CN107068995B - In-situ precipitated oxide coated lithium ion battery positive electrode material and preparation method and application thereof - Google Patents

In-situ precipitated oxide coated lithium ion battery positive electrode material and preparation method and application thereof Download PDF

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CN107068995B
CN107068995B CN201710080939.7A CN201710080939A CN107068995B CN 107068995 B CN107068995 B CN 107068995B CN 201710080939 A CN201710080939 A CN 201710080939A CN 107068995 B CN107068995 B CN 107068995B
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lithium ion
ion battery
lncmo
positive electrode
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CN107068995A (en
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潘洪革
张世明
高明霞
刘永锋
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Kegu Zhejiang Technology Co ltd
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Zhejiang University ZJU
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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    • 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
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    • 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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Abstract

The invention relates to the field of lithium ion battery anode materials, in particular to a preparation method of a novel in-situ precipitated oxide coated lithium ion battery anode material. A preparation method of a novel in-situ precipitated oxide coated lithium ion battery positive electrode material comprises the following steps: adding a raw material of a coating material in the preparation process of the oxide cathode material precursor, then carrying out oxidative decomposition and in-situ precipitation on the surface of the oxide cathode material matrix by the coating material in the high-temperature heat treatment process, and carrying out coating modification on the oxide cathode material matrix to obtain the oxide-coated oxide composite cathode material. The capacity of the lithium ion battery anode material coated and modified by the in-situ precipitated oxide can reach 295 mAmph/g at most in the first charge-discharge capacity, and the capacity retention rate reaches 100% after 300 cycles. The modified lithium ion battery anode material has excellent electrochemical performance and wide application prospect.

Description

In-situ precipitated oxide coated lithium ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention relates to the field of lithium ion battery anode materials, in particular to a preparation method of an in-situ precipitated oxide coated lithium ion battery anode material.
Background
With the development of science and technology and the progress of human society, the problems of energy exhaustion and environmental pollution are increasingly highlighted, and the development of novel efficient and clean energy conversion and storage technology and energy utilization mode becomes the key for solving the problems and realizing the sustainable development of human society. Lithium ion batteries are widely used in the fields of portable mobile electronic devices, electric tools, energy storage devices, electric vehicles and hybrid electric vehicles due to their high operating potential, high specific energy density, high specific power, high operating temperature range, long cycle life and good environmental friendliness. In particular, in recent years, the rapid development of electric vehicles and the miniaturization and lightening of electronic equipment have made higher demands on lithium ion batteries, and the development of novel lithium ion batteries with safety, high efficiency, high capacity, high rate and long cycle life has become a hotspot of current research, while electrode materials are decisive factors for determining the performance of the lithium ion batteries and are also a difficult point and a technical core of the development of the lithium ion batteries, wherein the anode material is a key component of the electrode materials.
However, researches report that structural change, corrosion and dissolution of metal elements, formation of a surface passivation layer, particle breakage, separation of active substances from a conductive agent and the like in the cycle process of the lithium ion battery cathode material are main reasons of poor cycle life, high first irreversible capacity and poor rate performance of the lithium ion battery cathode material. Therefore, in order to improve the cycle stability, the first coulombic efficiency and the rate capability of the lithium ion battery anode material, the surface structure of the lithium ion battery anode material needs to be improved, and the stability of the surface structure in the cycle process is ensured. Research reports that the surface coating can effectively improve the surface structure of the anode material and improve the cycle stability, rate capability and coulomb efficiency of the anode material.
The conventional oxide coating method generally comprises two steps: firstly, synthesizing various oxide matrix materials by various methods; in the second step, the oxide matrix material is mechanically mixed with the raw material for coating (such as by sol-gel method, mechanical ball milling method, etc.), and then the surface coating of the oxide cathode material is achieved by means of heat treatment. However, this coating method cannot achieve uniform, complete and close coating of the base material. Because the manganese oxide base material synthesized in the first step needs to be subjected to heat treatment at a high temperature, the obtained base material particles are seriously agglomerated, and therefore, the mechanical mixing mode cannot realize complete coating of each particle. In addition, the ex-situ coating method cannot realize the tight combination of the coating material and the matrix material. For the above reasons, this coating method has a limited effect on improving the electrochemical performance of the layered oxide positive electrode material.
Disclosure of Invention
The invention aims to provide a novel preparation method of an in-situ precipitated oxide coated lithium ion battery anode material, which is simple to operate, high in efficiency, strong in controllability, low in energy consumption and wide in application range. The coating layer precipitated in situ on the surface of the matrix of the anode material has the characteristics of uniformity, completeness, strong binding force and the like, can effectively keep the structural stability of the particle surface in the circulation process of the anode material, thereby effectively improving the electrochemical performance of the anode material and having wide application prospect. The material has the advantages of high capacity, good cycle stability and rate capability when being used as the anode material of the lithium ion battery. The preparation method of the composite material is simple and suitable for large-scale production. The second purpose of the invention is to provide a lithium ion battery anode using the anode material. It is a third object of the present invention to provide a lithium ion battery using the positive electrode.
In order to achieve the first object, the invention adopts the following technical scheme:
a preparation method of an in-situ precipitated oxide coated lithium ion battery positive electrode material comprises the following steps: adding the raw materials of the coating material in the preparation process of the oxide cathode material precursor, uniformly mixing, then carrying out oxidative decomposition and in-situ precipitation on the surface of the oxide cathode material matrix by the coating material in the high-temperature heat treatment process, and carrying out coating modification on the oxide cathode material matrix to obtain the oxide-coated oxide composite cathode material.
Said xLi2MnO3-(1-x)LiMO2M ═ Ni, Co, Mn, Cr, Fe; ternary material LiNixCoyMnzO2；LiCoO2；LiMn2O4；LiFePO4Can be used as the anode material of the lithium ion battery.
Preferably, said xLi2MnO3-(1-x)LiMO2X is more than or equal to 0.3 and less than or equal to 0.7, and the comprehensive electrochemical performance of the lithium-rich material is reduced when M is not more than Ni, Co, Mn, Cr and Fe and x is too small or too large, so that x is selected in a reasonable range. Ternary material LiNixCoyMnzO2X + y + z is 1, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, the ternary material can be formed, and the better electrochemical performance can be obtained by utilizing the mutually coordinated materials of the components in the ternary material.
Preferably, the coating material is a composite oxide of one or more of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, europium, terbium, yttrium, ytterbium, dysprosium, erbium, and europium. These oxides were chosen because of their compatibility with xLi2MnO3-(1-x)LiMO2M ═ Ni, Co, Mn, Cr, Fe; ternary material LiNixCoyMnzO2；LiCoO2；LiMn2O4；LiFePO4When the chemical property difference of the anode material is larger, the anode material can not be dissolved into the matrix material in the preparation process, but can be precipitated in situ in the matrix material. The adoption of two or more than two oxides for coating utilizes the advantages of various oxide coating layers to obtain a better composite coating material.
Preferably, the coating material is one or more than two composite oxides of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, europium, terbium, yttrium, ytterbium, dysprosium, erbium and europium, and the coating layer mass percentage content is 2-20%. The coating content is less and cannot reach uniform and complete coating effect, so that the coating effect is influenced; too much coating content, on the one hand, reduces the amount of active material and, on the other hand, hinders diffusion of electrons or ions in the active material and thus reduces its electrochemical performance.
Preferably, the raw materials used are acetates, nitrates, sulfates, carbonates, oxalates and metal oxides. Different raw materials have different solubilities and melting points, which have important influence on the composition distribution and phase composition of the synthetic material.
Preferably, the preparation method used is a spraying method, a coprecipitation method, a sol-gel method, a combustion method, a solid phase method, a molten salt method. The materials obtained by different synthesis methods have different phase structures, component distributions, morphologies, particle sizes and the like, and have important influence on various performances of the electrode materials.
Preferably, the adopted heat treatment temperature is 600-1000 ℃; the heat treatment atmosphere is oxygen and air; the heat treatment time is 5 to 48 hours. The phase structure, the component distribution, the morphology, the particle size and the like of the obtained material are different at different heat treatment temperatures, atmospheres and time, and have important influence on various performances of the electrode material.
The invention also provides the lithium ion battery anode material prepared by adopting any one of the technical schemes.
In order to achieve the second object, the invention adopts the following technical scheme:
the lithium ion battery anode material is used as a lithium ion battery anode material and a conductive agent to be subjected to ball milling and mixing. And mixing the mixed material with a binder to form slurry, coating the slurry on an aluminum foil, and drying to obtain the lithium ion battery anode.
Preferably, the conductive agent can be one or more mixed conductive agents of graphite, acetylene black, Super P, carbon nanotubes, graphene and Ketjen black.
Preferably, the content of the conductive agent is 5 to 20 mass percent.
Preferably, the mass percentage of the ball material ratio is 50: 1-200-1; the ball milling speed is 300-500 r/min; the ball milling time is 2-12 hours; the ball milling atmosphere is one or a mixture of more than two of air, oxygen, argon and nitrogen.
Preferably, the binder is an aqueous binder or a non-aqueous binder commonly known to those skilled in the art, such as polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTEE), Styrene Butadiene Rubber (SBR), sodium carboxymethylcellulose (CMC), or Sodium Alginate (SA); the mass percentage is 3-20%.
In order to achieve the third object, the invention adopts the following technical scheme:
the lithium ion battery adopts the technical scheme that the positive electrode of the lithium ion battery is a positive electrode, the positive electrode, electrolyte between the positive electrode and the negative electrode, and the electrolyteAnd assembling the diaphragm paper into the lithium ion battery. In the lithium ion battery of the present invention, the negative electrode material may be any of various conventional negative electrode active materials known to those skilled in the art, such as graphite, silicon and various silicon alloys, iron oxide, tin oxide and various tin alloys, titanium oxide, and the like. The electrolyte may be a conventional non-aqueous electrolyte commonly known to those skilled in the art, wherein the lithium salt in the electrolyte may be lithium hexafluorophosphate (LiPF)6) Lithium perchlorate (LiClO)4) Lithium hexafluoroarsenate (LiAsF)6) Lithium fluorohydroxysulfonate (LiC (SO)2CF3)3) One or more of them. The non-aqueous solvent can be one or more of dimethyl carbonate (DMC), diethyl carbonate (DEC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), Propylene Carbonate (PC) and Vinylene Carbonate (VC).
The invention provides a novel in-situ precipitation method for overcoming the defects of the existing coating mode, and a layer of nano oxide material is coated on the surface of a lithium ion battery anode material. When synthesizing the precursor of the anode material of the lithium ion battery, adding the precursor of the raw material of the anode material and the precursor of the raw material of the coating oxide according to the stoichiometric ratio, and uniformly mixing the precursors; in the high-temperature heat treatment process, the oxide is precipitated in situ on the surface of the anode material matrix to form a uniform and complete nano coating layer with strong binding force. The uniform, complete and strong-binding-force oxide coating layer can effectively keep the structural stability of the particle surface in the circulation process of the anode material, thereby effectively improving the electrochemical performance of the anode material. The capacity of the lithium ion battery anode material coated and modified by the in-situ precipitated oxide can reach 295 mAmph/g at most in the first charge-discharge capacity, and the capacity retention rate reaches 100% after 300 cycles. The modified lithium ion battery anode material has excellent electrochemical performance and wide application prospect.
Compared with the prior art, the invention has the following beneficial effects:
(1) the novel in-situ precipitation coating technology disclosed by the invention is a one-step coating technology and has the characteristics of simplicity, easiness in operation, low cost, low energy consumption and the like;
(2) the in-situ precipitated oxide coating technology of the material overcomes the defects of the traditional two-step coating technology, and has the coating characteristics of uniform and complete nano coating layers with strong binding force. The uniform, complete and strong-binding-force oxide coating can effectively inhibit structural change, metal element dissolution, surface passivation layer formation, particle fracture and active substance separation from a conductive agent in a circulation process. Thereby effectively improving the electrochemical properties of the oxide anode material, such as the first coulombic efficiency, the cycle life, the high rate performance and the like.
Drawings
FIG. 1 is a comparison of the XRD patterns of the product of example 1 of the present invention;
FIG. 2 is a (a, b) SEM image comparison of the product of example 1 of the present invention and (c-i) HTREM image comparison;
FIG. 3 is a comparison of the first charge and discharge curves for the product of example 1 of the present invention;
FIG. 4 is a comparison of the cycle performance curves for the product of example 1 of the present invention;
FIG. 5 is a comparison of the rate capability of the product of example 1 of the present invention;
FIG. 6 is a comparison of the cycle performance curves for the product of example 2 of the present invention;
FIG. 7 is a comparison of the XRD patterns of the product of example 3 of the present invention;
FIG. 8 is a comparison of the cycle performance curves for the product of example 3 of the present invention;
FIG. 9 is a comparison of the XRD patterns of the product of example 4 of the present invention;
FIG. 10 is a comparison of the cycle performance curves for the product of example 4 of the present invention;
FIG. 11 is a graph of the cycle performance of the product of example 5 of the present invention;
FIG. 12 is a graph of the cycle performance of the product of example 6 of the present invention;
FIG. 13 is a graph of the cycle performance of the product of example 7 of the present invention;
FIG. 14 is a comparison of the cycle performance curves for the product of example 8 of the present invention;
FIG. 15 is a comparison of the XRD patterns of the product of example 9 of the invention;
FIG. 16 is a (a, b) SEM image comparison of example 9 products of this invention and (c, d) HTREM image comparison;
FIG. 17 is a comparison of the first charge and discharge curves for the product of example 9 of the present invention;
FIG. 18 is a comparison of the cycle performance curves for the product of example 9 of the present invention;
FIG. 19 is a plot of the cycle performance of the product of example 24 of the present invention.
Detailed Description
The following examples are given to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
Spray pyrolysis method for synthesizing in-situ precipitated Er2O3Cladding with 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO@Er2O3) Positive electrode material
In-situ precipitation of Er2O3Cladding with 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO@Er2O3) Preparing a positive electrode material: adding Li, Ni, Co and Mn acetates into a certain amount of deionized water according to a stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then according to the mass percent of the coating amount, 10 percent (Er)2O310 wt%) erbium acetate (ErAC) was added to the reaction solution; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. The obtained precursor is thermally treated for 10 hours at 900 ℃ to obtain different Er2O3A coated LNCMO cathode material.
Applying LNCMO @ Er2O3The anode material and the binder are mixed according to a certain proportion, magnetic stirring is adopted for 4 hours to obtain uniform slurry, and then the slurry is uniformly coated on the aluminum foil to obtain the electrode material. The characterization cell adopts a 2025 button cell, the assembly process is completed in a glove box filled with Ar, and the water and oxygen contents are both less than 0.1 ppm. The positive electrode is the prepared electrode plate; the reference electrode and the counter electrode are metal lithium sheets; the septum is Celgard-2400; the electrolyte is LiPF6(1mol/L)/EC + DEC + EMC (1:1:1), the assembled cell was placed for testing.
FIG. 1 shows original LNCMO and 10% Er by mass2O3XRD of the coated LNCMO material. As shown in the figure, all diffraction peaks can be associated with the LiMO with a hexagonal structure2(R-3M) (PDF #85-1966) and monoclinic Li2MO3(M ═ Ni, Co, Mn, etc.) (C/2M) (PDF #84-1634) corresponds well. In addition, Er is clearly seen in the figure2O3Diffraction peaks of (Ia3) (PDF # 74-1983). Er with the mass percent of 10 percent compared with the uncoated LNCMO2O3There was no significant shift in XRD peaks for the coated LNCMO material, indicating Er2O3Does not cause the change of the crystal lattice structure of the LNCMO matrix material, and also suggests Er3+Does not enter into the crystal lattice structure of the LNCMO matrix material but is precipitated in situ on the surface of the matrix to form LNCMO @ Er2O3A composite material.
FIG. 2(a, b) respectively shows the original LNCMO material ErO0 and 10% Er by mass2O3SEM image of coated LNCMO material. The original LNCMO material and 10% Er by mass can be seen2O3The coated LNCMO material is composed of nanoparticles with uniform primary particle size of 100-200 nm. Except that the original LNCMO particles had a smoother surface and 10% Er by mass2O3The surface of the coated LNCMO particles is rough, and the main reason is Er2O3The LNCMO @ Er is precipitated on the surface of the LNCMO matrix to cause the LNCMO @ Er2O3The surface of the particles is rough. The original LNCMO material and 10% Er by mass in FIG. 2(c, f)2O3Low magnification TEM bright field images of coated LNCMO material further demonstrate Er2O3Precipitating on the surface of an LNCMO matrix to cause LNCMO @ Er2O3The surface of the particles is rough. FIG. 2(d, g) shows the original LNCMO material ErO0 and 10% Er by mass2O3HRTEM pictures of coated LNCMO material ErO 8. Picture display, in mass percent 8% Er2O3The surface of the coated particles of LNCMO material is present as a coating layer having a thickness of about 10 nm. The fast fourier transform in figure 2(e, f, g) confirms that,the coating layer on the surface is Er2O3And the bulk phase matrix material is LNCMO. The results prove that Er with the thickness of about 10 nanometers is precipitated in situ on the surface of an LNCMO matrix in the high-temperature heat treatment process by adding the erbium acetate material in the synthesis process of the LNCMO material precursor2O3The coating layer of (2).
FIG. 3(a, b) shows original LNCMO and 10% Er by mass2O3First charge and discharge curves of the coated LNCMO electrode material at a current density of 20 milliamps/gram. It can be seen from the curves that there are two different electrochemical reaction processes during the first charge of the electrode material, with the demarcation point being around 4.4 volts. Wherein the first electrochemical reaction is Ni2+And Co3+Oxidation reaction of (3). When the charging is continued from 4.4 to 4.8 volts, another electrochemical reaction occurs, which is Li+From Li2MnO3Is removed with O2Corresponding to Li2O from Li2MnO3Removing the electrode material to form electrochemically active MnO2. During the following discharge, Li+Re-embedding in the electrode material, Ni4+，Co4+，Mn4+The reduction process of (1). Meanwhile, the result shows that the original LNCMO and Er with the mass percent of 10 percent2O3The first charge-discharge specific capacity and the corresponding irreversible capacity of the coated LNCMO electrode material under the current density of 20 milliampere/gram. Their first discharge specific capacities were 290, 272 mAmp-hrs/g, respectively; the first irreversible capacity is respectively: 64, 39 mAmp-hrs/gram. The results show that Er2O3The coating can effectively reduce the irreversible capacity of the LNCMO anode material in the first circulation process, thereby improving the first coulombic efficiency.
FIG. 4 shows original LNCMO and 10% Er by mass2O3The result of the cycle performance curve of the coated LNCMO electrode material under the current density of 200 milliampere/gram shows that Er2O3The coating has great influence on the cycle performance of the LNCMO cathode material. Original LNCMO and Er with the mass percent of 10 percent under the current density of 200 milliampere/gram2O3Coating ofThe specific discharge capacity of the LNCMO electrode material for the first time is respectively as follows: 227, 206 milliamp hours/gram; after 300 cycles, the discharge specific capacities were respectively: 191, 208 mAmph/g, the corresponding capacity retention rates are: 84 and 102 percent. Thus, Er2O3The coating can effectively improve the cycling stability of the LNCMO cathode material. In addition, original LNCMO and 10% Er by mass2O3The cycle performance curve of the coated LNCMO electrode material can be seen, and Er is added in the initial stage of the cycle2O3There was a gradual increase in capacity for both the coated LNCMO positive electrode materials due to Er2O3The initial state of coating reduces the electrochemical activity of the LNCMO cathode material, and the electrochemical activity of the LNCMO is gradually released in the circulation process.
FIG. 5 shows original LNCMO and 10% Er by mass2O3Rate performance curve of the coated LNCMO electrode material. The results show that the uncoated ErO0 electrode material exhibits higher rate capacity below 1C rate, while the charge-discharge rate is higher>1C, Er2O3The coated electrode material exhibits a relatively high rate capability. At a high magnification of 10C, Er2O3The discharge rate capacity of the coated electrode material was 153 mAmp-hrs/g, whereas the discharge rate capacity of the original LNCMO electrode material was only 130 mAmp-hrs/g. The results show that Er2O3The in-situ precipitation coating can also improve the high rate performance of the LNCMO cathode material.
Example 2
Spray pyrolysis method for synthesizing in-situ precipitated Er2O3Cladding with 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO@Er2O3) Influence of cathode Material-different erbium starting materials
In-situ precipitation of Er2O3Cladding with 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO@Er2O3) Preparing a positive electrode material: adding a certain amount of Li, Ni, Co and Mn acetate according to stoichiometric ratioIn ionized water, mechanically stirring to obtain a uniform reaction solution; then according to the mass percent of the coating amount, 10 percent (Er)2O310 wt%) different kinds of erbium salt raw materials (erbium nitrate, erbium carbonate, erbium oxalate) were added to the reaction solution; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. The obtained precursor is thermally treated for 10 hours at 900 ℃ to obtain different Er2O3A coated LNCMO cathode material.
The preparation of the electrode and the assembly of the battery were the same as in example 1.
FIG. 6 shows LNCMO @ Er obtained from different erbium salt raw materials2O3Cycle performance curve of the positive electrode material. From the curves, it can be seen that different erbium salts produce LNCMO @ Er2O3The cycle performance of the anode material is greatly improved. In comparison, the LNCMO @ Er obtained from erbium nitrate and erbium oxalate2O3The cycle capacity of the positive electrode material is relatively high, but the erbium carbonate yields LNCMO @ Er2O3The cycling stability of the anode material is better.
Example 3
Preparation of LNCMO @ Er by coprecipitation method2O3Positive electrode material
In-situ precipitation of Er2O3Cladding with 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO@Er2O3) Preparing a positive electrode material: adding the nitrate of Li, Ni, Co and Mn into a certain amount of deionized water according to the stoichiometric ratio, and then coating 10 mass percent (Er)2O3And 10 wt%) adding erbium nitrate into the reaction solution, adjusting the pH value of the solution to 11 by using ammonia water, mechanically stirring for 10 hours, then obtaining a reactant by adopting a suction filtration mode, and drying for 12 hours at 120 ℃ to obtain a precursor. The obtained precursor is thermally treated for 10 hours at 900 ℃ to obtain different Er2O3A coated LNCMO cathode material.
The preparation of the electrode and the assembly of the battery were the same as in example 1.
FIG. 6 shows original LNCMO and 10% Er by mass2O3XRD of the coated LNCMO material. As shown in the figure, all diffraction peaks can be associated with the LiMO with a hexagonal structure2(M ═ Ni, Co, Mn, etc.) (R-3M) (PDF #85-1966) and monoclinic Li2MO3(M-Ni, Co, Mn, etc.) (C/2M) (PDF #84-1634) corresponds well. In addition, Er is clearly seen in the figure2O3Diffraction peaks of (Ia3) (PDF # 74-1983). Er with the mass percent of 10 percent compared with the uncoated LNCMO2O3There was no significant shift in XRD peaks for the coated LNCMO material, indicating Er2O3Does not cause the change of the crystal lattice structure of the LNCMO matrix material, and also suggests Er3+Does not enter into the crystal lattice structure of the LNCMO matrix material but is precipitated in situ on the surface of the matrix to form LNCMO @ Er2O3A composite material.
FIG. 7 shows original LNCMO and 10% Er prepared by coprecipitation method2O3The result of the cycle performance curve of the coated LNCMO electrode material under the current density of 200 milliampere/gram shows that Er2O3The coating has great influence on the cycle performance of the LNCMO cathode material. Original LNCMO and Er with the mass percent of 10 percent under the current density of 200 milliampere/gram2O3The first discharge specific capacities of the coated LNCMO electrode material are respectively as follows: 227, 220 milliamp hours/gram; after 300 cycles, the discharge specific capacities were respectively: 191, 208 mAmph/g, the corresponding capacity retention rates are: 84, 94 percent. Thus, Er2O3The coating can effectively improve the cycling stability of the LNCMO cathode material.
Example 4
Preparation of LNCMO @ Er by sol-gel method2O3Positive electrode material
In-situ precipitation of Er2O3Cladding with 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO@Er2O3) Preparing a positive electrode material: adding Li, Ni, Co and Mn acetate into a certain amount of ethanol solution according to the stoichiometric ratio, and then coating 10 mass percent (Er)2O310 wt.%) adding erbium acetateAdding the mixture into the reaction solution, magnetically stirring the mixture until sol is formed, and drying the sol for 12 hours at the temperature of 120 ℃ to obtain a gel precursor. The obtained precursor is thermally treated for 10 hours at 900 ℃ to obtain different Er2O3A coated LNCMO cathode material.
The preparation of the electrode and the assembly of the battery were the same as in example 1.
FIG. 8 shows original LNCMO and Er with the mass percent of 10% prepared by a sol-gel method2O3XRD of the coated LNCMO material. As shown in the figure, all diffraction peaks can be associated with the LiMO with a hexagonal structure2(M ═ Ni, Co, Mn, etc.) (R-3M) (PDF #85-1966) and monoclinic Li2MO3(M-Ni, Co, Mn, etc.) (C/2M) (PDF #84-1634) corresponds well. In addition, Er is clearly seen in the figure2O3Diffraction peaks of (Ia3) (PDF # 74-1983). Er with the mass percent of 10 percent compared with the uncoated LNCMO2O3There was no significant shift in XRD peaks for the coated LNCMO material, indicating Er2O3Does not cause the change of the crystal lattice structure of the LNCMO matrix material, and also suggests Er3+Does not enter into the crystal lattice structure of the LNCMO matrix material but is precipitated in situ on the surface of the matrix to form LNCMO @ Er2O3A composite material.
FIG. 9 shows original LNCMO and 10% Er prepared by sol-gel method2O3The result of the cycle performance curve of the coated LNCMO electrode material under the current density of 200 milliampere/gram shows that Er2O3The coating has great influence on the cycle performance of the LNCMO cathode material. Original LNCMO and Er with the mass percent of 10 percent under the current density of 200 milliampere/gram2O3The first discharge specific capacities of the coated LNCMO electrode material are respectively as follows: 227, 205 milliamp hours/gram; after 300 cycles, the discharge specific capacities were respectively: 191, 213 ma hour/g, corresponding capacity retention rates are: 84 and 104 percent. Thus, Er2O3The coating can effectively improve the cycling stability of the LNCMO cathode material.
Example 5
Spray pyrolysis method for synthesizing in-situ precipitationEr2O3Cladding with 0.7Li2MnO3-0.3LiNi0.33Co0.33Mn0.33O2(LNCMO-1@Er2O3) Positive electrode material
In-situ precipitation of Er2O3Cladding with 0.7Li2MnO3-0.3LiNi0.33Co0.33Mn0.33O2(LNCMO@Er2O3) Preparing a positive electrode material: adding Li, Ni, Co and Mn acetates into a certain amount of deionized water according to a stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then according to the mass percent of the coating amount, 10 percent (Er)2O310 wt%) erbium acetate (ErAC) was added to the reaction solution; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. The obtained precursor is thermally treated for 10 hours at 900 ℃ to obtain different Er2O3A coated LNCMO cathode material.
The preparation of the electrode and the assembly of the battery were the same as in example 1.
FIG. 10 shows 10% Er by mass2O3The result of the cycle performance curve of the coated LNCMO-1 electrode material under the current density of 200 milliampere/gram shows that Er2O3The coating has great influence on the cycle performance of the LNCMO-1 cathode material. Er with the mass percent of 10 percent at the current density of 200 milliampere/gram2O3The primary discharge specific capacities of the coated LNCMO-1 electrode material are respectively as follows: 218 mAmph/g; after 300 cycles, the discharge specific capacities were respectively: 203 ma-hr/g, corresponding to a capacity retention of 93%. Thus, Er2O3The coating can effectively improve the cycling stability of the LNCMO-1 cathode material.
Example 6
Spray pyrolysis method for synthesizing in-situ precipitated Er2O3Cladding with 0.4Li2MnO3-0.6LiNi0.33Co0.33Mn0.33O2(LNCMO-2@Er2O3) Positive electrode material
In-situ precipitation of Er2O3Cladding with 0.4Li2MnO3-0.6LiNi0.33Co0.33Mn0.33O2(LNCMO@Er2O3) Preparing a positive electrode material: adding Li, Ni, Co and Mn acetates into a certain amount of deionized water according to a stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then according to the mass percent of the coating amount, 10 percent (Er)2O310 wt%) erbium acetate (ErAC) was added to the reaction solution; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. The obtained precursor is thermally treated for 10 hours at 900 ℃ to obtain different Er2O3A coated LNCMO cathode material.
The preparation of the electrode and the assembly of the battery were the same as in example 1.
FIG. 11 shows 10% Er by mass2O3The result of the cycle performance curve of the coated LNCMO-2 electrode material under the current density of 200 milliampere/gram shows that Er2O3The coating has great influence on the cycle performance of the LNCMO-2 cathode material. Er with the mass percent of 10 percent at the current density of 200 milliampere/gram2O3The primary discharge specific capacities of the coated LNCMO-2 electrode material are respectively as follows: 200 mAmph/g; after 300 cycles, the discharge specific capacities were respectively: 198 mAmph/g, corresponding to a capacity retention of 99%. Thus, Er2O3The coating can effectively improve the cycling stability of the LNCMO-2 cathode material.
Example 7
Spray pyrolysis method for synthesizing in-situ precipitated Er2O3Coating with 0.3Li2MnO3-0.7LiNi0.33Co0.33Mn0.33O2(LNCMO-3@Er2O3) Positive electrode material
In-situ precipitation of Er2O3Coating with 0.3Li2MnO3-0.7LiNi0.33Co0.33Mn0.33O2(LNCMO-3@Er2O3) Preparing a positive electrode material: adding Li, Ni, Co and Mn acetates into a certain amount of deionized water according to a stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then according to the mass percent of the coating amount, 10 percent (Er)2O310 wt.%) ofErbium acetate (ErAC) was added to the reaction solution; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. The obtained precursor is thermally treated for 10 hours at 900 ℃ to obtain different Er2O3A coated LNCMO cathode material.
The preparation of the electrode and the assembly of the battery were the same as in example 1.
FIG. 12 shows 10% Er by mass2O3The result of the cycle performance curve of the coated LNCMO-3 electrode material under the current density of 200 milliampere/gram shows that Er2O3The coating has great influence on the cycle performance of the LNCMO-3 cathode material. Er with the mass percent of 10 percent at the current density of 200 milliampere/gram2O3The primary discharge specific capacities of the coated LNCMO-3 electrode material are respectively as follows: 194 milliamp hours/gram; after 300 cycles, the discharge specific capacities were respectively: 187 mAmp/g, corresponding to a capacity retention of 96%. Thus, Er2O3The coating can effectively improve the cycling stability of the LNCMO-3 cathode material.
Example 8
Spray pyrolysis method for synthesizing in-situ precipitated Er2O3Cladding with 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO@Er2O3) Positive electrode material
In-situ precipitation of Er2O3Cladding with 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO@Er2O3) Preparing a positive electrode material: adding Li, Ni, Co and Mn acetates into a certain amount of deionized water according to a stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then according to the mass percent of the coating amount, 10 percent (Er)2O310 wt%) erbium acetate (ErAC) was added to the reaction solution; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. The obtained precursor is respectively subjected to heat treatment for 10 hours at the temperature of 600,800,1200 ℃ to obtain different Er2O3A coated LNCMO cathode material.
The preparation of the electrode and the assembly of the battery were the same as in example 1.
FIG. 13 shows 10% Er prepared at different heat treatment temperatures2O3The results of the cycle performance curve of the coated LNCMO electrode material at a current density of 200 milliamperes/gram show that the heat treatment temperature is in accordance with LNCMO @ Er2O3The cycle performance of the positive electrode material has a great influence. LNCMO @ Er prepared at different heat treatment temperatures under the current density of 200 milliampere/gram2O3The specific capacity of the anode material in first discharge is respectively as follows: 223,221, 219 milliamp hours/gram; after 300 cycles, the discharge specific capacities were respectively: 190, 206, 180 ma hour/g, the corresponding capacity retention rates are: 84, 93 and 82 percent. Thus, Er2O3The coating can effectively improve the cycling stability of the LNCMO-3 cathode material.
Example 9
Spray pyrolysis method for synthesizing in-situ precipitated Ce2O3Cladding with 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO@Ce2O3) Positive electrode material
In situ precipitation of Ce2O3Cladding with 0.5Li2MnO3-0.5LiNi0.33Co0.33Mn0.33O2(LNCMO@Ce2O3) Preparing a positive electrode material: adding Li, Ni, Co and Mn acetates into a certain amount of deionized water according to a stoichiometric ratio, and mechanically stirring to obtain a uniform reaction solution; then according to the coating amount of 10 percent by mass (Ce)2O310 wt%) cerium acetate (CeAC) was added to the reaction solution; and carrying out spray pyrolysis on the reaction solution to obtain a precursor. The obtained precursor is thermally treated for 10 hours at 900 ℃ to obtain different Ce2O3A coated LNCMO cathode material.
The preparation of the electrode and the assembly of the battery were the same as in example 1.
FIG. 14 shows original LNCMO and 10% Ce by mass2O3XRD of the coated LNCMO material. As shown in the figure, all diffraction peaks can be associated with the LiMO with a hexagonal structure2(M＝Ni，Co，Mn，etc.)(R-3m)(PDF#85-1966) And monoclinic structure Li2MO3(M ═ Ni, Co, Mn, etc.) (C/2M) (PDF #84-1634) corresponds well. In addition, Ce is clearly seen in the figure2O3Diffraction peaks of the phases. 10% by mass Ce compared to uncoated LNCMO2O3There was no significant shift in the XRD peaks of the coated LNCMO material, indicating that Ce is present2O3Does not cause the change of the crystal lattice structure of the LNCMO matrix material, and also suggests that Ce is3+Does not enter the crystal lattice structure of the LNCMO matrix material but is precipitated on the surface of the matrix in situ to form LNCMO @ Ce2O3A composite material.
FIGS. 15(a, b) are respectively the original LNCMO material and 10% Ce by mass2O3Low magnification TEM bright field image of coated LNCMO material, the results confirm Ce2O3Precipitating on the surface of an LNCMO substrate to cause LNCMO @ Ce2O3The surface of the particles is rough. FIG. 15(c, d) shows the respective original LNCMO material Ce2O3And 10% by mass of Ce2O3HRTEM pictures of coated LNCMO material. The picture shows that the mass percent of Ce is 10 percent2O3The surface of the coated particles of LNCMO material is present as a coating layer having a thickness of about 10 nm.
FIGS. 16(a, b) show the original LNCMO and 10% Ce by mass, respectively2O3First charge and discharge curves of the coated LNCMO electrode material at a current density of 20 milliamps/gram. It can be seen from the curves that there are two different electrochemical reaction processes during the first charge of the electrode material, with the demarcation point being around 4.4 volts. Wherein the first electrochemical reaction is Ni2+And Co3+Oxidation reaction of (3). When the charging is continued from 4.4 to 4.8 volts, another electrochemical reaction occurs, which is Li+From Li2MnO3Is removed with O2Corresponding to Li2O from Li2MnO3Removing the electrode material to form electrochemically active MnO2. During the following discharge, Li+Re-embedding in the electrode material, Ni4+，Co4+，Mn4+The reduction process of (1). Meanwhile, the results show that the original LNCMO and 10 mass percent Ce are2O3The first charge-discharge specific capacity and the corresponding irreversible capacity of the coated LNCMO electrode material under the current density of 20 milliampere/gram. Their first discharge specific capacities were 293, 279 mAmp-hrs/g, respectively; the first irreversible capacity is respectively: 64, 45 mAmp-hrs/gram. The results show that Ce2O3The coating can effectively reduce the irreversible capacity of the LNCMO anode material in the first circulation process, thereby improving the first coulombic efficiency.
FIG. 17 shows the original LNCMO and 10% Ce by mass2O3The cycle performance curve of the coated LNCMO electrode material at a current density of 200 milliamps/gram shows that Ce2O3The coating has great influence on the cycle performance of the LNCMO cathode material. Original LNCMO and 10% Ce by mass at a current density of 200 mA/g2O3The first discharge specific capacities of the coated LNCMO electrode material are respectively as follows: 228, 218 mAmp-hrs/gram; after 300 cycles, the discharge specific capacities were respectively: 191, 205 ma hour/g, the corresponding capacity retention rates are: 84, 94 percent. Thus, Ce2O3The coating can effectively improve the cycling stability of the LNCMO cathode material.
Examples 10 to 17
Examples 10 to 17 the preparation process of example 1 was followed, using Y respectively2O3，La2O3，Ce2O3，Er2O3And the mixture of the oxide and the compound modifies the LNCMO anode material, and the result shows that the oxide and the mixed coating of the oxide can effectively improve the cycle stability of the LNCMO anode material.
Examples 18 to 23
Examples 18 to 123 the preparation methods of example 1 were each followed with Ce2O3，Er2O3IsooxideFor LiNi0.33Co0.33Mn0.33O2，LiCoO2，LiMn2O4When the anode material is coated and modified, the experimental result shows that Ce is coated and modified2O3，Er2O3Isoproxide pair LiNi0.33Co0.33Mn0.33O2，LiCoO2，LiMn2O4And the cycle stability of the anode materials can be effectively improved by coating the anode materials.
Example 24
Er with a mass percentage of 10% was prepared according to the preparation method in example 12O3A coated LNCMO cathode material.
Applying LNCMO @ Er2O3The anode material and the binder are mixed according to a certain proportion, magnetic stirring is adopted for 4 hours to obtain uniform slurry, and then the slurry is uniformly coated on the aluminum foil to obtain the electrode material. The characteristic cell adopts a 18650 cell, the assembly process is completed in a glove box filled with Ar, and the water and oxygen contents are both less than 0.1 ppm. The positive electrode is the prepared electrode plate; the reference electrode and the counter electrode are graphite sheets; the septum is Celgard-2400; the electrolyte is LiPF6(1mol/L)/EC + DEC + EMC (1:1:1), the assembled cell was placed for testing.
As shown in the results of FIG. 19, 10% Er by mass2O3When the first discharge specific capacity of a full battery taking the coated LNCMO as a positive electrode material and graphite as a negative electrode is 2550 milliamperes, the capacity retention rate after 500 cycles is 89%. When the initial discharge capacity of the full battery taking the unmodified LNCMO as the anode and the graphite as the cathode is 2510 milliampere, the capacity retention rate is only 72 percent after 500 cycles. The above results fully illustrate Er2O3The coated LNCMO cathode material can effectively prolong the cycle life of a battery using the coated LNCMO cathode material as a cathode material.

Claims (13)

1. A preparation method of an in-situ precipitated oxide coated lithium ion battery positive electrode material is characterized by comprising the following steps: adding a raw material precursor of a coating material in the preparation process of the lithium ion battery anode material precursor, uniformly mixing, and then in the high-temperature heat treatment process, oxidizing and decomposing the coating material on the surface of a base material and in-situ precipitating the coating material to obtain an in-situ precipitated and coated modified lithium ion battery composite anode material; the coating material is various metal oxides, including one or more composite oxides of lanthanum, cerium, praseodymium, neodymium, samarium, gadolinium, europium, terbium, yttrium, ytterbium, dysprosium, erbium and europium.
2. The method for preparing the in-situ precipitated oxide coated lithium ion battery positive electrode material according to claim 1, wherein the positive electrode material is xLi2MnO3-(1-x)LiMO2M ═ Ni, Co, Mn, Cr, Fe; ternary material LiNixCoyMnzO2；LiCoO2；LiMn2O4；LiFePO4。
3. The method for preparing the in-situ precipitated oxide coated lithium ion battery positive electrode material according to claim 2, wherein the positive electrode material xLi2MnO3-(1-x)LiMO2X is more than or equal to 0 and less than or equal to 1, and M is Ni, Co, Mn, Cr and Fe; ternary material LiNixCoyMnzO2，x+y+z＝1，0≤x≤1，0≤y≤1，0≤z≤1。
4. The method for preparing the in-situ precipitated oxide coated lithium ion battery positive electrode material as claimed in any one of claims 1 to 3, wherein the coating material accounts for 1 to 50 percent of the positive electrode material by mass.
5. The method for preparing the in-situ precipitated oxide coated lithium ion battery anode material according to any one of claims 1 to 3, wherein the precursor of the raw material used for the lithium ion battery anode material and the coating material is one or more of acetate, nitrate, sulfate, carbonate, oxalate and oxide.
6. The method for preparing the in-situ precipitated oxide coated lithium ion battery anode material according to any one of claims 1 to 3, wherein the method for preparing the lithium ion battery anode material precursor is a spraying method, a coprecipitation method, a sol-gel method, a combustion method, a solid phase method or a molten salt method.
7. The method for preparing the in-situ precipitated oxide coated lithium ion battery anode material according to any one of claims 1 to 3, wherein the heat treatment atmosphere is oxygen, air or vacuum; the adopted heat treatment temperature is 400-1400 ℃; the heat treatment time is 0.5 to 72 hours.
8. The lithium ion battery cathode material prepared by the preparation method according to any one of claims 1 to 7.
9. A lithium ion battery positive electrode, characterized in that: the lithium ion battery anode material of claim 8 is adopted as an anode material and is ball-milled and mixed with a conductive agent, then the mixture is mixed with a binder to form slurry, the slurry is coated on an aluminum foil, and after drying, the lithium ion battery anode is obtained.
10. The positive electrode of a lithium ion battery of claim 9, wherein: the conductive agent comprises one or more mixed conductive agents of graphite, acetylene black, Super P, carbon nano tubes, graphene, Ketjen black and various carbon materials; the content of the conductive agent is 2-30% by mass.
11. The positive electrode of a lithium ion battery of claim 10, wherein: the ball material ratio is 5: 1-300: 1; the ball milling speed is 100 to 800 revolutions per minute; the ball milling time is 0.5 to 48 hours; the ball milling atmosphere is as follows: one or more of air, oxygen, nitrogen, hydrogen, argon, carbon dioxide and helium.
12. The positive electrode of a lithium ion battery of claim 9, wherein: the binder comprises one or more than two mixed binders of polyvinylidene fluoride (PVDF), Polytetrafluoroethylene (PTEE), Polyacrylonitrile (PAN), Styrene Butadiene Rubber (SBR), sodium carboxymethylcellulose (CMC) or Sodium Alginate (SA); the mass percentage of the binder is 1-20%.
13. A lithium ion battery, characterized by: the positive electrode according to claim 9, a negative electrode capable of deintercalating lithium ions, and an electrolyte interposed between the negative electrode and the positive electrode.
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