, a method of making the above battery negative electrode is provided. According to an embodiment of the invention, with reference to fig. 1, the method comprises:
s100: mixing metal lithium, fast ion conductor, adhesive and solvent
In this step, metallic lithium, a fast ion conductor, and a binder are dispersed in a solvent in a dry environment to obtain a mixed solution. In the dispersing process, the types and proportions of the lithium metal, the fast ion conductor and the binder are as described above, and the amount of the solvent is such that the mass concentration of the resulting mixed solution is 1 to 10%, for example, 1%, 1.1% … … 9.9.9%, 10%. The inventors have found that too low or too high a concentration of the mixed solution does not control the uniformity and homogeneity of the coating during the coating process too well. Meanwhile, the solvent used includes at least one of n-hexane, toluene, xylene, ethylene carbonate, and dimethyl carbonate.
S200: applying the mixed solution on the surface of the negative electrode substrate
In this step, the mixed solution is applied to the surface of the negative electrode substrate and dried and rolled to form a coating layer including metallic lithium, a fast ion conductor and a binder on the surface of the negative electrode substrate. Specifically, the above mixed solution may be applied to the above negative electrode substrate by means including, but not limited to, spin coating, blade coating, gravure printing, and drop coating.
According to the method for preparing the battery negative electrode, the mixed solution obtained by mixing the metal lithium, the fast ion conductor, the binder, the organic solvent and the water is applied to the surface of the negative electrode substrate and dried, the fast ion conductor in the mixed solution can guide the ordered deposition of lithium ions on the surface of the negative electrode substrate and can effectively inhibit the growth of lithium dendrites in the charging and discharging processes, and therefore the lithium battery loaded with the battery negative electrode has excellent first effect, energy density and cycle life. It should be noted that the features and advantages described above for the battery negative electrode also apply to the method for preparing the battery negative electrode, and are not described herein again.
In a third aspect of the present invention, a lithium battery is provided. According to an embodiment of the invention, the lithium battery has the battery negative electrode or the battery negative electrode prepared by the method. Thus, the lithium battery has excellent first efficiency, energy density and cycle life. It should be noted that the features and advantages described above for the battery negative electrode and the preparation method thereof are also applicable to the lithium battery, and are not described herein again.
In a fourth aspect of the present invention, a vehicle is presented. According to an embodiment of the present invention, the vehicle has the lithium battery described above. Therefore, the endurance mileage of the automobile can be improved by loading the lithium battery having excellent first efficiency, energy density and cycle life. It should be noted that the features and advantages described above for the lithium battery are also applicable to the vehicle and will not be described here.
The following embodiments of the present invention are described in detail, and it should be noted that the following embodiments are exemplary only, and are not to be construed as limiting the present invention. In addition, all reagents used in the following examples are commercially available or can be synthesized according to methods herein or known, and are readily available to those skilled in the art for reaction conditions not listed, if not explicitly stated.
Example 1
In a drying room environment with the dew point of less than-40 ℃, lithium powder (the particle size is 20 microns, a protective layer comprising lithium carbonate is formed on the surface of the lithium powder), LLZO oxide electrolyte and styrene butadiene rubber are dispersed into n-hexane solution according to the mass ratio of 30:67:3 to prepare a mixed solution with the solid content of 5 wt%, then the mixed solution is coated on a silicon-based negative electrode plate which is dried in advance by a scraper, the coated electrode plate is placed into a vacuum oven for vacuum drying, after the solvent is removed, the protective layer on the surface of the lithium powder is crushed by a roller press, fresh lithium is exposed, and the lithium powder is uniformly distributed and leveled on the surface of the negative electrode, so that the battery negative electrode is obtained.
Punching the obtained negative electrode material into a circular sheet with the diameter of 16mm, assembling the circular sheet with an NCM positive electrode material into a full cell for charge and discharge tests, wherein the diaphragm is a PE film, and the electrolyte is LiPF6(concentration of 1mol/L in electrolyte) is dissolved in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) with a volume ratio of 1:1:1, the first effect is shown in figures 2 and 3, and the charge-discharge efficiency retention rate after 55 cycles of charge-discharge is shown in figure 4.
Example 2
In a drying room environment with the dew point of less than-30 ℃, lithium powder (the particle size is 5 microns, a protective layer comprising lithium fluoride is formed on the surface of the lithium powder), LLZTO oxide electrolyte and polyvinylidene fluoride are dispersed into a toluene solution according to the mass ratio of 60:35:5 to prepare a mixed solution with the solid content of 3 wt%, then the mixed solution is dropwise coated on a carbon-based negative electrode sheet which is dried in advance, the coated electrode sheet is placed into a vacuum oven for vacuum drying, after the solvent is removed, the protective layer on the surface of the lithium powder is crushed by rolling through a roller press, fresh lithium is exposed, and the lithium powder is uniformly distributed and leveled on the surface of the negative electrode, so that the battery negative electrode is obtained.
Punching the obtained negative electrode material into a circular sheet with the diameter of 16mm, assembling the circular sheet with an NCM positive electrode material into a full cell for charge and discharge tests, wherein the diaphragm is a PE film, and the electrolyte is LiPF6(the concentration in the electrolyte is 1mol/L) is dissolved in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) with the volume ratio of 1:1:1, the first effect is 90 percent, and the charge-discharge efficiency is ensured after 55 times of circulating charge-dischargeThe concentration is kept at 88%.
Example 3
In a drying room environment with the dew point of less than-35 ℃, lithium powder (the particle size is 100 microns, a protective layer comprising lithium oxide is formed on the surface of the lithium powder), LATP oxide electrolyte and polytetrafluoroethylene are dispersed into a xylene solution according to the mass ratio of 50:40:10 to prepare a mixed solution with the solid content of 7 wt%, the mixed solution is rotationally coated on a silicon-based negative electrode plate dried in advance, the coated electrode plate is placed into a vacuum oven for vacuum drying, after the solvent is removed, the protective layer on the surface of the lithium powder is crushed through a roller press, fresh lithium is exposed, and the lithium powder is uniformly distributed and leveled on the surface of the negative electrode to obtain the battery negative electrode.
Punching the obtained negative electrode material into a circular sheet with the diameter of 16mm, assembling the circular sheet with an NCM positive electrode material into a full cell for charge and discharge tests, wherein the diaphragm is a PE film, and the electrolyte is LiPF6(the concentration in the electrolyte is 1mol/L) is dissolved in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) with the volume ratio of 1:1:1, the first effect is 91 percent, and the charge-discharge efficiency is maintained to be 86 percent after 55 times of cyclic charge-discharge.
Example 4
In a drying room environment with a dew point of less than-25 ℃, lithium powder (with the particle size of 50 microns and a protective layer comprising lithium hydroxide formed on the surface of the lithium powder) and lithium nitride and polyimide are dispersed into a ethylene carbonate solution according to the mass ratio of 40:50:10 to prepare a mixed solution with the solid content of 8 wt%, then the mixed solution is gravure-printed on a carbon-based negative electrode plate dried in advance, the coated electrode plate is placed into a vacuum oven for vacuum drying, after a solvent is removed, the protective layer on the surface of the lithium powder is crushed by rolling through a roller press, fresh lithium is exposed, and the lithium powder is uniformly distributed and leveled on the surface of the negative electrode to obtain the battery negative electrode.
Punching the obtained negative electrode material into a circular sheet with the diameter of 16mm, assembling the circular sheet with an NCM positive electrode material into a full cell for charge and discharge tests, wherein the diaphragm is a PE film, and the electrolyte is LiPF6(the concentration in the electrolyte is 1mol/L) is dissolved in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) with the volume ratio of 1:1:1, and the first effect is89%, and the charge-discharge efficiency is kept at 85% after 55 times of cyclic charge-discharge.
Example 5
In a drying room environment with the dew point of less than minus 45 ℃, lithium powder (the particle size is 70 microns, a protective layer comprising lithium hydroxide is formed on the surface of the lithium powder), lithium iodide and carboxymethyl cellulose are dispersed into a dimethyl carbonate solution according to the mass ratio of 35:60:5 to prepare a mixed solution with the solid content of 10 wt%, then the mixed solution is gravure-printed on a silica-based negative electrode sheet which is dried in advance, the coated electrode sheet is placed into a vacuum oven for vacuum drying, after the solvent is removed, the protective layer on the surface of the lithium powder is crushed by a roller press, fresh lithium is exposed, and the lithium powder is uniformly distributed and leveled on the surface of the negative electrode, so that the battery negative electrode is obtained.
Punching the obtained negative electrode material into a circular sheet with the diameter of 16mm, assembling the circular sheet with an NCM positive electrode material into a full cell for charge and discharge tests, wherein the diaphragm is a PE film, and the electrolyte is LiPF6(the concentration in the electrolyte is 1mol/L) is dissolved in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) with the volume ratio of 1:1:1, the first effect is 89%, and the charge-discharge efficiency is maintained to be 84% after 55 times of cyclic charge-discharge.
Comparative example 1
In a drying room environment with a dew point of less than-40 ℃, dispersing lithium powder (the particle size is 20 microns, and a protective layer comprising lithium carbonate is formed on the surface of the lithium powder) and styrene-butadiene rubber into a normal hexane solution according to a mass ratio of 30:2 to prepare a mixed solution with a solid content of 5 wt%, coating the mixed solution on a silicon-based negative electrode sheet (same as in example 1) which is dried in advance by using a scraper, putting the coated electrode sheet into a vacuum oven for vacuum drying, removing the solvent, crushing the protective layer on the surface of the lithium powder by using a roller press to expose fresh lithium, and uniformly distributing and flattening the lithium powder on the surface of the negative electrode to obtain the battery negative electrode.
Punching the obtained negative electrode material into a circular sheet with the diameter of 16mm, assembling the circular sheet with an NCM positive electrode material into a full cell for charge and discharge tests, wherein the diaphragm is a PE film, and the electrolyte is LiPF6(concentration of 1mol/L in electrolyte) Ethylene Carbonate (EC)/dimethyl carbonate (DE) dissolved in volume ratio of 1:1:1C) The first effect of the mixed solution of Ethyl Methyl Carbonate (EMC) is shown in fig. 2 and 3, and the charge-discharge efficiency retention rate after 55 cycles of charge-discharge is shown in fig. 4.
Comparative example 2
A silicon-based negative plate (same as the embodiment 1) is punched into a circular plate with the diameter of 16mm, and the circular plate and the NCM positive electrode material are assembled into a full cell for charge and discharge tests, wherein a diaphragm is a PE film, and electrolyte is LiPF6(concentration of 1mol/L in electrolyte) is dissolved in a mixed solution of Ethylene Carbonate (EC)/dimethyl carbonate (DEC)/Ethyl Methyl Carbonate (EMC) with a volume ratio of 1:1:1, the first effect is shown in figures 2 and 3, and the charge-discharge efficiency retention rate after 55 cycles of charge-discharge is shown in figure 4.
And (4) conclusion: as can be seen from fig. 2 to 4, the retention rates of the charge and discharge efficiencies of the lithium batteries corresponding to example 1 and comparative example 1 after 55 cycles of charge and discharge are higher than that of comparative example 2, which indicates that the two pre-lithium modes of example 1 and comparative example 1 can improve the first efficiency and the cycle life of the corresponding lithium batteries, but the retention rates of the charge and discharge efficiencies of the lithium batteries corresponding to example 1 after the first efficiency and 55 cycles of charge and discharge are higher than that of comparative example 1, which indicates that the pre-lithium mode of example 1 can improve the first efficiency and the cycle life of the lithium batteries better than that of comparative example 1, and the lithium batteries corresponding to examples 2 to 5 have excellent first efficiency and cycle life, which indicates that the first efficiency and the cycle life can be improved by using the pre-lithium mode of the present application.
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 battery negative electrode, comprising:
a negative electrode substrate including at least one of a carbon-based material, a silicon-based material, and a silicon-oxygen-based material;
a coating disposed on at least a portion of a surface of the negative electrode substrate, and the coating comprising metallic lithium, a fast ion conductor, and a binder.
2. The battery anode according to claim 1, wherein the mass ratio of the metallic lithium to the fast ion conductor to the binder is (1-80): (1-80): (1-10).
3. The battery negative electrode according to claim 1 or 2, wherein the metallic lithium has a particle size of 5 to 100 μm,
preferably, the outer surface of the metallic lithium has a protective layer including at least one of lithium carbonate, lithium fluoride, lithium iodide, lithium oxide, lithium hydroxide, and an organic lithium salt.
4. The battery anode of claim 1, wherein the fast ion conductor comprises at least one of an oxide electrolyte and a ceramic, preferably an oxide electrolyte.
5. The battery anode of claim 4, wherein the oxide electrolyte comprises at least one of LLZO, LLZTO, and LATP.
6. The battery negative electrode of claim 1, wherein the binder comprises at least one of polyvinylidene fluoride, styrene butadiene rubber, polytetrafluoroethylene, polyacrylic acid, carboxymethyl cellulose, and polyimide.
7. A method of making the battery anode of any of claims 1-6, comprising:
mixing metal lithium, a fast ion conductor, a binder and a solvent to obtain a mixed solution;
the mixed solution is applied on the surface of a negative electrode substrate and dried and rolled so as to form the coating on the surface of the negative electrode substrate.
8. The method according to claim 7, wherein the mass concentration of the mixed solution is 1-10%;
optionally, the solvent comprises at least one of n-hexane, toluene, xylene, ethylene carbonate, and dimethyl carbonate.
9. A lithium battery having a negative electrode as claimed in any one of claims 1 to 6 or prepared by a method as claimed in claim 7 or 8.
10. A vehicle characterized in that it has the lithium battery of claim 9.
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