CN115332526A - Positive electrode lithium supplement additive, preparation method thereof and lithium ion battery - Google Patents

Positive electrode lithium supplement additive, preparation method thereof and lithium ion battery Download PDF

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CN115332526A
CN115332526A CN202110503358.6A CN202110503358A CN115332526A CN 115332526 A CN115332526 A CN 115332526A CN 202110503358 A CN202110503358 A CN 202110503358A CN 115332526 A CN115332526 A CN 115332526A
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positive electrode
lithium
supplement additive
lithium supplement
ion battery
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张热喝
李媛
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Shanghai Cenat New Energy Co Ltd
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G31/00—Compounds of vanadium
    • C01G31/006—Compounds containing, besides vanadium, two or more other elements, with the exception of oxygen or hydrogen
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/006—Compounds containing, besides manganese, two or more other elements, with the exception of oxygen or hydrogen
    • 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
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The application relates to the technical field of batteries, and provides a positive electrode lithium supplement additive, a preparation method thereof and a lithium ion battery. The chemical formula of the positive electrode lithium supplement additive provided by the application is Li 4 M x V 3‑x O 8 Wherein, 0<x<3,M is a transition metal. The lithium supplement additive for the anode is a vanadium-position transition metal doped lithium vanadate material which is in a monoclinic system and belongs to a layered structure, and has the advantages of high capacity, stable structure and the like. Tests prove that the first coulombic efficiency of the lithium ion battery with the positive electrode lithium supplement additive added in the positive plate is obviously improved。

Description

Positive electrode lithium supplement additive, preparation method thereof and lithium ion battery
Technical Field
The application belongs to the technical field of batteries, and particularly relates to a positive electrode lithium supplement additive, a preparation method thereof and a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, high voltage, long cycle life and the like, and is widely applied to the fields of power automobiles, 3C and energy storage. With the push of policy and the demand of the consumers for the endurance mileage of new energy vehicles, the development of high specific energy power batteries is the research focus of those skilled in the art.
In order to increase the energy density of the lithium ion battery, it is necessary to use a material having a high capacity for both the positive electrode material and the negative electrode material, for example, NCM811, NCA, or the like is used for the positive electrode material, and silicon carbon, silicon oxygen, or the like is used for the negative electrode material. However, silicon carbon, silicon oxygen and other silicon negative electrode materials often form an SEI film on the surface of the negative electrode during the first charging process to consume active lithium in the positive electrode, resulting in lower first coulombic efficiency.
In order to solve this problem, those skilled in the art often adopt methods such as lithium supplement to the positive electrode, lithium supplement to the negative electrode, lithium supplement to the diaphragm, and lithium supplement to the current collector. The method for supplementing lithium to the negative electrode mainly comprises the steps of directly mixing and contacting lithium powder and a lithium band lithium supplementing material with a negative electrode active material, and has certain dangerousness, difficulty in controlling uniformity and high requirements on equipment and production environment; the method for replenishing lithium for the diaphragm and the current collector mainly coats a lithium-rich material on the surfaces of the diaphragm and the current collector, and the method is easy to cause the increase of the thickness and the mass of the battery to influence the weight energy density of the battery; the method for supplementing lithium to the positive electrode mainly uses an additive of a sacrificial lithium salt, is safe, can be directly mixed with a positive electrode active material to prepare slurry, does not need to change the prior process and develop new equipment, and can be used for uniformly supplementing lithium. However, the effect of the conventional positive electrode lithium supplement additive on improving the first coulombic efficiency of the lithium ion battery is limited.
Disclosure of Invention
The application aims to provide a positive electrode lithium supplement additive and a preparation method thereof, and aims to solve the problem of low initial coulombic efficiency of a lithium ion battery comprising a silicon negative electrode.
Further, the application also provides a lithium ion battery.
The technical scheme adopted by the application is as follows:
in a first aspect, the present application provides a positive electrode lithium supplement additive having a chemical formula of Li 4 M x V 3-x O 8 Wherein, 0<x<3,M is a transition metal.
In some embodiments, 0.5-inch-woven x-woven cloth is 1.5.
In some embodiments, the M is at least one of Mn, ti, pb, zr, ge, sn.
The positive electrode lithium supplement additive is a vanadium-position transition metal doped lithium vanadate material which is in a monoclinic system and belongs to a layered structure, and has the advantages of high capacity, stable structure and the like. Tests show that the first coulombic efficiency of the lithium ion battery with the positive electrode lithium supplement additive added in the positive plate is obviously improved.
In a second aspect, the present application provides a method for preparing a lithium supplement additive for a positive electrode, which comprises adding Li 4 V 3 O 8 And MO 2 The sol-gel method is adopted to prepare the material with the chemical formula of Li 4 M x V 3-x O 8 The positive electrode lithium supplement additive of (1);
wherein, 0<x<3，MO 2 Is a transition metal oxide.
In some embodiments, li 4 V 3 O 8 And MO 2 The sol-gel method is adopted to prepare the material with the chemical formula of Li 4 M x V 3-x O 8 The step of adding lithium to the positive electrode comprises:
subjecting the Li to 4 V 3 O 8 And the MO 2 Mixing treatment is carried out in the solution, and then calcination treatment is carried out.
In some embodiments, the mixing process comprises: stirring for 8-24 hours at 60-80 ℃.
In some embodiments, the calcination treatment comprises: calcining for 12-24 hours at 500-1000 ℃ under air atmosphere.
In some embodiments, li is substituted 4 V 3 O 8 And MO 2 In the step of performing a mixing treatment in a solution, the Li 4 V 3 O 8 And the MO 2 The molar ratio of (1) to (0.2-1).
In some embodiments, the MO 2 Is MnO 2 、TiO 2 、PbO 2 、ZrO 2 、GeO 2 、SnO 2 At least one of (1).
The preparation method provided by the application adopts transition metal oxidationThe material is a doped metal source and is doped in Li by a sol-gel method 4 V 3 O 8 Realizes the doping of transition metal M at the vanadium site, thereby preparing the compound with the chemical formula of Li 4 M x V 3-x O 8 The method is simple, the prepared anode lithium supplement additive is small in particle size and uniform in particle size, and the first coulombic efficiency of the lithium ion battery can be effectively improved by placing the anode lithium supplement additive on an anode plate.
In a third aspect, the present application provides a lithium ion battery, including a positive electrode sheet, the positive electrode sheet including: the positive electrode lithium supplement additive or the positive electrode lithium supplement additive prepared by the preparation method.
In some embodiments, the positive electrode sheet further comprises a positive electrode active material, and the positive electrode lithium supplement additive is used in an amount of 0.1 to 10% by weight based on the total weight of the positive electrode active material.
According to the lithium ion battery provided by the application, the positive plate is added with the positive lithium supplement additive, so that the lithium ion battery has good first coulombic efficiency.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings required for the embodiments or the prior art descriptions will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
Fig. 1 is XRD patterns of the positive electrode lithium supplement additives prepared in examples 1 to 4 and the positive electrode lithium supplement additive of comparative example 1, wherein the XRD patterns of the positive electrode lithium supplement additives of example 4, example 3, example 2, example 1 and comparative example 1 are shown in sequence from top to bottom.
Detailed Description
In order to make the technical problems, technical solutions and beneficial effects to be solved by the present application more clearly apparent, the present application is further described in detail below with reference to the embodiments. It should be understood that the specific embodiments described herein are merely illustrative of and not restrictive on the broad application.
The embodiment of the application provides a positive electrode lithium supplement additive, and the chemical formula of the positive electrode lithium supplement additive is Li 4 M x V 3- x O 8 Wherein, 0.5<x<1.5, M is a transition metal.
In some embodiments, 0.5-x-1.5, when x is less than 0.5, the effect of improving the specific capacity of the battery is limited; when x is larger than 1.5, the original crystal structure of the material may be changed, and the material performance may be unstable.
In some embodiments, M is at least one of Mn, ti, pb, zr, ge, sn.
Different from the prior art, the positive electrode lithium supplement additive provided by the embodiment of the application is a vanadium-site transition metal doped lithium vanadate material. In one test example, li is used 4 Mn x V 3-x O 8 (0.5<x<1.5 For example), the microstructure of the lithium vanadate material is observed, and the lithium supplement additive Li of the positive electrode is found 4 M x V 3-x O 8 Is monoclinic, is a layered structure, has a high capacity: (>376 mAh/g), stable structure and the like, and simultaneously, the first coulombic efficiency of the lithium ion battery with the positive electrode lithium supplement additive added in the positive plate is tested, and the discovery that Li is added by the positive electrode lithium supplement additive 4 M x V 3-x O 8 And the first coulomb efficiency of the lithium ion battery can be obviously improved.
In order to prepare the positive electrode lithium supplement additive, the embodiment of the application also provides a preparation method of the positive electrode lithium supplement additive.
A preparation method of a positive electrode lithium supplement additive, which is prepared by adding Li 4 V 3 O 8 And MO 2 The sol-gel method is adopted to prepare the material with the chemical formula of Li 4 M x V 3-x O 8 The positive electrode lithium supplement additive of (1);
wherein 0<x<3，MO 2 Is a transition metal oxide.
In the embodiment of the application, transition metal oxide is used as a doping metal source, and a sol-gel method is adopted to prepare Li 4 V 3 O 8 Realizes the vanadium position doping transitionMetal M to produce a compound of the formula Li 4 M x V 3-x O 8 The positive electrode lithium supplement additive of (1). In addition, the lithium supplement additive of the positive electrode prepared by the sol-gel method has small particle size and uniform particles, so that the prepared additive with uniform particle size does not influence the processing performance of the positive electrode material.
In particular, li 4 V 3 O 8 As a host material, a transition metal oxide is doped in the host material to form a compound having a chemical formula of Li 4 M x V 3-x O 8 The positive electrode lithium supplement additive of (1).
Li 4 V 3 O 8 The preparation method of (3) can be referred to the preparation method of lithium vanadate conventional in the field, such as: mixing and ball-milling a lithium source and a vanadium source according to a proportion, and calcining after drying.
In some embodiments, li 4 V 3 O 8 The preparation method comprises the following steps: weighing a lithium source and a vanadium source according to the molar ratio of lithium ions to vanadium ions of 4 4 V 3 O 8 . The lithium source is an organic or inorganic substance containing lithium, including but not limited to lithium carbonate, lithium oxalate, lithium hydroxide, lithium acetate, etc., and the vanadium source is an organic or inorganic substance containing vanadium, including but not limited to vanadium pentoxide, ammonium vanadate, etc.
MO 2 The transition metal oxide is used as a guest material and is used for providing doping metal, so that the transition metal doping type lithium vanadate material is synthesized. In some embodiments, MO 2 Is MnO 2 、TiO 2 、PbO 2 、ZrO 2 、GeO 2 、SnO 2 At least one of (a).
The sol-gel method is commonly used for preparing inorganic compounds or inorganic materials in the form of nano particles, and in order to further improve the effect of a positive electrode lithium supplement additive on the improvement of the first coulombic efficiency of a lithium ion battery, the applicant prepares the lithium ion battery with a chemical formula of Li by adopting the sol-gel method 4 M x V 3-x O 8 The process of the anode lithium supplement additive is further optimized.
In some embodiments, li is 4 V 3 O 8 And MO 2 The sol-gel method is adopted to prepare the material with the chemical formula of Li 4 M x V 3-x O 8 The step of adding lithium to the positive electrode comprises: mixing Li 4 V 3 O 8 And MO 2 Mixing treatment is carried out in the solution, and then calcining treatment is carried out.
In a further embodiment, the mixing process comprises: stirring for 8-24 hours at 60-80 ℃. So as to consist of Li 4 V 3 O 8 And MO 2 The mixture formed can be mixed homogeneously in the liquid phase.
In a further embodiment, the calcination treatment comprises: calcining at 500-1000 deg.C for 12-24 hr in air atmosphere.
In further examples, li 4 V 3 O 8 And MO 2 In the step of performing the mixing treatment in the solution, li 4 V 3 O 8 And MO 2 Is 1 (0.2-1), so as to synthesize the compound with the chemical formula of Li 4 M x V 3-x O 8 (0.5<x<1.5 Positive electrode lithium supplement additive of (1).
It is understood that Li is added 4 V 3 O 8 And MO 2 The solution in the step of mixing in the solution may be a single solvent or a mixed solution of a plurality of solvents. In some embodiments, the solution is a single organic solvent, preferably ethanol.
In summary, the embodiments of the present application use Li 4 V 3 O 8 And MO 2 On the basis of combining the raw materials with the sol-gel method, the process conditions of the sol-gel method are controlled within the preferable range, so that the prepared anode lithium supplement additive has the advantages of high capacity, stable structure and the like.
On the basis of the technical scheme, the embodiment of the application further provides the lithium ion battery.
Correspondingly, this lithium ion battery positive plate includes positive plate, and this positive plate includes: the positive electrode lithium supplement additive or the positive electrode lithium supplement additive prepared by the preparation method.
According to the lithium ion battery provided by the embodiment of the application, the positive electrode lithium supplement additive is added on the positive electrode piece, so that the lithium ion battery has good first coulombic efficiency.
Specifically, the composition of the positive electrode sheet may refer to a positive electrode sheet conventional in the art, such that the positive electrode sheet includes the positive electrode lithium supplement additive. In some embodiments, the positive electrode sheet is composed of a current collector and a positive electrode material layer formed on a surface of the current collector, and the lithium supplement additive is added to the positive electrode material layer or coated on a surface of the positive electrode material layer.
The current collector is used for carrying the positive electrode material layer, and may be selected from metal foils conventional in the art, such as copper foil, aluminum foil, and the like, which are not particularly limited in the embodiments of the present application.
The positive electrode material layer is formed on the surface of the current collector, and is usually composed of a positive electrode active material, a conductive agent and a binder, in addition to the positive electrode lithium supplement additive. For the types of the positive electrode active material, the conductive agent and the binder, reference can be made to the conventional materials in the art, for example, the positive electrode active material includes but is not limited to lithium cobaltate, lithium nickel cobalt manganese oxide, lithium iron phosphate, etc., the conductive agent includes but is not limited to Super-C, KS-6, VGCF, multi-wall CNT, single-wall CNT, etc., and the binder includes but is not limited to PVDF, PTFE, etc.
In some embodiments, the positive electrode sheet further comprises a positive electrode active material, and the amount of the positive electrode lithium supplement additive is 0.1-10%, preferably 0.5-10% of the total weight of the positive electrode active material. By controlling the dosage of the positive electrode lithium supplement additive within the weight range, the first coulombic efficiency of the lithium ion battery can be obviously improved. When the amount of the positive electrode lithium supplement additive added is too low, the effect of lithium supplement is not achieved, but when the amount of the positive electrode lithium supplement additive added exceeds a value of 10%, there is a risk of lithium precipitation.
In the last embodiment, the mass ratio of the positive active material, the positive lithium supplement additive, the conductive agent and the binder is (85-94.5): 0.1-10): 3, preferably (85-94.5): 0.5-10): 3, so that under the condition of ensuring that the first coulombic efficiency of the lithium ion battery is improved, the improvement of the structural stability and the conductive performance of the positive plate is facilitated.
On the basis of the above embodiments, the method for manufacturing a lithium ion battery according to the embodiments of the present application may refer to conventional techniques in the art, for example, a positive electrode active material, a positive electrode lithium supplement additive, a conductive agent and a binder are proportionally mixed to prepare a positive electrode slurry, and then the positive electrode slurry is coated, rolled, cut on a current collector to prepare a positive electrode sheet, and then assembled with a silicon negative electrode to form the lithium ion battery.
The practice of the invention is illustrated by the following examples.
Example 1
This example prepares a positive electrode lithium supplement additive Li 4 Mn 0.75 V 2.25 O 8 The preparation method comprises the following steps:
(1) According to Li + And V 4+ The molar ratio of lithium carbonate to ammonium vanadate is 4 4 V 3 O 8 。
(2) According to Li 4 V 3 O 8 And MnO with MnO 2 In a molar ratio of 1:3, ratio of Li 4 V 3 O 8 And MnO 2 Stirring in ethanol at 80 ℃ for 20h, and calcining at 900 ℃ for 21h in air atmosphere to obtain Li 4 Mn 0.75 V 2.25 O 8 。
Example 2
This example prepares a positive electrode lithium supplement additive Li 4 Mn 1 V 2 O 8 The preparation method is different from that of the embodiment 1 in that: in step (2), mn 4+ And V 4+ In a molar ratio of 1.
Example 3
This example prepares a positive electrode lithium supplement additive Li 4 Mn 1.25 V 1.75 O 8 The preparation method is different from the example 1 in that: in step (2), mn 4+ And V 4+ Is 5.
Example 4
This example prepares a positive electrode lithium supplement additive Li 4 Mn 1.5 V 1.5 O 8 The preparation method is different from that of the embodiment 1 in that: in step (2), mn 4+ And V 4+ 1 is 1.
Embodiments 5 to 20 provide a lithium ion battery, where the positive electrode lithium supplement additive and the amount thereof are shown in table 1, and the preparation method of the lithium ion battery includes the following steps:
(1) Adding NCM811, a positive electrode lithium supplement additive, multi-wall CNT and PVDF into NMP according to the mass ratio of (85-94.5) to (0.5-10) to (3) to mix evenly, and preparing positive electrode slurry;
(2) Coating the anode slurry prepared in the step (1) on an aluminum foil, rolling and cutting to prepare an anode plate;
(3) According to the anode active material: conductive agent: PAA: CMC =90, in a ratio of 2;
(4) The lithium ion battery was assembled taking the positive electrode sheet prepared in step (2), the negative electrode sheet prepared in step (3), the single-sided ceramic-coated separator and the electrolyte solution (1.2molLiPF6, EC/DMC (3), 2% FEC, 1% VC).
Comparative example 1
The present comparative example provides a lithium ion battery, and the difference between the preparation method of the lithium ion battery addition and the example 5 is that: the positive electrode lithium supplement additive is Li 4 V 3 O 8 。
Comparative example 2
The present comparative example provides a lithium ion battery, which is prepared by a method different from examples 5 to 20 in that: the positive electrode slurry is not added with a positive electrode lithium supplement additive.
1. The positive electrode lithium supplement additives prepared in examples 1, 2, 3 and 4 and the positive electrode lithium supplement additive prepared in comparative example 1 were taken, and the microstructure of the material was observed using an X-ray diffractometer (XRD), and the result is shown in fig. 1.
2. The lithium ion batteries prepared in examples 5 to 20 and comparative examples 1 to 2 were used to test the cycle performance and the first coulombic efficiency of each battery, respectively, and table 1 shows the test results. As shown by the results, the cycle performance of the lithium ion batteries of examples 5 to 20 was improved to various degrees, relative to those of comparative examples 1 to 2. Meanwhile, the first effect and the cycle of the positive electrode lithium supplement additive tend to be improved and then reduced along with the increase of the using amount of the positive electrode lithium supplement additive, and the reason for the first effect and the cycle tend to be understood as the lithium dendrite phenomenon can occur when lithium ions provided by the positive electrode lithium supplement additive exceed a threshold value, so that the first effect and the cycle performance of the positive electrode lithium supplement additive are influenced.
TABLE 1
Figure BDA0003057286740000091
Note: "-" indicates no addition.
The above description is only exemplary of the present application and should not be taken as limiting the present application, as any modification, equivalent replacement, or improvement made within the spirit and principle of the present application should be included in the protection scope of the present application.

Claims (10)

1. The positive electrode lithium supplement additive is characterized in that the chemical formula of the positive electrode lithium supplement additive is Li 4 M x V 3-x O 8 Wherein, 0<x<3,M is a transition metal.
2. The positive lithium supplement additive of claim 1, wherein 0.5 straw x is woven to cover 1.5; and/or
And M is at least one of Mn, ti, pb, zr, ge and Sn.
3. The preparation method of the anode lithium supplement additive is characterized in that Li is added 4 V 3 O 8 And MO 2 Using solPreparation of chemical formula Li by gel method 4 M x V 3-x O 8 The positive electrode lithium supplement additive of (1);
wherein, 0<x<3，MO 2 Is a transition metal oxide.
4. The method according to claim 3, wherein Li is added 4 V 3 O 8 And MO 2 The sol-gel method is adopted to prepare the material with the chemical formula of Li 4 M x V 3-x O 8 The step of adding lithium to the positive electrode comprises:
subjecting the Li to 4 V 3 O 8 And the MO 2 Mixing treatment is carried out in the solution, and then calcination treatment is carried out.
5. The method of claim 4, wherein the mixing process comprises: stirring for 8-24 hours at 60-80 ℃.
6. The method of claim 4, wherein the calcining treatment comprises: calcining for 12-24 hours at 500-1000 ℃ under air atmosphere.
7. The method according to claim 4, wherein Li is added 4 V 3 O 8 And MO 2 In the step of performing a mixing treatment in a solution, the Li 4 V 3 O 8 And the MO 2 The molar ratio of (1) to (0.2-1).
8. The process according to any of claims 3 to 7, wherein said MO is present in a solution 2 Is MnO 2 、TiO 2 、PbO 2 、ZrO 2 、GeO 2 、SnO 2 At least one of (1).
9. A lithium ion battery comprising a positive electrode sheet, wherein the positive electrode sheet comprises: the positive electrode lithium supplement additive according to claim 1 or 2 or the positive electrode lithium supplement additive prepared by the preparation method according to any one of claims 3 to 8.
10. The lithium ion battery of claim 9, wherein the positive plate further comprises a positive active material, and the positive lithium supplement additive is present in an amount of 0.1% to 10% by weight of the total weight of the positive active material.
CN202110503358.6A 2021-05-10 2021-05-10 Positive electrode lithium supplement additive, preparation method thereof and lithium ion battery Pending CN115332526A (en)

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