CN109244355B - Method for producing lithium-supplemented negative electrode, and lithium ion secondary battery - Google Patents
Method for producing lithium-supplemented negative electrode, and lithium ion secondary battery Download PDFInfo
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/04—Processes of manufacture in general
- H01M4/0402—Methods of deposition of the material
- H01M4/0421—Methods of deposition of the material involving vapour deposition
- H01M4/0423—Physical vapour deposition
- H01M4/0426—Sputtering
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H—ELECTRICITY
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- 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
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- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
Provided are a negative electrode for lithium supplement, a method of preparing the same, and a lithium ion secondary battery including the negative electrode for lithium supplement. The method for preparing the lithium-supplemented negative electrode comprises the following steps: a lithium film and/or a lithium composite material film is formed on the surface of the negative electrode material layer through vacuum coating, so that the lithium supplement amount can be accurately controlled according to different battery systems, lithium consumed by the battery to form an SEI film is supplemented, and the capacity of the battery is improved.
Description
Technical Field
The invention relates to the field of lithium ion secondary batteries, in particular to a negative electrode for lithium supplement, a preparation method thereof and a lithium ion secondary battery comprising the negative electrode for lithium supplement.
Background
In recent years, with the demand of electrical appliances such as smart phones, tablet computers, electric vehicles and the like for high specific energy chemical power sources, high specific energy chemical power sources are urgently needed. The current lithium ion secondary battery has limited space for developing specific energy, the specific energy of the battery can be greatly improved by a mode of supplementing lithium by a negative electrode, and the reason for improving the specific energy of the battery by supplementing lithium by the negative electrode is that the negative electrode forms a solid electrolyte interface film (SEI film) to consume partial lithium ions when the battery is charged for the first time, so that the coulombic efficiency of charging and discharging for the first time is low, for example, the first coulombic efficiency of a carbon material is about 90 percent, and the first coulombic efficiency of a silicon-based material is 65 to 85 percent. By adopting a method of supplementing lithium to the negative electrode, the first coulombic efficiency can be improved by about 10-20%, and the specific energy of the lithium ion secondary battery is correspondingly improved.
It has been reported that the specific energy of a lithium ion secondary battery is improved by a negative electrode lithium supplement method, and chinese patent publication No. CN102916165A realizes negative electrode lithium supplement by spraying or dripping an organic lithium solution on the surface of a negative electrode sheet to reduce lithium ions in the organic lithium solution to obtain metallic lithium. The organic lithium reagent is expensive, and a substance with stronger reducibility than metallic lithium needs to be added to reduce lithium ions into the metallic lithium, so that the cost is increased, and the process route for supplementing lithium is complex; the Chinese patent publication No. CN104993098A adopts lithium powder as a lithium source for lithium supplement of a cathode, the lithium powder has small particles and micron-sized particle diameters, the phenomenon that the particles fly everywhere during operation exists, the requirement on the operation environment is strict, and potential safety hazards exist.
Disclosure of Invention
In view of the above problems in the prior art, the present invention is directed to a simple and practical method for preparing a lithium-complementary negative electrode, which can provide different amounts of lithium complementary for different battery systems.
The above object of the present invention can be achieved by the following technical means.
According to an aspect of the present invention, there is provided a method of preparing a negative electrode for lithium supplement of a lithium ion secondary battery, comprising: and forming a lithium film and/or a lithium composite material film on the surface of the active material layer of the negative pole piece through vacuum coating.
According to another aspect of the present invention, there is provided a lithium-supplemented negative electrode obtained by the above method.
According to still another aspect of the present invention, there is provided a lithium ion secondary battery including the above-described negative electrode for lithium supplement.
The lithium-supplement cathode obtained by the method can be applied to lithium ion secondary batteries in batches, can provide different lithium supplement amounts aiming at different battery systems, and improves the specific energy of the lithium ion secondary batteries. For example: in a battery system with the lithium-supplemented silicon-carbon material as a negative electrode and the nickel-cobalt-aluminum ternary material as a positive electrode, the specific capacity can reach over 174mAh/g (under the charge-discharge rate of 0.2C).
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the drawings without creative efforts.
Fig. 1 is a front view of a rolled lithium-compensated anode according to an embodiment of the present invention.
Fig. 2 is a cross-sectional view of the lithium coiled negative electrode of fig. 1 taken along line a-a.
Detailed Description
Some embodiments of the invention are described below with reference to the accompanying drawings. It is to be understood that other various embodiments can be devised and modified by those skilled in the art in light of the teachings of this disclosure without departing from the scope or spirit of the invention. The following detailed description is, therefore, not to be taken in a limiting sense.
Unless otherwise indicated, all numbers expressing feature sizes, quantities, and physical characteristics used in the specification and claims are to be understood as being modified in all instances by the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth in the specification and attached claims are approximations that can be calculated by one skilled in the art using the teachings disclosed herein to achieve the desired properties, and such approximations are suitable. The use of numerical ranges by endpoints includes all numbers within that range and any range within that range, for example, 1 to 5 includes 1, 1.1, 1.3, 1.5, 2, 2.75, 3, 3.80, 4, and 5, and the like.
In the description of the present invention, it is to be understood that the terms "upper", "lower", and the like, indicate orientations or positional relationships based on those shown in the drawings, are merely for convenience in describing the present invention and simplifying the description, and do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present invention.
Fig. 1 shows a front view of a lithium-compensated anode according to an embodiment of the present invention. The lithium-supplementing negative electrode is in a roll form and adopts a current collector two-side coating mode. The current collector 3 has a negative electrode material layer 2 on both sides thereof, and a lithium film or a lithium composite film 1 is provided on the negative electrode material layer 2. Fig. 2 is a cross-sectional view of the lithium coiled negative electrode of fig. 1 taken along line a-a. It should be noted that the widths of the lithium film or lithium composite film 1, the negative electrode material layer 2 and the current collector 3 in fig. 1 and 2 may be arbitrarily set, and are not necessarily to scale in the drawings, but the widths of the lithium film or lithium composite film 1 and the negative electrode material layer 2 do not exceed the width of the current collector 3. In addition, in the case of forming a lithium composite film for lithium supplement, the lithium composite film may have a single-layer structure (i.e., a single-layer lithium composite film) or a multi-layer structure, for example, a lithium layer/lithium composite layer/lithium layer, or more layers of alternating lithium layer/lithium composite layer structures.
Current collectors useful in the present invention include metal foils and carbon-coated metal foils, for example, copper foil, nickel foil, carbon-coated copper foil, and the like. The metal foil, such as copper foil, may have a thickness of 5 to 10 μm. The thickness of the carbon coating in the carbon coating metal foil can be 1-5 microns.
The negative electrode material layer may be formed on one or both sides of the current collector by a coating method. For example, a slurry containing a negative electrode active material, a conductive agent, a binder, and a solvent may be applied to a current collector to form a coating layer, and dried to obtain a negative electrode material layer. The negative electrode active material may include a carbon material-based negative electrode active material and a silicon-based negative electrode active material. Examples of the carbon material-based negative active material include artificial graphite, natural graphite, soft carbon, hard carbon, mesocarbon microbeads, graphene, and the like; examples of the silicon-based negative active material include silicon carbon materials, silica-carbon composites, nano-silicon-carbon composites, silicon alloys, and the like. The conductive agent, the binder, and the solvent are those commonly used in the art, for example, the conductive agent may include acetylene black, Super P, carbon fiber, carbon nanotube, ketjen black, graphene, etc., the binder may include PVDF (polyvinylidene fluoride), PTFE (polytetrafluoroethylene), CMC (carboxymethyl cellulose), polyimide, polyacrylic acid, sodium alginate, SBR (styrene-butadiene) rubber, polyurethane, etc., and the solvent may include NMP (N-methylpyrrolidone), etc. The thickness of the negative electrode material layer (the thickness of the single-sided negative electrode material layer) may be 0.030mm to 0.15 mm.
In the present invention, the lithium film or the lithium composite film is formed on the negative electrode material layer by vacuum coating. In some embodiments, the rolled negative electrode plate (including the current collector and the negative electrode material layer formed on one or both sides of the current collector) may be unwound by means of an unwinding and winding device and passed through a vacuum coating device, wherein a lithium film or a lithium composite film is formed on the negative electrode material layer by vacuum coating. The thickness of the lithium film or the lithium composite film may be 100 nm to 15 μm, preferably 1 to 15 μm. The multi-layered film of the lithium composite material may be formed by multiple plating.
The lithium composite material that can be used in the present invention is a binary or multi-element composite material formed of metallic lithium and at least one other element selected from the group consisting of aluminum element, magnesium element, boron element, silicon element, indium element, zinc element, silver element, calcium element, and manganese element. For example, the lithium composite material may include a binary or multicomponent alloy of metallic lithium with at least one other element. The mass content of the at least one other element in the lithium composite material is 0.1-40%, preferably 1-20%.
The vacuum coating can be 10-2～10-5Pa vacuum degree and 500-1500 ℃. The coating time may be about 1 to 20 seconds. When the composite material film is vacuum evaporated, a metal lithium source and one or more other element sources can be arranged in a vacuum coating device, the metal lithium source is heated (the one or more other element sources can also be heated simultaneously), the metal lithium is evaporated, a lithium film (the thickness of the lithium film can be less than a few microns, for example less than 2 microns) is rapidly coated on the surface of the negative electrode material, and then one lithium film is coated on the surface of the negative electrode materialOne or more other element sources are warmed to evaporate the other elements. Because the volatilization speed of high-temperature steam atoms of other elements is high under the high vacuum condition, the penetrating power is strong, when the high-temperature steam atoms are deposited on the lithium film, partial steam atoms can penetrate into the middle of the lithium film or are deposited on the surface of the lithium film, and because the activity and the self-welding performance of the metal lithium atoms are extremely strong, the steam atoms and the metal lithium atoms instantly generate the processes of mutual dissolution, melting and solidification, and form a lithium-other element composite material film with lithium. The lithium metal plating may be performed again to form a lithium/other element/lithium composite film.
Through the mode, the lithium supplement amount can be accurately controlled according to different battery systems, lithium consumed by an SEI (solid electrolyte interphase) film formed by the battery is supplemented, and the capacity of the battery is improved.
The following are some exemplary embodiments of the invention.
Embodiment 4 is the method of embodiment 3, wherein the lithium composite material comprises a binary or multicomponent alloy of metallic lithium and at least one other element.
Embodiment 5 is the method of embodiment 3, wherein the at least one other element is present in the lithium composite material in an amount of 0.1% to 40%, preferably 1% to 20%, by mass.
Detailed description of the inventionMode 6 is the method of embodiment 1, wherein the vacuum coating is performed at 10-2～10-5Pa vacuum degree and 500-1500 ℃.
Embodiment 7 is the method of embodiment 3, wherein the lithium composite film is formed by vacuum evaporating metallic lithium prior to vacuum evaporating the at least one other element, and optionally again alternately vacuum evaporating metallic lithium, or optionally again alternately vacuum evaporating metallic lithium and the at least one other element.
Embodiment 8 is the method of embodiment 1, wherein the negative electrode material layer includes a negative electrode active material including at least one of a carbon-based negative electrode active material and a silicon-based negative electrode active material.
Embodiment 9 is the method of embodiment 8, wherein the carbon-based negative active material includes artificial graphite, natural graphite, soft carbon, hard carbon, mesocarbon microbeads and graphene; the silicon-based negative active material comprises a silicon-carbon material, silicon oxide, a silicon oxide-carbon composite material, nano silicon, a nano silicon-carbon composite material and a silicon alloy.
Embodiment 10 is the method of embodiment 1, wherein the lithium-compensated negative electrode includes a current collector, and the negative electrode material layer is formed on one or both sides of the current collector.
Embodiment 12 is the method of embodiment 10, wherein the negative electrode material layer is obtained by coating a slurry containing a negative electrode active material, a conductive agent, a binder, and a solvent onto a current collector.
Embodiment 13 is the method of embodiment 1, wherein the lithium-supplemented negative electrode is in a roll form or a sheet form.
Embodiment 14 is a lithium-supplemented negative electrode obtained by the method according to any one of embodiments 1 to 13.
Embodiment 15 is a lithium ion secondary battery including the lithium-complementary negative electrode described in embodiment 14.
Examples
Hereinafter, the present invention will be described in more detail by way of examples, which are merely illustrative and should not be construed as limiting the scope of the present invention.
Example 1:
a preparation of negative electrode material
Mixing artificial graphite (Tianjin fibrate Rui New energy science and technology Co., Ltd.) as a negative electrode active material, PVDF as a binder and acetylene black as a conductive agent in a solvent NMP according to a mass ratio of 80:10:10 to form slurry, and coating the slurry on two sides of a rolled copper foil current collector by virtue of an automatic coating machine to obtain a negative electrode.
B preparation of lithium-supplementing cathode
Drying the prepared coiled cathode in a vacuum oven, and performing vacuum coating in a vacuum coating device by using a winding and unwinding device at 10-2And (3) carrying out vacuum evaporation on a lithium film on the surface of the negative electrode under the Pa pressure and at the temperature of 600-1200 ℃ to obtain the negative electrode with two sides respectively plated with the lithium film with the thickness of 2 microns.
C comparative experiment of charging and discharging
(1) Adopting artificial graphite as a cathode material, LiFePO4(Hunan fir new material Co., Ltd.) as a positive electrode material, 1mol/L LiPF6-EC/EMC (volume ratio 1:1, EC: ethylene carbonate, EMC: methyl ethyl carbonate, Dongguan fir battery material Co., Ltd.) was charged and discharged at 0.2C rate, and the first coulombic efficiency of the battery was 90.4%.
(2) The negative electrode is artificial graphite plated with a lithium film with the thickness of 2 microns, other structures and components of the battery are the same as those in the step (1), the first discharge capacity of the battery is improved, and the first coulombic efficiency is 97.9%.
Example 2:
a preparation of negative electrode material
A negative electrode active material nano silicon (the particle diameter is 35nm, Beijing Deke island gold science and technology Co., Ltd.)/artificial graphite composite material (the silicon content is 10 percent), PAA (polyacrylic acid) serving as a binder and a conductive agent: and mixing the carbon black in a solvent NMP according to the mass ratio of 85:10:5 to form slurry, and coating a negative electrode material on the two sides of the coiled current collector copper foil through a coating machine to obtain the negative electrode.
B preparation of lithium-supplemented negative electrode
Drying the prepared coiled negative electrode in a vacuum oven, and performing vacuum coating in a vacuum coating device by means of a coiling and uncoiling device at 10 DEG-2And (3) carrying out vacuum evaporation on a lithium film on the surface of the negative electrode under the Pa pressure and at the temperature of 600-1200 ℃ to obtain the lithium supplement negative electrode with two sides respectively plated with the lithium film with the thickness of 5 microns.
C Charge and discharge experiment
(1) The preparation method comprises the following steps of (1) adopting a nano silicon/artificial graphite composite material as a negative electrode material, an NCM (nickel cobalt manganese) ternary material as a positive electrode material, 1mol/L of electrolyte LiPF6-EC/DMC (volume ratio is 1:1, EC: ethylene carbonate, DMC: dimethyl carbonate, Dongguan fir battery material Co., Ltd.), an electrolyte additive: the lithium-ion battery comprises 2 wt% of vinylene carbonate, 3 wt% of lithium bis (oxalato) borate and 3 wt% of trithioethylene carbonate, and is charged and discharged at a rate of 0.2C, and the first coulombic efficiency of the battery is 70.1%.
(2) The cathode adopts a nano-silicon/artificial graphite composite material plated with a lithium film with the thickness of 5 microns, the others are consistent with those in the step (1), and the first coulombic efficiency of the battery is improved by 88.4%.
Example 3:
same as example 2 except that
A preparation of negative electrode material
The active substance is a composite material of silicon oxide (New energy science and technology Co., Ltd.)/artificial graphite (wherein the content of the silicon oxide is 20%)
B preparation of lithium-supplemented negative electrode
The obtained lithium-supplementing negative electrode is a negative electrode with two sides respectively plated with a lithium film with the thickness of 3 microns.
C charge-discharge experiment verification
(1) The negative electrode adopts a lithium-plated silicon oxide/artificial graphite composite material, the positive electrode adopts an NCA (nickel cobalt aluminum) ternary material, the electrolyte and the additive of the electrolyte are consistent with those in the embodiment 2, the battery is charged and discharged at the multiplying power of 0.2C, and the first coulombic efficiency of the battery is 75%.
(2) The negative electrode adopts a silicon oxide/artificial graphite composite material plated with a lithium film with the thickness of 2 microns, the others are consistent with those in the step (1), and the first coulombic efficiency of the battery is improved by 92%.
Example 4:
a preparation of negative electrode Material
Mixing active substance artificial graphite, a binder PVDF and a conductive agent carbon black in a solvent NMP according to a mass ratio of 80:10:10 to obtain slurry, and coating the slurry on two sides of a rolled current collector copper foil by means of an automatic coating machine to obtain a negative electrode.
B preparation of lithium-supplementing cathode
And drying the prepared coiled negative electrode in a vacuum oven, and obtaining the negative electrode with two sides respectively plated with a lithium-magnesium composite material film (the magnesium content accounts for 1 percent of the total lithium-magnesium content) with the thickness of 1 micron by a rolling and unreeling device through a vacuum coating technology.
The specific preparation conditions of the lithium-magnesium composite film are as follows (1) under the vacuum degree of 10-2Two crucibles are arranged at the upstream and the downstream under the pressure Pa, one crucible is used for containing solid metal lithium, and the other crucible is used for containing solid metal magnesium; (2) setting the heating temperature of a lithium ingot to be 600-1200 ℃, heating a crucible, and quickly plating a lithium film with the thickness of 1 micron on the surface of a negative electrode material; (3) heating metal lithium, heating a crucible containing metal magnesium, wherein the set temperature is 500-1100 ℃, quickly plating a layer of nanometer thick magnesium film material on a plated lithium film, and because the volatilization speed of metal magnesium high-temperature steam atoms is higher and the penetrating power is higher under the high vacuum condition, when depositing on the lithium film, part of magnesium steam atoms can penetrate into the middle of the lithium film or deposit on the surface of the lithium film.
C comparative experiment of charging and discharging
(1) The negative electrode adopts artificial graphite, and the positive electrode adopts LiCoO2The material (Hu nan fir new material Co., Ltd.) has an electrolyte of 1mol/L LiPF6-EC/DMC (volume ratio 1:1, EC:ethylene carbonate, DMC: dimethyl carbonate, a fir battery material ltd), was charged and discharged at a rate of 0.2C, and the initial coulombic efficiency of the battery was 89.2%.
(2) The negative electrode adopts artificial graphite plated with a lithium-magnesium composite material film with the thickness of 1 micron, the other parts are the same as those in the step (1), the first discharge capacity of the battery is obviously improved, and the first coulombic efficiency is 98.1 percent.
The specific test data are shown in the following table
Practical application of the present invention is not limited to the above-described specific examples 1, 2, 3, and 4, and the present invention can be applied to all lithium ion secondary battery systems.
Claims (17)
1. A method of preparing a negative electrode for lithium replenishment of a lithium ion secondary battery, characterized in that the method comprises: forming a lithium composite material film on the surface of the negative electrode material layer through vacuum coating,
the lithium composite material film is formed by vacuum evaporation of metal lithium and then vacuum evaporation of at least one other element.
2. The method of claim 1, further comprising: after vacuum evaporation of at least one further element, metal lithium is again alternately vacuum evaporated.
3. The method of claim 1, further comprising: after vacuum evaporation of the at least one further element, metal lithium and the at least one further element are again alternately vacuum evaporated.
4. The method of claim 1, wherein the lithium composite film has a thickness of 100 nm to 15 μm.
5. The method of claim 1, wherein the lithium composite material is a binary or multi-element composite material formed by metallic lithium and at least one other element selected from the group consisting of aluminum, magnesium, boron, silicon, indium, zinc, silver, calcium, and manganese.
6. The method of claim 5, wherein the lithium composite material comprises a binary or multicomponent alloy of metallic lithium and at least one other element.
7. The method of claim 5, wherein the at least one additional element is present in the lithium composite material in an amount of 0.1% to 40% by weight.
8. The method of claim 7, wherein the at least one other element is present in the lithium composite material in an amount of 1% to 20% by weight.
9. The method of claim 1 wherein said vacuum coating is at 10-2～10-5Pa vacuum degree and 500-1500 ℃.
10. The method of claim 1, wherein the negative electrode material layer comprises a negative electrode active material comprising at least one of a carbon-based negative electrode active material and a silicon-based negative electrode active material.
11. The method according to claim 10, wherein the carbon-based negative active material comprises artificial graphite, natural graphite, soft carbon, hard carbon, and graphene.
12. The method of claim 10, wherein the silicon-based negative active material comprises silicon carbon material, silica-carbon composite, nanosilicon-carbon composite, and silicon alloys.
13. The method according to claim 1, wherein the negative electrode for lithium supplement comprises a current collector, and the negative electrode material layer is formed on one side or both sides of the current collector by coating a slurry containing a negative electrode active material, a conductive agent, a binder, and a solvent on the current collector.
14. The method of claim 13, wherein said current collector comprises copper foil, nickel foil, carbon coated copper foil.
15. The method of claim 1, wherein the lithium-supplemented negative electrode is in roll form or sheet form.
16. A lithium-supplemented negative electrode obtained by the method according to any one of claims 1 to 15.
17. A lithium ion secondary battery comprising the lithium-supplemented negative electrode according to claim 16.
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| CN111560595A (en) * | 2020-03-30 | 2020-08-21 | 维达力实业(深圳)有限公司 | Returning type lithium supplementing method for silicon-containing negative electrode material, negative electrode piece and battery |
| CN111613771B (en) * | 2020-06-29 | 2022-03-22 | 蜂巢能源科技有限公司 | Battery cathode and preparation method and application thereof |
| CN111987288A (en) * | 2020-08-26 | 2020-11-24 | 复阳固态储能科技(溧阳)有限公司 | Method for in-situ lithium supplement of lithium ion energy storage device electrode and application |
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| CN114864866A (en) * | 2022-06-21 | 2022-08-05 | 合肥国轩高科动力能源有限公司 | Lithium-magnesium composite cathode, preparation method thereof, lithium-sulfur battery prepared by lithium-magnesium composite cathode and all-solid-state battery |
| CN114843441B (en) * | 2022-07-01 | 2022-10-18 | 宁德新能源科技有限公司 | Electrochemical device, method for manufacturing the same, and electronic device |
| CN117117111A (en) * | 2023-02-20 | 2023-11-24 | 荣耀终端有限公司 | Electrochemical device and electronic device |
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