CN113140722B - Positive electrode lithium supplement material and preparation method and application thereof - Google Patents

Positive electrode lithium supplement material and preparation method and application thereof Download PDF

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CN113140722B
CN113140722B CN202110438281.9A CN202110438281A CN113140722B CN 113140722 B CN113140722 B CN 113140722B CN 202110438281 A CN202110438281 A CN 202110438281A CN 113140722 B CN113140722 B CN 113140722B
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sintering
lithium
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supplement material
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CN113140722A (en
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孙化雨
李�昊
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai Co Ltd
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Envision Power Technology Jiangsu Co Ltd
Envision Ruitai Power Technology Shanghai 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
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
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    • 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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • 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
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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Abstract

The invention provides a positive electrode lithium supplement material and a preparation method and application thereof, wherein the positive electrode lithium supplement material comprises Li2‑xNi1‑ yMyO2And coating with Li2‑xNi1‑yMyO2Superficial MemOnA coating layer; the invention adopts low-cost metal elements to carry out precursor coprecipitation doping, and replaces part of Ni while reducing the cost2+The mixed lithium-nickel discharging is reduced, the structure is stabilized in the cell circulation process, the oxygen release amount is reduced, and the lithium-nickel mixed discharging in Li2‑xNi1‑ yMyO2Surface coating MemOnThe coating layer greatly reduces the residual lithium content of the finished product, improves the processing and gas production performance, and can inhibit the dissolution deposition anode of transition metals of nickel, copper and iron from damaging an SEI film, thereby improving the cycle.

Description

Positive electrode lithium supplement material and preparation method and application thereof
Technical Field
The invention belongs to the field of lithium ion batteries, and relates to a positive electrode lithium supplement material, and a preparation method and application thereof.
Background
Lithium ion batteries have the advantages of high voltage, high specific energy, good safety performance, and the like, and have been widely used in portable electronic products and electric vehicles. With the rapid development of new energy automobiles, smart grids and distributed energy storage, higher requirements are put forward on the energy density of new energy devices, and high-capacity electrode materials are urgently needed to be researched. High-capacity electrode materials are often accompanied by lower first effect, and in the first charge and discharge process of a lithium ion battery, with the formation of SEI films on the surfaces of positive and negative electrodes, limited active lithium ions in the battery can be inevitably consumed, so that the total active lithium ions are reduced, the capacity and performance of the electrode materials cannot be fully exerted, and the energy density of the battery is difficult to further improve.
Currently, a negative electrode prelithiation additive material is widely researched, but the problems of low potential, high reactivity, poor stability in a room temperature environment and the like exist, and the application of the negative electrode prelithiation additive material is greatly limited by the unsuitability of the solvent, the adhesive, heat treatment and the like used in the existing battery production. Electrochemical prelithiation of the anode material can also be achieved with excess lithium in the cathode material. In recent years, the positive electrode prelithiation additive has been drawing attention due to advantages such as high compatibility with existing processes and high prelithiation capacity. The positive pole prelithiation is to add the lithium supplement additive directly into the positive pole pulping preparation process, the process is compatible with the existing process, and excess active lithium is provided during the first charging to make up for the capacity loss caused by the SEI film. However, most of the positive electrode lithium supplement materials are rich in lithium, have high residual alkali content, have high environmental requirements, are unstable in air, and are easy to react with moisture, carbon dioxide and the like in the air, so that the capacity is reduced. Secondly, the lithium supplement material is added during the mixing of the positive electrode slurry and is easy to react with moisture in NMP to generate alkali, so that the PVDF of the positive electrode binder is inactivated, and the environmental requirements of the existing lithium supplement material in the using and storing processes are extremely strict.
CN109546226A mentions that Li is a lithium-supplementing substance5FeO4The preparation method comprises the steps of mixing a positive active substance, a conductive agent, a binder and a non-aqueous solvent to form slurry, coating the slurry on a positive current collector, baking and cutting to obtain a novel positive plate, and then pairing, winding and assembling the novel positive plate and a negative plate into a shell to prepare the 18650 battery, wherein the capacity of a battery core is obviously improved. But also causes the residue of non-lithium source components in the lithium supplement material, leaves more impurities, and causes the problems of serious self-discharge of the battery cell, reduced discharge capacity and the like.
CN1290209C reports that a battery is prepared by mixing lithium metal, a negative electrode material and a nonaqueous liquid to form a slurry, coating the slurry on a negative electrode current collector, and drying the slurry, which can improve the first efficiency, but because of the high reactivity of lithium metal, the whole operation needs to be performed in an environment of anhydrous drying, resulting in difficult operation and high equipment cost investment.
The above scheme has the problems of low capacity, high cost or low efficiency, and the like, so it is urgently needed to develop a high-capacity, low-cost and high-battery-efficiency lithium supplement material for application in lithium ion batteries.
Disclosure of Invention
The invention aims to provide a positive electrode lithium supplement material, and a preparation method and application thereof, wherein the positive electrode lithium supplement material comprises Li2-xNi1-yMyO2And coating with Li2-xNi1-yMyO2Superficial MemOnA coating layer; wherein M comprises any one or combination of at least two of Cu, Fe or V, Me comprises any one or combination of at least two of Ti, Al, Zr or B, 0<x<2，0<y<1，0<(x+y)<1，m>1，n>1, the invention adopts high-dose low-cost metal elements to carry out coprecipitation doping on precursors, reduces the cost and replaces a part of Ni2+The mixed lithium-nickel discharging is reduced, the structure is stabilized in the cell circulation process, the oxygen release amount is reduced, and the lithium-nickel mixed discharging in Li2-xNi1-yMyO2Surface coating MemOnThe coating layer greatly reduces the residual lithium content of the finished product, improves the processing and gas production performance, and can inhibit the dissolution deposition anode of transition metals of nickel, copper and iron from damaging an SEI film, thereby improving the cycle.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a positive electrode lithium supplement material comprising Li2-xNi1-yMyO2And coating with Li2-xNi1-yMyO2Superficial MemOnA coating layer; wherein M comprises any one or combination of at least two of Cu, Fe or V, Me comprises any one or combination of at least two of Ti, Al, Zr or B, 0<x<2, for example: 0.1, 0.3, 0.5, 0.8, 1, 1.2, 1.5 or 1.8Etc. 0<y<1, for example: 0.1, 0.3, 0.5, 0.8 or 0.9 etc., 0<(x+y)<1, m.gtoreq.1, for example: 1.2 or 3, etc., n.gtoreq.1, for example: 1.2 or 3, etc.
The invention adopts large dosage of low-cost metal elements to carry out coprecipitation doping on the precursor, reduces the cost and replaces a part of Ni2+The lithium nickel mixed discharge is reduced, the structure is stabilized in the cell circulation process, and the oxygen release amount is reduced. The invention is in Li2-xNi1-yMyO2Surface coating MemOnThe coating layer greatly reduces the residual lithium content of the finished product, improves the processing and gas production performance, and can inhibit the dissolution deposition anode of transition metals of nickel, copper and iron from damaging an SEI film, thereby improving the cycle.
Preferably, the Li2-xNi1-yMyO2Is of a binary rhombic structure.
Preferably, D50 of the positive electrode lithium supplement material is 1-20 μm, for example: 1 μm, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, or the like.
Preferably, the Li accounts for 100 percent of the mass of the positive electrode lithium supplement material2-xNi1-yMyO2Is 99.8 to 99.95 percent, such as: 99.8%, 99.85%, 99.88%, 99.9%, 99.92%, 99.95%, etc.
Preferably, said MemOnThe mass fraction of the coating layer is 0.05-0.2%, for example: 0.05%, 0.08%, 0.1%, 0.12%, 0.15%, 0.2%, etc.
In a second aspect, the present invention provides a method for preparing the positive electrode lithium-supplementing material according to the first aspect, wherein the method comprises the following steps:
(1) mixing Ni source and M source, adding alkali source, regulating pH value, dewatering and once sintering to obtain Ni1-yMy(OH)2A precursor;
(2) ni obtained in the step (1)1-yMy(OH)2And mixing the precursor, a lithium source and Me oxide, and performing secondary sintering treatment to obtain the anode lithium supplement material.
The invention isThe method can reduce Li preparation2Ni1-xMxO2The cost of the raw materials is reduced, and the uniform mixing effect can be achieved by direct dry ball milling.
Preferably, the Ni source of step (1) comprises Ni (NO)3)2、NiSO4、NiCO3、Ni(OH)2、NiCl2、NiBr2Or NiI2Any one or a combination of at least two of them.
Preferably, the M source comprises any one of iron nitrate, iron sulfate, iron chloride, copper nitrate, copper sulfate, copper chloride, vanadium nitrate, vanadium chloride or vanadium sulfate or a combination of at least two thereof.
Preferably, the alkali source comprises ammonia and/or sodium hydroxide.
Preferably, the pH value in the step (1) is 8-11, such as: 8. 8.2, 8.5, 9, 9.5, 10, 10.5, or 11, etc.
Preferably, the dehydration of step (1) comprises filtration, washing and drying.
Preferably, the temperature of the primary sintering in the step (1) is 100-600 ℃, for example: 100 ℃, 200 ℃, 300 ℃, 400 ℃, 500 ℃ or 600 ℃, etc.
Preferably, the temperature rise rate of the primary sintering in the step (1) is 10-150 ℃/h, for example: 10 ℃/h, 30 ℃/h, 50 ℃/h, 80 ℃/h, 100 ℃/h or 150 ℃/h and the like.
Preferably, the time of the primary sintering in the step (1) is 1-10 h, for example: 1h, 3h, 5h, 8h or 10h and the like.
Preferably, the lithium source in step (2) comprises any one of lithium oxide, lithium hydroxide or lithium carbonate or a combination of at least two thereof.
Preferably, the Me oxide of step (2) comprises any one of titanium oxide, aluminum oxide, zirconium oxide or boron oxide or a combination of at least two thereof.
Preferably, the vacuum degree of the mixing in the step (2) is 75-80 kpa, for example: 75kpa, 76kpa, 77kpa, 78kpa, 79kpa, or 80kpa, and the like.
Preferably, the atmosphere of the secondary sintering in the step (2) is inert gas.
Preferably, the secondary sintering of step (2) includes one-step sintering and two-step sintering.
Preferably, the temperature of the one-step sintering is 400-500 ℃, for example: 400 ℃, 420 ℃, 450 ℃, 480 ℃, or 500 ℃ and the like.
Preferably, the temperature rise speed of the one-step sintering is 1-10 ℃/h, for example: 1 ℃/h, 2 ℃/h, 3 ℃/h, 4 ℃/h, 5 ℃/h, 6 ℃/h, 7 ℃/h, 8 ℃/h, 9 ℃/h or 10 ℃/h and the like.
Preferably, the time of the one-step sintering is 1-3 h, for example: 1h, 1.2h, 1.5h, 2h, 2.5h or 3h and the like.
Preferably, the temperature of the two-step sintering is 600-1000 ℃, for example: 600 deg.C, 700 deg.C, 800 deg.C, 900 deg.C or 1000 deg.C, etc.
Preferably, the temperature rise speed of the two-step sintering is 5-15 ℃/h, for example: 5 ℃/h, 8 ℃/h, 10 ℃/h, 12 ℃/h or 15 ℃/h and the like.
Preferably, the two-step sintering time is 8-12 h, for example: 8h, 9h, 10h, 11h or 12h and the like.
The invention adopts direct heating after low-temperature presintering for high-temperature sintering, simplifies the preparation process of the material, and can reduce the process cost of material preparation
As a preferable scheme of the invention, the preparation method comprises the following steps:
(1) mixing a Ni source and an M source, adding an alkali source, adjusting the pH to 8-11, dehydrating, heating to 100-600 ℃ at a speed of 10-150 ℃/h, and sintering for 1-10 h to obtain Ni1-yMy(OH)2A precursor;
(2) ni obtained in the step (1)1-yMy(OH)2And mixing the precursor, a lithium source and Me oxide, heating to 400-500 ℃ at the speed of 1-10 ℃/H, sintering for 1-3H, heating to 600-1000 ℃ at the speed of 5-15 ℃/H, and sintering for 8-12H to obtain the anode lithium supplement material.
In a third aspect, the present invention provides a positive electrode plate, which contains the positive electrode lithium supplement material according to the first aspect.
In a fourth aspect, the invention provides a lithium ion battery, which comprises the positive electrode plate according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention adopts large dosage of low-cost metal elements to carry out coprecipitation doping on the precursor, reduces the cost and replaces a part of Ni2+Reducing mixed Li-Ni discharge, stabilizing structure and reducing oxygen release during cell circulation2-xNi1-yMyO2Surface coating MemOnThe coating layer greatly reduces the residual lithium content of the finished product, improves the processing and gas production performance, and can inhibit the dissolution deposition anode of transition metals of nickel, copper and iron from damaging an SEI film, thereby improving the cycle.
(2) The method of the invention can reduce Li preparation2Ni1-xMxO2The cost of the raw materials is reduced, and the uniform mixing effect can be achieved by direct dry ball milling.
(3) The first charge capacity of a battery prepared by using the positive electrode lithium supplement material can reach 233.2mAh g-1Above, the first discharge capacity can reach 198.1mAh g-1Above, the first coulombic efficiency can reach above 85.81%, and the capacity retention rate of circulation 100 circles can reach above 87.8%.
Drawings
Fig. 1 is an SEM image of the positive electrode lithium supplement material described in example 1.
Fig. 2 is a comparative graph of the positive electrode lithium supplement materials described in example 1 and comparative example 1.
Fig. 3 is a TEM image of the positive electrode lithium supplement material described in example 1.
Fig. 4 is a TEM image of the positive electrode lithium supplement material described in comparative example 1.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a positive electrode lithium supplement material, which is prepared by the following method:
(1) dissolving 0.8mol/L nickel nitrate and 0.8mol/L copper nitrate in water to obtain a nickel and copper salt solution with the concentration of 0.8mol/L, adding 1mol/L ammonia water while stirring, adjusting the pH to 9.5, standing for 8h, filtering, washing and drying to obtain a solid mixture, heating the solid mixture to 300 ℃ at the heating rate of 50 ℃/h, and sintering for 6h to obtain a precursor;
(2) and (2) mixing the precursor obtained in the step (1) and lithium carbonate according to a molar ratio of 1.5:1, adding 0.1 mass percent of alumina, mixing under a vacuum degree of 78kpa to obtain mixed powder, heating to 450 ℃ at a heating rate of 6 ℃/H in a nitrogen inert atmosphere, sintering for 2H in one step, heating to 800 ℃ at 10 ℃/H, and sintering for 10H in the second step. And naturally cooling the anode material in the furnace to room temperature, and crushing the anode material until the particle size of D50 is 8 mu m to obtain the anode lithium supplement material.
The SEM image of the positive electrode lithium supplement material is shown in FIG. 1.
Example 2
The embodiment provides a positive electrode lithium supplement material, which is prepared by the following method:
(1) dissolving 0.8mol/L nickel sulfate and 0.8mol/L copper nitrate in water to obtain 1.0mol/L Ni and copper salt solution, stirring while adding 1.2mol/L ammonia water, adjusting the pH value to 10, standing for 8h, filtering, washing and drying to obtain a solid mixture, heating the solid mixture to 320 ℃ at a heating rate of 55 ℃/h, and sintering for 7h to obtain a precursor;
(2) and (2) mixing the precursor obtained in the step (1) with lithium hydroxide according to a molar ratio of 1.5:1, adding titanium oxide with the mass fraction of 0.15%, mixing under the vacuum degree of 76kpa to obtain mixed powder, heating to 480 ℃ at the heating rate of 8 ℃/H in the nitrogen inert atmosphere, sintering for 2H in one step, heating to 900 ℃ at the temperature of 15 ℃/H, and sintering for 12H in the second step. And naturally cooling the anode material in the furnace to room temperature, and crushing the anode material until the particle size of D50 is 10 mu m to obtain the anode lithium supplement material.
Example 3
This example is different from example 1 only in that the temperature of one-step sintering in step (2) is 400 ℃, and other conditions and parameters are completely the same as those in example 1.
Example 4
This example is different from example 1 only in that the temperature of one-step sintering in step (2) is 500 ℃, and other conditions and parameters are exactly the same as those in example 1.
Example 5
This example is different from example 1 only in that the temperature of the two-step sintering in step (2) is 600 ℃, and other conditions and parameters are exactly the same as those in example 1.
Example 6
This example differs from example 1 only in that the temperature of the two-step sintering in step (2) is 1000 ℃ and the other conditions and parameters are exactly the same as those in example 1.
Comparative example 1
Nickel-based precursor Ni (OH) synthesized by coprecipitation method2(ii) a Mixing the precursor Ni (OH)2And lithium salt Li2Ball-milling and mixing O according to the mol ratio of Li/Ni to 2:1, wherein the mixing time is 5h, and the rotating speed is 500rpm to obtain mixed powder; sintering the mixed powder at 250 ℃ for 2h and 450 ℃ for 2h in nitrogen atmosphere, and then heating to 800 ℃ at the heating rate of 5 ℃/min for 10h to obtain Li2NiO2。
Comparative example 2
This comparative example differs from example 1 only in that no alumina is added and the other conditions and parameters are exactly the same as in example 1.
Mixing the lithium supplement materials obtained in the examples 1-6 and the comparative examples 1-2 with the nickel cobalt lithium manganate ternary positive electrode material according to the mass ratio a: b (1: 10), wherein the mixing mode is ball milling for 2 hours, and the rotating speed is 500rpm, so as to obtain a positive electrode active substance mixture; mixing the positive active material mixture with conductive carbon black and PVDF according to the mass ratio of 8:1:1, adding NMP as a solvent, and stirring to obtain positive slurry; coating the positive electrode slurry on an aluminum foil, drying for 6 hours in a vacuum drying oven at 110 ℃ to obtain a positive electrode plate, and preparing the positive electrode plate in a glove box Mikeluona according to the formula: stirring materials with NCM (carbon fiber), CNT (carbon fiber), PVDF (polyvinylidene fluoride) in a ratio of 97.2:1.0:0.8:1.0, homogenizing, and then making a charging model: 2016. the compaction is 3.2-3.6 g/cc. Then drying the pole piece, wherein the drying conditions are as follows: the temperature is 110 ℃/6h, and the prepared button electricity is kept stand for 12 h.
The flow is set on the test equipment, Xinwei tester, and the test current: 0.1C, constant current and constant voltage charging, 0.1C constant current discharging, and the cut-off condition of the constant voltage section: 50uA, voltage: 2.8-4.25V. The charge and discharge capacity and the first effect were read, and the test results are shown in table 1:
TABLE 1
Figure BDA0003034062390000091
As can be seen from Table 1, the first charge capacity of the batteries prepared by using the positive electrode lithium-supplementing material of the present invention can reach 233.2mAh g as shown in examples 1 to 6-1Above, the first discharge capacity can reach 198.1mAh g-1Above, the first coulombic efficiency can reach above 85.81%, and the capacity retention rate of circulation 100 circles can reach above 87.8%.
By comparing the embodiment 1 with the embodiments 3 to 4, the performance of the lithium supplement material can be influenced by the temperature of the one-step sintering in the step (2), and the positive electrode lithium supplement material with good effect can be prepared by controlling the temperature of the one-step sintering at 400 to 500 ℃.
By comparing the embodiment 1 with the embodiments 5 to 6, the performance of the lithium supplement material prepared by the two-step sintering in the step (2) can be influenced, and the lithium supplement material with a good effect can be prepared by controlling the temperature of the two-step sintering at 600-1000 ℃.
Compared with the comparative example 1, the invention adopts large dosage of low-cost metal elements to perform precursor coprecipitation doping, reduces the cost and replaces a part of Ni2+The lithium nickel mixed discharge is reduced, the structure is stabilized in the cell circulation process, and the oxygen release amount is reduced.
From a comparison of example 1 and comparative example 2, the invention is based on Li2-xNi1-yMyO2Surface coating MemOnThe coating layer greatly reduces the residual lithium content of the finished product, improves the processing and gas production performance, and simultaneously can inhibit the dissolution deposition anode of the transition metals of nickel, copper and iron from damaging the SEI film, thereby improving the cycle。
The phase contrast of the positive electrode lithium supplement material described in example 1 and comparative example 1 is shown in fig. 2, and it can be seen from fig. 2 that the undoped lithium supplement material has a distinct NiO phase, which deteriorates the charge capacity, decreases the structural stability, and deteriorates the electrochemical properties such as cell capacity, rate, power, cycle, etc. The Cu-doped lithium supplement material has no obvious NiO phase, the obtained material has high purity, high charge capacity and stable structure, the circulating gas production is reduced, and the circulating and storing performances are effectively improved.
TEM images of the positive electrode lithium-supplement materials described in example 1 and comparative example 1 are shown in FIGS. 3-4, and can be obtained by comparing FIGS. 3-4, the invention adopts low-cost metal elements to perform precursor coprecipitation doping, and replaces a part of Ni while reducing the cost2+And the mixed lithium-nickel discharge is reduced.
The applicant declares that the above description is only a specific embodiment of the present invention, but the scope of the present invention is not limited thereto, and it should be understood by those skilled in the art that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are within the scope and disclosure of the present invention.

Claims (28)

1. The positive electrode lithium supplement material is characterized by comprising Li2-xNi1-yMyO2And coating with Li2- xNi1-yMyO2Superficial MemOnA coating layer;
wherein M comprises any one or a combination of at least two of Cu, Fe or V, Me comprises any one or a combination of at least two of Ti, Al, Zr or B, 0< x <2, 0< y <1, 0< (x + y) <1, M >1, n > 1;
the positive electrode lithium supplement material is prepared by the following method:
(1) mixing Ni source and M source, adding alkali source, regulating pH value, dewatering and once sintering to obtain Ni1-yMy(OH)2A precursor;
(2) ni obtained in the step (1)1-yMy(OH)2Mixing the precursor, a lithium source and Me oxide, and performing secondary sintering treatment to obtain the positive electrode lithium supplement material;
wherein, the mixing mode in the step (2) is dry ball milling.
2. The positive electrode lithium supplement material according to claim 1, wherein the Li is Li2-xNi1-yMyO2Is of a binary rhombic structure.
3. The positive electrode lithium supplement material according to claim 1, wherein D50 of the positive electrode lithium supplement material is 1 to 20 μm.
4. The positive electrode lithium supplement material according to claim 1, wherein the Li is 100% by mass of the positive electrode lithium supplement material2-xNi1-yMyO2The mass fraction of the components is 99.8-99.95%.
5. The positive electrode lithium supplement material according to claim 1, wherein Me is present in an amount of 100% by mass of the positive electrode lithium supplement materialmOnThe mass fraction of the coating layer is 0.05-0.2%.
6. A method for preparing the lithium supplement material for the positive electrode according to any one of claims 1 to 5, wherein the method comprises the following steps:
(1) mixing Ni source and M source, adding alkali source, regulating pH value, dewatering and once sintering to obtain Ni1-yMy(OH)2A precursor;
(2) ni obtained in the step (1)1-yMy(OH)2Mixing the precursor, a lithium source and Me oxide, and performing secondary sintering treatment to obtain the positive electrode lithium supplement material;
wherein, the mixing mode in the step (2) is dry ball milling.
7. The method of claim 6, wherein the Ni source of step (1) comprises Ni (NO)3)2、NiSO4、NiCO3、Ni(OH)2、NiCl2、NiBr2Or NiI2Any one or a combination of at least two of them.
8. The method of claim 6, wherein the M source comprises any one of iron nitrate, iron sulfate, iron chloride, copper nitrate, copper sulfate, copper chloride, vanadium nitrate, vanadium chloride, or vanadium sulfate, or a combination of at least two thereof.
9. The method of claim 6, wherein the alkali source comprises ammonia and/or sodium hydroxide.
10. The method according to claim 6, wherein the pH in the step (1) is 8 to 11.
11. The method of claim 6, wherein the dehydrating of step (1) comprises filtering, washing and drying.
12. The method according to claim 6, wherein the temperature of the primary sintering in the step (1) is 100 to 600 ℃.
13. The preparation method according to claim 6, wherein the temperature rise rate of the primary sintering in the step (1) is 10 to 150 ℃/h.
14. The preparation method according to claim 6, wherein the time for the primary sintering in the step (1) is 1-10 h.
15. The method of claim 6, wherein the lithium source of step (2) comprises any one of lithium oxide, lithium hydroxide, or lithium carbonate, or a combination of at least two thereof.
16. The method according to claim 6, wherein the Me oxide of step (2) comprises any one or a combination of at least two of titanium oxide, aluminum oxide, zirconium oxide, or boron oxide.
17. The method according to claim 6, wherein the mixing in the step (2) is carried out under a vacuum of 75 to 80 kpa.
18. The method according to claim 6, wherein an atmosphere in the secondary sintering in the step (2) is an inert gas.
19. The method of claim 6, wherein the secondary sintering of step (2) comprises one-step sintering and two-step sintering.
20. The method according to claim 19, wherein the temperature of the one-step sintering is 400 to 500 ℃.
21. The preparation method according to claim 19, wherein the temperature rise rate of the one-step sintering is 1-10 ℃/h.
22. The method according to claim 19, wherein the time for the one-step sintering is 1 to 3 hours.
23. The method of claim 19, wherein the temperature of the two-step sintering is 600 to 1000 ℃.
24. The method according to claim 19, wherein the temperature rise rate of the two-step sintering is 5 to 15 ℃/h.
25. The method of claim 19, wherein the two-step sintering is performed for 8 to 12 hours.
26. The method of claim 6, comprising the steps of:
(1) mixing a Ni source and an M source, adding an alkali source, adjusting the pH to 8-11, dehydrating, heating to 100-600 ℃ at a speed of 10-150 ℃/h, and sintering for 1-10 h to obtain Ni1-yMy(OH)2A precursor;
(2) ni obtained in the step (1)1-yMy(OH)2And mixing the precursor, a lithium source and Me oxide, heating to 400-500 ℃ at the speed of 1-10 ℃/H, sintering for 1-3H, heating to 600-1000 ℃ at the speed of 5-15 ℃/H, and sintering for 8-12H to obtain the anode lithium supplement material.
27. A positive electrode plate, characterized in that the positive electrode plate comprises the positive electrode lithium-supplementing material according to any one of claims 1 to 5.
28. A lithium ion battery comprising the positive electrode sheet of claim 27.
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