CN111799454A - High-nickel layered material with niobium-containing nano surface layer and preparation method thereof - Google Patents

High-nickel layered material with niobium-containing nano surface layer and preparation method thereof Download PDF

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CN111799454A
CN111799454A CN202010689921.9A CN202010689921A CN111799454A CN 111799454 A CN111799454 A CN 111799454A CN 202010689921 A CN202010689921 A CN 202010689921A CN 111799454 A CN111799454 A CN 111799454A
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linbo
lithium
nickel
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coating layer
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CN111799454B (en
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刘中柱
郭爱民
王波
蔡飞鹏
秦显忠
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Energy Research Institute of Shandong Academy of Sciences
CITIC Metal Ningbo Co Ltd
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Energy Research Institute of Shandong Academy of Sciences
CITIC Metal Ningbo 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
    • 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
    • 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
    • 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
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

A high-nickel layered electrode material with a nano surface layer containing Nb comprises Nb5+Gradient doped sublayer and LiNbO3/T‑Nb2O5Composite surface coating layer; the LiNbO3/T‑Nb2O5The composite surface coating layer is made of LiNbO3And T-Nb2O5Two compounds of LiNbO3/T‑Nb2O5The structure of the composite surface coating layer is structure (a) and/or (b), wherein structure (a) is T-Nb2O5Coated with LiNbO5Structure (b) is T-Nb2O5And LiNbO3Mixing occurs in the same layer; the Nb5+Nb in gradient doped layer5+Gradually decreases from the particle surface inwards; the LiNbO3/T‑Nb2O5In the composite surface coating layer, T-Nb2O5The mass percentage of (B) is 1-99%. The electrode material is prepared by constructing Nb5+Gradient doped subsurface layer and T-Nb2O5/LiNbO5The composite surface coating layer effectively relieves the problems of unstable surface structure and residual active lithium ion surface, inhibits the reaction of active materials and organic electrolyte, and obviously enhances the structural stability and the thermal stability of the materials, thereby obviously improving the multiplying power, the circulation and the safety performance of the battery.

Description

High-nickel layered material with niobium-containing nano surface layer and preparation method thereof
Technical Field
The invention relates to a high-nickel layered material with a niobium-containing nano surface layer and a preparation method thereof, belonging to the field of lithium battery electrode materials.
Background
High nickel layered transition metal oxide positive electrode material (LiNi)1-xMxO2Where M ═ Co, Mn, Al, etc., 0.6 ≦ 1-x ≦ 1) has the advantages of high energy density, low cost, and relative safety, has been applied to a plurality of fields such as electric automobile power batteries, electric tool batteries, etc., and is one of the most promising positive electrode materials for lithium ion batteries.
However, the high nickel layered cathode material still has inherent key technical problems to be solved urgently. Firstly, the surface structure transformation and oxygen release reaction caused by cation mixing, the nickel content on the surface of the high nickel layered material is high, when charging to higher voltage (>4.3V)，Ni2+Is oxidized into Ni4+，Ni4+Strong oxidizability, easy reaction with organic electrolyte and Ni generation4+→Ni2 +A transition of (a); and Ni2+With Li+The ionic radii are similar and are easy to passThe transition metal layer migrates to the lithium layer, causing "cation-mixed rows" that cause a transition in the surface structure from the lamellar → spinel-like → rock salt phase. The structural transformation starts from the surface layer and gradually "creeps" towards the core region, causing a decrease in rate capability and cycling stability. When the structure is converted, oxygen is released from the surface crystal lattice of the material, and the reaction of the released oxygen and the organic electrolyte is intensified under high temperature and high voltage to generate CO2CO and the like; when accidents such as collision, needling and the like occur or naked fire occurs, the rapidly released gas reacts violently with the combustible organic electrolyte, and the combustion and even explosion occur, so that the thermal runaway phenomenon is caused, and the safety of the battery is seriously influenced.
Another key technical problem with high nickel layered materials is surface lithium residue. In the preparation of high nickel layered materials, excess lithium is required to inhibit cation shuffling and achieve the desired stoichiometric ratio and performance. Excessive lithium remains on the surface of the material and is easily mixed with CO in the air2Reacts with water vapor to form LiOH and Li2CO3Surface lithium impurities. And the higher the nickel content in the electrode material, the more serious the problem of lithium remaining. The lithium residue shows alkalinity, so that the pH value of the material is too high, and the material reacts with solvent-N-methyl pyrrolidone (NMP) in a binder in the slurry mixing process to generate a gel phenomenon, so that the slurry mixing of the positive electrode is difficult. Furthermore, during long cycle, Li2CO3Can react with organic electrolyte to generate CO2、O2And the gas causes the phenomenon of gas expansion, and the performance of the battery is seriously influenced. Due to LiOH and Li2CO3The lithium is an inert phase, which hinders the transmission of lithium ions and electrons on the interface of the anode and the electrolyte and influences the rate performance of the material.
Ion doping is one of the effective means for suppressing cation misclassification, and the main doping ions include Al3+、Ti4+、Mg2+And Zr4+Plasma metal ion, and PO4 3-、BO4 5-/BO3 3-And plasma is adopted. The ion doping mainly has the functions of inhibiting mixed cation, and improving ion and electricityDaughter conductance, fixed lattice oxygen, and the like. However, the single ion doping often cannot effectively remove the lithium residue on the surface, and cannot effectively avoid the occurrence of surface side reactions.
Most of lithium residues on the surface of the high nickel material can be removed by water washing. However, extensive water rinsing can "wash out" lithium in the inner layer of the material, affecting the electrochemical and storage properties of the material. Direct heating in a pure oxygen atmosphere can also remove surface lithium residues, however, the thermal decomposition products of lithium residues are Li2The O exists in the form of O, and is easy to react with water vapor and CO again when exposed to air2Reaction to produce LiOH and Li2CO3。
The surface coating isolates the active material from the organic electrolyte, inhibits the surface side reaction and can obviously improve the cycle stability and safety of the material. However, conventional lithium-inert cladding materials such as Al2O3、AlF3、MgO，AlPO4Etc., the ionic conductance is low, possibly causing a reduction in rate performance. And lithium conductive cladding, e.g. Li3PO4、Li2SiO3、Li2O·2B2O3And the like, because of higher ionic conductivity, the material not only plays a role of a physical protective layer, but also does not reduce the rate capability of the material. Despite the many advantages of lithium conductivity, active lithium sources are still introduced during the manufacturing process and the problem of removing active lithium residues remains.
Therefore, for the high nickel layered material, the single coating or doping effect is limited, and the problems of unstable surface structure and lithium residue cannot be solved at the same time, so a novel material structure design and a preparation method are needed, and the problems are solved at the same time.
Disclosure of Invention
The results of the prior research show that Nb5+The doped layered transition metal oxide anode material can inhibit mixed discharge of cations and remarkably improve the multiplying power and the cycling stability of the material; LiNbO3The coated modified anode material has high lithium ion conductivity, so that the rate capability of the material can not be reduced while organic electrolyte is effectively isolated. Thus, it is possible to provideConstruction of Nb5+Doped and/or LiNbO3The structure has synergistic effect, and obviously improves multiplying power, circulation and safety performance.
T-Nb2O5The (T-phase niobium oxide) has a special lithium ion transmission channel, has excellent rate performance and can be compared with the most excellent solid electrolyte, and the T-phase niobium oxide is used as a high-rate negative electrode material of a lithium battery at present. Using T-Nb2O5As a source of niobium, in the construction of Nb5+doped/LiNbO3Coating while making excess niobium source (T-Nb)2O5) The surface of the residual material can continue to serve as a physical protective layer without reducing the rate capability of the material.
The invention solves the problems of unstable surface structure and surface lithium residue of the high nickel layered anode material by constructing the composite niobium-containing nanoscale surface layer on the surface of the high nickel layered material.
The invention discloses a high nickel layered electrode material with a niobium-containing nano surface layer, which comprises Nb5+Gradient doped sublayer and LiNbO3/T-Nb2O5Composite surface coating layer; the LiNbO3/T-Nb2O5The composite surface coating layer is made of LiNbO3And T-Nb2O5Two compounds of LiNbO3/T-Nb2O5The structure of the composite surface coating layer is structure (a) and/or (b), wherein structure (a) is T-Nb2O5Coated with LiNbO5Structure (b) is T-Nb2O5And LiNbO3Mixing occurs in the same layer; the Nb5+Nb in gradient doped layer5+Gradually decreases from the particle surface inwards.
The LiNbO3/T-Nb2O5The structures (a) and (b) of the composite surface coating layer are randomly generated because LiOH/Li is distributed on the surface of the material2CO3Lithium remains but is unevenly distributed on the surface layer of the electrode material, and is coated with T-Nb2O5After, during the heat treatment, T-Nb2O5With LiOH/Li2CO3Reaction to produce LiNbO3Unreacted residues remain on the surface, and therefore, T-Nb2O5How much remains, depending on LiOH/Li2CO3Residual amount and T-Nb2O5The amount of the addition.
The LiNbO3/T-Nb2O5The thickness of the composite surface coating layer is 1-50nm, preferably 5-10 nm.
The LiNbO3/T-Nb2O5In the composite surface coating layer, T-Nb2O5Is 1 to 99%, preferably 3 to 50%, more preferably 5 to 20% by mass.
The T-Nb2O5/LiNbO3Composite surface coating layer and high nickel layered anode material LiNixM1-xO2Is 0.1 to 5 percent, preferably 0.5 to 2 percent;
high nickel layered material, and LiNi as base material for the reason of its preparation process and materialxM1-xO2The surfaces will contain LiOH/Li2CO3Lithium remains, the larger the value of x, the higher the amount of lithium remaining. LiNixM1-xO2Coated with T-Nb2O5Then, after a medium temperature heat treatment (between about 500 ℃ and 600 ℃), the reaction solution can react with LiOH/Li2CO3React to generate LiNbO3And unreacted T-Nb2O5It remains on the surface of the material to form LiNbO3/T-Nb2O5The composite structure and the reaction mechanism are as follows:
Li2CO3+Nb2O5→2LiNbO3+CO2
2LiOH+Nb2O5→2LiNbO3+H2O
due to LiOH/Li2CO3Does not completely cover the surface of the material, and therefore, in the areas where no lithium remains, T-Nb2O5After coating and heat treatment, LiNbO may not appear3Thus, T-Nb may occur2O5And LiNbO3In the case of the same layer. The Nb5+The thickness of the gradient doped sublayer was 10-200nm, preferably 20-100 nm;
a preparation method of a high-nickel layered electrode material with a niobium-containing nano surface layer comprises the following steps:
(1) mixing a lithium source and a transition metal precursor in proportion, adding a dispersing agent, and performing ball milling and mixing; the ratio of the lithium source to the transition metal precursor in step (1) is 1.05 to 1.15, preferably 1.08 to 1.10, in terms of moles of lithium and transition metal;
(2) carrying out heat treatment on the product obtained after ball milling and mixing in the step (1) in an oxidizing atmosphere to obtain a high-nickel anode material with lithium residues on the surface;
(3) mixing nano T-Nb2O5Coating the surface of the high-nickel anode material with lithium residues on the surface obtained by sintering in the step (2) to obtain nano T-Nb2O5A coated high nickel layered positive electrode material;
(4) the nanometer T-Nb obtained in the step (3)2O5The coated high-nickel layered anode material is calcined at the temperature of 450-600 ℃ for 2-12h to obtain the high-nickel layered electrode material with the niobium-containing nano surface layer.
The Nb5+The gradient doped sublayer is coated with T-Nb2O5Then, heat treatment is carried out to partially coat Nb with the coating layer5+Diffused into the material surface layer. Nb5+Is gradually reduced from the surface of the particles inwards.
Preferably, the dispersant in step (1) is one of water and ethanol.
Preferably, the lithium source in step (1) is Li2CO3And LiOH, preferably LiOH; the transition metal precursor in the step (1) is NixM1-x(OH)2Or NixM1-xCO3Wherein M is one or combination of Co, Mn and Al, x is 0.01-0.4, preferably x is 0.1-0.4, preferably the transition metal precursor is Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.1Mn0.1(OH)2、Ni0.7Co0.15Mn0.15(OH)2、Ni0.9Co0.05Mn0.05(OH)2And Ni0.6Co0.2Mn0.2CO3And Ni0.8Co0.15Al0.05(OH)2One kind of (1).
Preferably, the oxidizing atmosphere in step (2) is O2Or air, preferably an oxygen atmosphere; the temperature of the heat treatment is 750-900 ℃, and the heat treatment time is 10-25 hours.
Preferably, the high nickel positive electrode material having lithium remaining on the surface in the step (2) has lithium remaining (LiOH + Li)2CO3) The mass percentage of (B) is 0.1% -1%.
Preferably, the molecular formula of the high-nickel cathode material with lithium residues on the surface in the step (2) is LiNi1-xMxO2Wherein M is one or the combination of more of Co, Mn and Al, x is 0.01-0.4, preferably x is 0.1-0.4, and the preferred high-nickel cathode material is LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.7Co0.15Mn0.15O2、LiNi0.9Co0.05Mn0.05O2And LiNi0.8Co0.15Al0.05O2One kind of (1).
Preferably, the nano T-Nb in the step (3)2O5Particle diameter of<100nm, preferably 10-30 nm.
Preferably, the coating mode in the step (3) is one of ball milling, solid phase fusion and ultrasonic oscillation liquid phase coating, and is preferably solid phase fusion.
Advantageous technical effects
The invention constructs Nb on the surface of the high-nickel anode material5+Gradient doped subsurface layer and T-Nb2O5/LiNbO5The composite surface coating layer effectively relieves the problems of unstable surface structure and residual active lithium ion surface, inhibits the reaction of active materials and organic electrolyte, and obviously enhances the structural stability and the thermal stability of the materials, thereby obviously improving the multiplying power, the circulation and the safety performance of the battery.
Drawings
FIG. 1 is LiNbO3And T-Nb2O5The structure of the composite surface coating layer (a) is shown schematically;
FIG. 2 is LiNbO3And T-Nb2O5Structure (b) of the composite surface coating layer;
FIG. 3 is Nb surface gradient doping/LiNbO3And T-Nb2O5Scanning electron microscope photos of the composite coated high nickel layered material;
Detailed Description
The invention is further illustrated by the following examples
Example 1
500g of Ni0.6Co0.2Mn0.2(OH)2Mixed with 141g of LiOH (Li: TM ═ 1.08) and 100mL of deionized water was added as a dispersant, and ball milled at 200 rpm for 30 min. Putting the sample after lithium mixing into a vacuum drying oven, drying for 4h at 110 ℃ until the dispersing agent is completely volatilized, and then carrying out heat treatment on the dried mixture at high temperature of 900 ℃ for 12h to obtain the high-nickel ternary material LiNi0.6Co0.2Mn0.2O2(NCM 622). 500g of sintered product NCM622 and 5g of T-Nb with the grain size of 30nm are taken2O5(T-Nb2O51 wt. -%/NCM) and treated in a solid phase fusion machine for 30 min. And taking out the mixed product, and carrying out high-temperature heat treatment for 5 hours at 500 ℃ in an oxygen atmosphere to obtain a final product, namely NCM622-Nb 1-SF.
Example 2
10g of Ni0.8Co0.1Mn0.1(OH)2Mixed with 2.85g of LiOH (Li: TM ═ 1.10), and 2mL of ethanol was added as a dispersant, and ball-milled at 200 rpm for 30 min. Putting the product after lithium mixing into a vacuum drying oven, drying for 4h at 110 ℃ until the dispersing agent is completely volatilized, and then carrying out heat treatment on the dried mixture for 15h at high temperature of 750 ℃ to obtain the high-nickel ternary material LiNi0.8Co0.1Mn0.1O2(NCM 811). 10g of sintered product NCM811 and 0.2g of T-Nb with the grain size of 20nm are taken2O5(T-Nb2O52 wt. -%/NCM) and 2mL of water was added as a dispersant and ball milled for 30 min. And taking out the mixed product, and carrying out high-temperature heat treatment for 5h at 500 ℃ in an oxygen atmosphere to obtain a final product, namely NCM811-Nb 2.
Example 3
10g of Ni0.8Co0.15Al0.05(OH)2Mixed with 2.87g of LiOH (Li: TM ═ 1.10) and 2mL of water was added as a dispersant, and ball milled at 200 rpm for 30 min. Putting the product after lithium mixing into a vacuum drying oven, drying for 4h at 110 ℃ until the dispersing agent is completely volatilized, and carrying out heat treatment on the dried mixture at the high temperature of 750 ℃ for 15h to obtain the high-nickel ternary material LiNi0.8Co0.15Al0.05O2(NCA). 10g of NCA sintered product and 0.2g of T-Nb with the grain size of 30nm are taken2O5(T-Nb2O52 wt. -%/NCM) and 2mL of water was added as a dispersant and ball milled for 30 min. And taking out the mixed product, and carrying out high-temperature heat treatment for 6h at 550 ℃ in an oxygen atmosphere to obtain a final product, namely NCA-Nb 2.
Comparative example 1
10g of Ni0.6Co0.2Mn0.2(OH)2Mixed with 2.82g of LiOH (Li: TM ═ 1.08) and 2mL of deionized water was added as a dispersant, and ball milled at 200 rpm for 30 min. Putting the product after lithium mixing into a vacuum drying oven, drying for 4h at 110 ℃ until the dispersing agent is completely volatilized, and then carrying out heat treatment on the dried mixture at high temperature of 900 ℃ for 12h to obtain the high-nickel ternary material LiNi0.6Co0.2Mn0.2O2(NCM 622). Comparative example 1 no niobium-containing nano surface layer was supported and the other steps were the same as in example 1.
Comparative example 2
10g of Ni0.6Co0.2Mn0.2(OH)2Mixed with 2.82g LiOH (Li: TM ═ 1.08) and 2mL of deionized water was added as a dispersant and mixed at 200 rpm for 30 min. Putting the product after lithium mixing into a vacuum drying oven, drying at 110 deg.C for 4h until the dispersant is completely volatilized, and drying the mixture at 90 deg.CHeat treating at 0 deg.c for 12 hr to obtain high nickel ternary material LiNi0.6Co0.2Mn0.2O2(NCM 622). 10g of sintered product NCM622 and 0.1g of H-Nb with the grain size of 30nm are taken2O5(H-Nb2O51 wt./NCM) and 2mL of water was added as a dispersant and ball milled for 30 min. And taking out the mixed product, and carrying out high-temperature heat treatment for 5 hours at 500 ℃ in an oxygen atmosphere to obtain a final product, namely NCM622-Nb 1-H. Comparative example 2 using H-Nb2O5The other steps were the same as in example 1.
Comparative example 3
10g of Ni0.6Co0.2Mn0.2(OH)2Mixed with 2.82g LiOH (Li: TM ═ 1.08) and 2mL of deionized water was added as a dispersant and mixed at 200 rpm for 30 min. Putting the product after lithium mixing into a vacuum drying oven, drying for 4h at 110 ℃ until the dispersing agent is completely volatilized, and carrying out heat treatment on the dried mixture at high temperature of 900 ℃ for 12h to obtain the high-nickel ternary material LiNi0.6Co0.2Mn0.2O2(NCM 622). 10g of the sintered product NCM622 and 0.1g of T-Nb with a grain size of 30nm2O5(T-Nb2O51 wt./NCM) and 2mL of water was added as a dispersant and ball milled for 30 min. And taking out the mixed product, and carrying out high-temperature heat treatment for 5 hours at 400 ℃ in an oxygen atmosphere to obtain a final product, namely NCM622-Nb 1-400. Comparative example 3 the clad sintering temperature was 400 c and the other steps were the same as in example 1.
Comparative example 4
10g of Ni0.6Co0.2Mn0.2(OH)2Mixed with 2.82g LiOH (Li: TM ═ 1.08) and 2mL of deionized water was added as a dispersant and mixed at 200 rpm for 30 min. And (3) putting the product after lithium mixing into a vacuum drying oven, and drying for 4 hours at the temperature of 110 ℃ until the dispersing agent is completely volatilized. Carrying out heat treatment on the dried mixture at the high temperature of 900 ℃ for 12h to obtain the high-nickel ternary material LiNi0.6Co0.2Mn0.2O2(NCM 622). 10g of the sintered product NCM622 and 0.1g of T-Nb with a grain size of 30nm2O5(T-Nb2O51 wt./NCM) and 2mL of water was added as a dispersant and ball milled for 30 min. And taking out the mixed product, and carrying out high-temperature heat treatment for 5h at 700 ℃ in an oxygen atmosphere to obtain a final product, namely NCM622-Nb 1-700. Comparative example 3 the clad sintering temperature was 700 c and the other steps were the same as in example 1.
Comparative example 5
10g of Ni0.6Co0.2Mn0.2(OH)2Mixed with 2.82g of LiOH (Li: TM ═ 1.08) and 2mL of deionized water was added as a dispersant, and ball milled at 200 rpm for 30 min. Putting the sample after lithium mixing into a vacuum drying oven, drying for 4h at 110 ℃ until the dispersing agent is completely volatilized, and then carrying out heat treatment on the dried mixture at high temperature of 900 ℃ for 12h to obtain the high-nickel ternary material LiNi0.6Co0.2Mn0.2O2(NCM 622). 10g of the sintered product NCM622 and 0.1g of T-Nb with a grain size of 30nm2O5(T-Nb2O51 wt./NCM) and 2mL of water was added as a dispersant and ball milled for 30 min. And taking out the mixed product, and carrying out high-temperature heat treatment for 5 hours at 500 ℃ in an oxygen atmosphere to obtain a final product, namely NCM622-Nb 1-BM. Wherein the coating T-Nb in example 52O5In a manner different from that of example 1.
Comparative example 6
10g of Ni0.8Co0.1Mn0.1(OH)2Mixed with 2.85g of LiOH (Li: TM ═ 1.10), and 2mL of ethanol was added as a dispersant, and ball-milled at 200 rpm for 30 min. Putting the product after lithium mixing into a vacuum drying oven, drying for 4h at 110 ℃ until the dispersing agent is completely volatilized, and then carrying out heat treatment on the dried mixture for 15h at high temperature of 750 ℃ to obtain the high-nickel ternary material LiNi0.8Co0.1Mn0.1O2(NCM 811). 10g of sintered product NCM811 and 0.2g of T-Nb with the grain size of 20nm are taken2O5(T-Nb2O52 wt. -%/NCM) and 2mL of water was added as a dispersant and ball milled for 30 min. Taking out the mixed product, and performing high-temperature heat treatment at 500 deg.C for 5 hr in oxygen atmosphere to obtain final productUnder the name NCM811-Nb 2.
Comparative example 7
10g of Ni0.8Co0.15Al0.05(OH)2Mixed with 2.87g of LiOH (Li: TM ═ 1.10) and 2mL of deionized water was added as a dispersant, and ball milled at 200 rpm for 30 min. Putting the product after lithium mixing into a vacuum drying oven, drying for 4h at 110 ℃ until the dispersing agent is completely volatilized, carrying out heat treatment on the dried mixture for 15h at the high temperature of 750 ℃ in an oxygen atmosphere to obtain the high-nickel ternary material LiNi0.8Co0.15Al0.05O2(NCA)。
Example 1 and comparative examples 1 to 5 are both LiNi0.6Co0.2Mn0.2O2(NCM622) as a base material, and electrode performance tests were conducted on the above examples and comparative examples, and the results are shown in Table 1.
TABLE 1 Properties of examples and comparative examples using NCM622 as the base Material
Figure BDA0002588960480000071
Example 2 and comparative example 6 are both LiNi0.8Co0.1Mn0.1O2(NCM811) as a base material, and electrode performance tests were conducted on the above examples and comparative examples, and the results are shown in Table 2.
TABLE 2 comparison of the properties of example 2 with comparative example 6 using NCM811 as the base material
Figure BDA0002588960480000072
Example 3 and comparative example 7 are both LiNi0.8Co0.15Al0.05O2(NCA) as a base material, and electrode performance tests were conducted on the above examples and comparative examples, and the results are shown in Table 3.
TABLE 3 Properties of examples and comparative examples using NCA as the base Material
Figure BDA0002588960480000073
Figure BDA0002588960480000081
The above examples are only for illustrating the technical solutions of the present invention, and are not limited thereto. Although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A high-nickel layered electrode material with a nano surface layer containing Nb comprises Nb5+Gradient doped sublayer and LiNbO3/T-Nb2O5Composite surface coating layer; the LiNbO3/T-Nb2O5The composite surface coating layer is made of LiNbO3And T-Nb2O5Two compounds of LiNbO3/T-Nb2O5The structure of the composite surface coating layer is structure (a) and/or (b), wherein structure (a) is T-Nb2O5Coated with LiNbO5Structure (b) is T-Nb2O5And LiNbO3Mixing occurs in the same layer; the Nb5+Nb in gradient doped layer5+Gradually decreases from the particle surface inwards; the LiNbO3/T-Nb2O5In the composite surface coating layer, T-Nb2O5The mass percentage of (B) is 1-99%.
2. The electrode material of claim 1, wherein said LiNbO3/T-Nb2O5The thickness of the composite surface coating layer is 1-50nm, preferably 5-10 nm.
3. The method of claim 1Electrode material, characterized in that said Nb5+The thickness of the gradient-doped sublayer is from 10 to 200nm, preferably from 20 to 100 nm.
4. A method for producing a high nickel layered electrode material having a niobium-containing nano surface layer as claimed in any one of claims 1 to 3, comprising the steps of:
(1) mixing a lithium source and a transition metal precursor in proportion, adding a dispersing agent, and performing ball milling and mixing; the ratio of the lithium source to the transition metal precursor in step (1) is 1.05 to 1.15, preferably 1.08 to 1.10, in terms of moles of lithium and transition metal;
(2) carrying out heat treatment on the product obtained after ball milling and mixing in the step (1) in an oxidizing atmosphere to obtain a high-nickel anode material with lithium residues on the surface;
(3) mixing nano T-Nb2O5Coating the surface of the high-nickel anode material with lithium residues on the surface obtained by sintering in the step (2) to obtain nano T-Nb2O5A coated high nickel layered positive electrode material;
(4) the nanometer T-Nb obtained in the step (3)2O5The coated high-nickel layered anode material is calcined at the temperature of 450-600 ℃ for 2-12h to obtain the high-nickel layered electrode material with the niobium-containing nano surface layer.
5. The method according to claim 4, wherein the dispersant used in step (1) is one of water and ethanol.
6. The method according to claim 4, wherein the lithium source in step (1) is Li2CO3And LiOH, preferably LiOH; the transition metal precursor in the step (1) is NixM1-x(OH)2Or NixM1-xCO3Wherein M is one or more of Co, Mn and Al, x is 0.01-0.4, preferably x is 0.1-0.4, and preferably the transition metal precursor is Ni0.6Co0.2Mn0.2(OH)2、Ni0.8Co0.1Mn0.1(OH)2、Ni0.7Co0.15Mn0.15(OH)2、Ni0.9Co0.05Mn0.05(OH)2And Ni0.6Co0.2Mn0.2CO3And Ni0.8Co0.15Al0.05(OH)2One kind of (1).
7. The method of claim 4, wherein in step (2) the oxidizing atmosphere is O2Or air, preferably an oxygen atmosphere; the temperature of the heat treatment is 750-900 ℃, and the heat treatment time is 10-25 hours.
8. The method according to claim 4, wherein the mass percentage of lithium in the high nickel positive electrode material in the step (2) is 0.1% to 1%.
9. The method of claim 4, wherein the high nickel positive electrode material of formula LiNi in step (2)1- xMxO2Wherein M is one or the combination of more of Co, Mn and Al, x is 0.01-0.4, preferably x is 0.1-0.4, and the preferred high-nickel cathode material is LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.7Co0.15Mn0.15O2、LiNi0.9Co0.05Mn0.05O2And LiNi0.8Co0.15Al0.05O2One kind of (1).
10. The method of claim 4, wherein said nano-T-Nb is performed in step (3)2O5Is less than 100nm, preferably 10-30 nm.
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