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CN105938899B - A kind of preparation method and application of fast-ionic conductor coating modification anode material for lithium-ion batteries - Google Patents

A kind of preparation method and application of fast-ionic conductor coating modification anode material for lithium-ion batteries Download PDF

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CN105938899B
CN105938899B CN201610381733.3A CN201610381733A CN105938899B CN 105938899 B CN105938899 B CN 105938899B CN 201610381733 A CN201610381733 A CN 201610381733A CN 105938899 B CN105938899 B CN 105938899B
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lithium
positive electrode
anode material
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electrode material
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CN105938899A (en
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张治安
赖延清
徐�明
张凯
李劼
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Central South University
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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
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
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    • 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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    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract

The invention discloses a kind of preparation method and applications of fast-ionic conductor coated lithium ion battery positive electrode；This method is to be stirred to react with lithium-containing solution by after nanoscale aluminium powder and positive electrode ball milling mixing, obtain alumine hydroxide colloid clad anode material presoma；The alumine hydroxide colloid clad anode material presoma is calcined under high-temperature, up to the anode material for lithium-ion batteries with the good fast-ionic conductor coating modification of dense uniform, stability, it can be used for preparing the lithium ion cell positive of high rate capability and high circulation performance, and the preparation method is at low cost, it is easy to operate, the features such as environmental-friendly, can be applied on a large scale industrialization production.

Description

Preparation method and application of fast ion conductor coated modified lithium ion battery positive electrode material
Technical Field
The invention relates to a preparation method of a modified lithium ion battery anode material, in particular to a preparation method of a modified lithium ion battery anode material coated by a fast ion conductor and application of the modified lithium ion battery anode material in preparation of a lithium ion battery with a long cycle life, and belongs to the technical field of lithium ion batteries.
Background
Nowadays, the rapid development of mobile electronic devices, such as smart phones, digital cameras, notebook computers, and electric and hybrid cars, has promoted the rapid advance of lithium ion secondary battery technology. However, the current lithium ion battery cathode materials, such as lithium cobaltate, spinel lithium manganate and lithium iron phosphate, all have the disadvantage of short cycle life, and cannot meet the requirements of future pure electric equipment. Therefore, research and development of a cathode material having a high cycle life has become a common goal of researchers all over the world.
The coating modification is a protection method for forming a uniform coating layer on the surface of target material particles by adopting a material with excellent physical and chemical properties. Researchers use the fast ion conductor to coat the anode material, and the result shows that the fast ion conductor coated modified anode material has better rate performance and cycle performance. However, in the conventional coating method, the preparation process of the fast ion conductor has the disadvantages of complicated operation and high cost, and it is difficult to realize large-scale industrial production. Therefore, it is imperative to find a preparation method which is simple in operation, low in cost and environment-friendly.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a fast ion conductor LiAlO2The method for coating the modified lithium ion battery anode material with the fast ion conductor has the advantages of compact and uniform coating layer and good stability, is simple to operate, low in cost and environment-friendly, and is beneficial to industrial production.
The invention also aims to provide the application of the fast ion conductor coated modified lithium ion battery cathode material in the lithium ion battery, and the lithium ion battery with high rate performance and long cycle life can be obtained.
In order to realize the technical purpose, the invention provides a preparation method of a fast ion conductor coated modified lithium ion battery anode material, which comprises the steps of ball-milling and mixing superfine (nano-scale) aluminum powder and the anode material, and stirring and reacting the mixture with a lithium-containing solution at the temperature of 40-80 ℃ to obtain an aluminum hydroxide colloid coated anode material precursor; the fast ion conductor LiAlO2And calcining the coated anode material precursor at the temperature of 500-900 ℃ to obtain the coated anode material.
In the preferred scheme, the mass of the superfine (nano-scale) aluminum powder is 0.5 to 10.0 percent of the mass of the anode material.
Preferably, the positive electrode material is LiM with a spinel structure2O4M ═ Ni and/or Mn; and/or LiMO having a layered structure2M is at least one of Ni, Co, and Mn; and/or lithium-rich manganese positive electrode material xLi2MnO3·(1-x)LiMO2，0.1<x<0.9, M ═ at least one of Ni, Co, and Mn.
Preferably, the concentration of the lithium-containing solution is between 0.1mol/L and 10 mol/L.
More preferably, the lithium-containing solution contains LiCl or LiNO3、LiOH、Li2CO3、CH3At least one lithium salt of COOLi.
In a preferred scheme, the superfine (nano-scale) aluminum powder is subjected to pre-activation treatment by an acid corrosion method.
More preferably, the acid etching method is a dipping treatment using hydrochloric acid, sulfuric acid or nitric acid having a concentration of 0.1mol/L to 1.0 mol/L.
According to the preferable scheme, ball milling is realized by a planetary ball mill or a roller ball mill, the rotating speed of the ball mill is 400-800 p/min, and the ball milling time is 1-8 h.
In a more preferred embodiment, the calcination time is 5 to 20 hours.
The grain size distribution of the superfine (nano-scale) aluminum powder adopted by the invention is 50 nm-500 nm. The superfine (nano-scale) aluminium powder belongs to the conventional products on the market.
The invention also provides application of the fast ion conductor coated modified lithium ion battery anode material, and the fast ion conductor coated modified lithium ion battery anode material is applied to preparation of a lithium ion battery.
The method for preparing the fast ion conductor coated modified lithium ion battery anode material comprises the following specific steps:
1) adopting a planetary ball mill to carry out the treatment on superfine (nano-scale) aluminum powder with the grain diameter of 50 nm-500 nm and LiM with a spinel structure2O4(M ═ Ni, and/or Mn), and/or LiMO having a layered structure2(M ═ at least one of Ni, Co, and Mn), and/or a lithium-rich manganese positive electrode material xLi2MnO3·(1-x)LiMO2 (0.1<x<0.9, wherein M is at least one of Ni, Co and Mn), and the mixture is ball-milled and mixed by a planetary ball mill or a roller ball mill, the ball-milling rotating speed is controlled to be 400-600 r/min, and the ball-milling time is controlled to be 1-5 h; the mass percentage of the nano-scale aluminum powder and the anode material is (0.5-10.0%): 100%; the ball milling medium can be selectedAt least one of agate balls, steel balls or ceramic balls; the superfine (nano-scale) aluminum powder can be subjected to activation pretreatment by adopting an acid corrosion method;
2) LiCl and LiNO are used as raw materials3、LiOH、Li2CO3、CH3Taking at least one of COOLi as a lithium source, preparing a lithium-containing solution with the concentration ranging from 0.1mol/L to 10mol/L, then adding the mixture obtained in the step 1) into the lithium-containing solution, and continuously stirring for 0.5h to 5.0h under the water bath condition at the temperature of 40 ℃ to 80 ℃ to obtain xLi+·Al(OH)3·yH2O-coated positive electrode material;
3) filtering the product obtained after the reaction in the step 2), washing to obtain a precipitate, and drying the precipitate in a vacuum oven at 80 ℃ for 12 hours to obtain dried xLi+·Al(OH)3·yH2And O coats the anode material precursor.
4) Transferring the precursor obtained in the step 3) into a muffle furnace, preserving the heat for 5-20 hours at 500-900 ℃, and naturally cooling to room temperature to obtain the fast ion conductor LiAlO2And modifying the coated lithium ion cathode material.
The fast ion conductor LiAlO prepared by the invention2The method for preparing the lithium ion battery by coating the modified lithium ion cathode material comprises the following steps: the fast ion conductor LiAlO2Coating modified lithium ion positive electrode material, conductive agent (conductive carbon black), binder (PVDF) and a small amount of NMP, grinding and fully mixing to form uniform paste, coating the paste on an aluminum foil substrate to be used as a test electrode, and taking metal lithium as a counter electrode to prepare a button cell, wherein the electrolyte is 1M LiPF6/ EC:DMC(V:V＝1:1)。
The technical scheme of the invention is that a ball milling method or an acid corrosion method is utilized to carry out surface activation treatment on superfine aluminum powder, activated nano aluminum powder reacts with water under proper conditions to generate aluminum hydroxide, the generated hydroxide surface adsorbs lithium ions with charges and can be uniformly adsorbed on the surface of a positive electrode material to form a layer of xLi+·Al(OH)3·yH2O-cladding layer, xLi+·Al(OH)3·yH2Further dehydrating O at high temperature to produce LiAlO2Nanosheets, produced LiAlO2The nano-sheet grows on the surface of the anode material in situ to obtain compact and uniform LiAlO with good stability2And (4) coating.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the fast ion conductor (LiAlO) prepared by the technical scheme of the invention2) LiAlO coated in lithium ion battery anode material2The coating is compact and uniform, has good stability, can effectively prevent the corrosion of electrolyte to the anode material in the charge-discharge cycle process of the lithium ion battery, greatly prolongs the cycle life of the lithium ion battery, has the function of rapidly transmitting lithium ions, and improves the electrochemical performance of the lithium ion battery.
Preparation of fast ion conductor (LiAlO) by the invention2) The method for coating the lithium ion battery anode material fully utilizes the principle that the nano-scale aluminum powder reacts with water to generate aluminum hydroxide sol, and the chlorine hydroxide sol has better adsorption property and is decomposed at high temperature to generate corresponding oxides. A compact, uniform and high-stability fast ion conductor layer is formed on the surface of the anode material, so that the anode active substance can be effectively prevented from being dissolved and lost due to contact with an electrolyte solution, and the cycle life of the battery is greatly prolonged; meanwhile, the ionic and electronic conductivity of the electrode is greatly improved, and the electrochemical performance of the lithium ion battery is improved.
The fast ion conductor layer coated lithium ion battery anode material is prepared by combining low-temperature synthesis of precursor material and high-temperature sintering, the method is low in raw material cost, simple to operate and environment-friendly, and the defect of the traditional fast ion conductor LiAlO is overcome2In the coating modification method, the defects of high raw material cost, complex operation process, complex process and the like are overcome.
The method for preparing the fast ion conductor LiAlO2The method for coating the lithium ion battery anode material activates the metal surface by a ball milling method or an acid corrosion method, thereby greatly improving the gold contentBelongs to the efficiency of reaction with water, simplifies the process and mildens the conditions.
Fast ion conductor (LiAlO) of the present invention2) The coated lithium ion battery anode material is used for preparing an anode, is applied to a lithium ion battery, shows excellent cycle performance and greatly prolongs the cycle life.
Drawings
FIG. 1 shows LiNi before coating modification in example 10.5Co0.2Mn0.3O2Scanning Electron Micrograph (SEM) of the positive electrode material.
FIG. 2 shows LiAlO in example 12Coating modified LiNi0.5Co0.2Mn0.3O2Scanning Electron Micrograph (SEM) of the positive electrode material.
FIG. 3 shows LiNi which has not been modified by coating0.5Co0.2Mn0.3O2Cathode material and LiAlO prepared in example 12Coating modified LiNi0.5Co0.2Mn0.3O2Positive electrode material 100 cycles performance graph.
Detailed Description
The following examples are intended to illustrate the invention in further detail; and the scope of the claims of the present invention is not limited by the examples.
Example 1
(1) According to LiAlO2Respectively weighing superfine (nano-scale) aluminum powder with the particle size of 300nm and LiNi according to the mass percentage of 1 percent relative to the anode material0.5Co0.2Mn0.3O2And adding the anode material into a steel ball milling tank with the capacity of 250mL and containing agate balls, and then adjusting the rotating speed to 400p/min for grinding for 2 h.
(2) Aluminum powder and LiNi which are ground and activated in the step (1)0.5Co0.2Mn0.3O2The positive electrode material mixture was added to a three-necked flask containing 100mL of a 1mol/L LiCl solution, and the reaction was stirred at 50 ℃ for 1 hour.
(3) Washing the precipitate obtained in the step (2) with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, then filtering, and keeping the filter cake in a blast oven at 80 ℃ for 12 hours to obtain xLi+·Al(OH)3·yH2And O coats the precursor of the anode material.
(4) Putting the precursor obtained in the step (3) into a crucible, and preserving the heat for 5 hours at 450 ℃ to obtain LiAlO2Coated LiNi0.5Co0.2Mn0.3O2And (3) a positive electrode material.
(5) 0.48g of the LiAlO prepared above was weighed2Coating modified LiNi0.5Co0.2Mn0.3O2Adding 0.05g of conductive carbon black as a conductive agent, 0.05g of PVDF as a binder and a small amount of NMP into the positive electrode material, grinding and fully mixing to form uniform paste, coating the paste on an aluminum foil substrate to be used as a test electrode, and taking metal lithium as a counter electrode to prepare a button cell, wherein the electrolyte of the button cell is 1M LiPF6DMC (V: V ═ 1:1), the test charge-discharge rate was 1C.
LiAlO prepared by the present example2Coating modified LiNi0.5Co0.2Mn0.3O2The material characteristics and the electrochemical properties of the cathode material are shown in figures 1-3:
FIG. 1 shows that LiNi is not modified by coating0.5Co0.2Mn0.3O2The anode material is of a sphere-like structure consisting of primary particles with the size of 500-800 nm, and the surface of the anode material is smooth.
The passage through LiAlO can be seen in FIG. 22Coating modified LiNi0.5Co0.2Mn0.3O2Surface of anode material particleHas uniformly distributed flaky coating layers.
The use of LiAlO is illustrated in FIG. 32Coating modified LiNi0.5Co0.2Mn0.3O2When the electrode made of the anode material is subjected to constant current discharge at the rate of 1C at room temperature, the specific capacity can still be kept at 180 mAh/g after the electrode is cycled for 100 times; showing good cycling performance.
Example 2
(1) According to LiAlO2Respectively weighing superfine aluminum powder (nano-scale) with the particle size of 100nm and LiNi according to the mass percent of 0.5 percent relative to the anode material0.85Co0.05Mn0.1O2And adding the anode material into a steel ball milling tank with the capacity of 250mL and containing agate balls, and then adjusting the rotating speed to 500p/min for grinding for 4 hours.
(2) Aluminum powder and LiNi which are ground and activated in the step (1)0.85Co0.05Mn0.1O2The positive electrode material mixture was added to 100mL of LiNO of 0.5mol/L concentration3The reaction was stirred at 60 ℃ for 2h in a three-necked flask of the solution.
(3) Washing the precipitate obtained in the step (2) with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, then filtering, and keeping the filter cake in a blast oven at 80 ℃ for 12 hours to obtain xLi+·Al(OH)3·yH2And O coats the precursor of the anode material.
(4) Putting the precursor obtained in the step (3) into a crucible, and preserving the heat for 8 hours at 500 ℃ to obtain LiAlO2Coated LiNi0.85Co0.05Mn0.1O2And (3) a positive electrode material.
(5) 0.48g of the LiAlO prepared above was weighed2Coating modified LiNi0.85Co0.05Mn0.1O2Adding 0.05g of conductive carbon black as a conductive agent, 0.05g of PVDF as a binder and a small amount of NMP into the positive electrode material, grinding and fully mixing to form uniform pasteCoating the aluminum foil substrate with the electrolyte of 1M LiPF to serve as a test electrode and using metal lithium as a counter electrode to manufacture a button cell6DMC (V: V ═ 1:1), the test charge-discharge rate was 1C.
LiAlO prepared by the present example2Coating modified LiNi0.85Co0.05Mn0.1O2The positive electrode material is provided with an electrode and assembled with a metal lithium sheet into a button cell, and when the button cell is subjected to constant current discharge at room temperature of 1C, the specific capacity can still be maintained at 188mAh/g after 100 times of circulation, so that the button cell shows good circulation performance.
Example 3
(1) According to LiAlO2Respectively weighing superfine aluminum powder (nano-scale) with the particle size of 100nm and LiNi according to the mass percentage of 2 percent relative to the anode material0.333Co0.333Mn0.333O2And adding the anode material into a steel ball milling tank with the capacity of 250mL and containing agate balls, and then adjusting the rotating speed to 600p/min for grinding for 5 h.
(2) Aluminum powder and LiNi which are ground and activated in the step (1)0.333Co0.333Mn0.333O2The cathode material mixture was added to a three-necked flask containing 100mL of a 2mol/LLIOH solution, and the reaction was stirred at 80 ℃ for 5 hours.
(3) Washing the precipitate obtained in the step (2) with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, then filtering, and keeping the filter cake in a blast oven at 80 ℃ for 12 hours to obtain xLi+·Al(OH)3·yH2And O coats the precursor of the anode material.
(4) Putting the precursor obtained in the step (3) into a crucible, and preserving the heat for 10 hours at the temperature of 600 ℃ to obtain LiAlO2Coated LiNi0.333Co0.333Mn0.333O2And (3) a positive electrode material.
(5) 0.48g of the LiAlO prepared above was weighed2Coating modified LiNi0.333Co0.333Mn0.333O2Adding 0.05g of conductive carbon black as a conductive agent, 0.05g of PVDF as a binder and a small amount of NMP into the positive electrode material, grinding and fully mixing to form uniform paste, coating the paste on an aluminum foil substrate to be used as a test electrode, and taking metal lithium as a counter electrode to prepare a button cell, wherein the electrolyte of the button cell is 1M LiPF6DMC (V: V ═ 1:1), the test charge-discharge rate was 1C.
LiAlO prepared by the present example2Coating modified LiNi0.333Co0.333Mn0.333O2The positive electrode material is provided with an electrode and assembled with a metal lithium sheet into a button cell, and when the button cell is subjected to constant current discharge at room temperature of 1C, the specific capacity can still be kept at 175mAh/g after 100 cycles, so that the button cell shows good cycle performance.
Example 4
(1) According to LiAlO2Respectively weighing superfine aluminum powder (nanometer level) with particle size of 500nm and 0.3Li in a mass percent of 4% relative to the anode material2MnO3·0.7LiNi0.5Co0.2Mn0.3O2And adding the anode material into a steel ball milling tank with the capacity of 250mL and containing agate balls, and then adjusting the rotating speed to 800p/min for grinding for 8 hours.
(2) Aluminum powder and 0.3Li after being ground and activated in the step (1)2MnO3·0.7LiNi0.5Co0.2Mn0.3O2Adding the mixture of the anode materials into a container with 100mL of 3mol/LCH3COOLi solution in a three-neck flask, and stirring at 60 ℃ for reaction for 4 h.
(3) Washing the precipitate obtained in the step (2) with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, then filtering, and keeping the filter cake in a blast oven at 80 ℃ for 12 hours to obtain xLi+·Al(OH)3·yH2And O coats the precursor of the anode material.
(4) Putting the precursor obtained in the step (3) into a crucible, and preserving the heat for 18 hours at 800 ℃ to obtainLiAlO2Coated 0.3Li2MnO3·0.7LiNi0.5Co0.2Mn0.3O2And (3) a positive electrode material.
(5) 0.48g of the LiAlO prepared above was weighed2Coated modified 0.3Li2MnO3·0.7LiNi0.5Co0.2Mn0.3O2Adding 0.05g of conductive carbon black as a conductive agent, 0.05g of PVDF as a binder and a small amount of NMP into the positive electrode material, grinding and fully mixing to form uniform paste, coating the paste on an aluminum foil substrate to be used as a test electrode, and taking metal lithium as a counter electrode to prepare a button cell, wherein the electrolyte of the button cell is 1M LiPF6DMC (V: V ═ 1:1), the test charge-discharge rate was 1C.
LiAlO prepared by the present example2Coated modified 0.3Li2MnO3·0.7 LiNi0.5Co0.2Mn0.3O2The positive electrode material is provided with an electrode and assembled with a metal lithium sheet into a button cell, and when the button cell is subjected to constant current discharge at room temperature of 1C, the specific capacity can still be kept at 255mAh/g after 100 times of circulation, so that good circulation performance is shown.
Example 5
(1) According to LiAlO2Respectively weighing superfine aluminum powder (nano-scale) with the particle size of 300nm and 0.5Li in a mass percent of 10 percent relative to the anode material2MnO3·0.5LiNi0.333Co0.333Mn0.333O2And adding the anode material into a steel ball milling tank with the capacity of 250mL and containing agate balls, and then adjusting the rotating speed to 600p/min for grinding for 5 h.
(2) Aluminum powder and 0.5Li after being ground and activated in the step (1)2MnO3·0.5LiNi0.333Co0.333Mn0.333O2The mixture of the positive electrode material was added to 100mL of LiNO with a concentration of 1mol/L3The reaction was stirred at 70 ℃ for 4h in a three-necked flask of the solution.
(3) With deionized waterWashing the precipitate obtained in the step (2) for 3 times, then washing the precipitate for 3 times by using absolute ethyl alcohol, then filtering the precipitate, and keeping the temperature of a filter cake in a blast oven at 80 ℃ for 12 hours to obtain xLi+·Al(OH)3·yH2And O coats the precursor of the anode material.
(4) Putting the precursor obtained in the step (3) into a crucible, and preserving the heat for 12 hours at 400 ℃ to obtain LiAlO2Coated 0.5Li2MnO3·0.5LiNi0.333Co0.333Mn0.333O2And (3) a positive electrode material.
(5) 0.48g of the LiAlO prepared above was weighed2Coated modified 0.5Li2MnO3·0.5LiNi0.333Co0.333Mn0.333O2Adding 0.05g of conductive carbon black as a conductive agent, 0.05g of PVDF as a binder and a small amount of NMP into the positive electrode material, grinding and fully mixing to form uniform paste, coating the paste on an aluminum foil substrate to be used as a test electrode, and taking metal lithium as a counter electrode to prepare a button cell, wherein the electrolyte of the button cell is 1M LiPF6DMC (V: V ═ 1:1), the test charge-discharge rate was 1C.
LiAlO prepared by the present example2Coated modified 0.5Li2MnO3·0.5LiNi0.333Co0.333Mn0.333O2The positive electrode material is provided with an electrode and assembled with a metal lithium sheet into a button cell, and when the button cell is subjected to constant current discharge at room temperature of 1C, the specific capacity can still be maintained at 268mAh/g after 100 times of circulation, so that good circulation performance is shown.
Example 6
(1) Adding superfine aluminum powder (nano-scale) with the particle size of 300nm into a three-neck flask with the capacity of 250mL and containing hydrochloric acid with the concentration of 0.1mol/L for soaking and activating treatment.
(2) Respectively weighing the activated aluminum powder and the activated LiNi in the step (1) according to the mass percentage of 2.0 percent relative to the anode material0.5Mn1.5O4Adding positive electrode material into the containerIn a three-necked flask with 100mL of a 2.5mol/LLICl solution, the reaction was stirred at 80 ℃ for 4 hours.
(3) Washing the precipitate obtained in the step (2) with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, then filtering, and keeping the filter cake in a blast oven at 80 ℃ for 12 hours to obtain xLi+·Al(OH)3·yH2And O coats the precursor of the anode material.
(4) Putting the precursor obtained in the step (3) into a crucible, and preserving the heat for 8 hours at the temperature of 600 ℃ to obtain LiAlO2Coated LiNi0.5Mn1.5O4And (3) a positive electrode material.
(5) 0.48g of the LiAlO prepared above was weighed2Coating modified LiNi0.5Mn1.5O4Adding 0.05g of conductive carbon black as a conductive agent, 0.05g of PVDF as a binder and a small amount of NMP into the positive electrode material, grinding and fully mixing to form uniform paste, coating the paste on an aluminum foil substrate to be used as a test electrode, and taking metal lithium as a counter electrode to prepare a button cell, wherein the electrolyte of the button cell is 1M LiPF6DMC (V: V ═ 1:1), the test charge-discharge rate was 1C.
LiAlO prepared by the present example2Coating modified LiNi0.5Mn1.5O4The positive electrode material is provided with an electrode and assembled with a metal lithium sheet into a button cell, and when the button cell is subjected to constant current discharge at room temperature of 1C, the specific capacity can still be kept at 139mAh/g after 100 times of circulation, the voltage is kept at 4.5V, and good circulation performance is shown.
Example 7
(1) Adding superfine aluminum powder (nano-scale) with the particle size of 300nm into a three-neck flask with the capacity of 250mL and containing hydrochloric acid with the concentration of 0.8mol/L for soaking and activating treatment.
(2) Respectively weighing the activated aluminum powder and the activated LiNi in the step (1) according to the mass percentage of 2.0 percent relative to the anode material0.5Mn1.5O4The positive electrode material is added intoA reaction was stirred at 80 ℃ for 4 hours in a three-necked flask containing 100mL of a 2.5mol/L LiCl solution.
(3) Washing the precipitate obtained in the step (2) with deionized water for 3 times, then washing with absolute ethyl alcohol for 3 times, then filtering, and keeping the filter cake in a blast oven at 80 ℃ for 12 hours to obtain xLi+·Al(OH)3·yH2And O coats the precursor of the anode material.
(4) Putting the precursor obtained in the step (3) into a crucible, and preserving the heat for 8 hours at the temperature of 600 ℃ to obtain LiAlO2Coated LiNi0.5Mn1.5O4And (3) a positive electrode material.
(5) 0.48g of the LiAlO prepared above was weighed2Coating modified LiNi0.5Mn1.5O4Adding 0.05g of conductive carbon black as a conductive agent, 0.05g of PVDF as a binder and a small amount of NMP into the positive electrode material, grinding and fully mixing to form uniform paste, coating the paste on an aluminum foil substrate to be used as a test electrode, and taking metal lithium as a counter electrode to prepare a button cell, wherein the electrolyte of the button cell is 1M LiPF6DMC (V: V ═ 1:1), the test charge-discharge rate was 1C.
LiAlO prepared by the present example2Coating modified LiNi0.5Mn1.5O4The positive electrode material is provided with an electrode and assembled with a metal lithium sheet into a button cell, and when the button cell is subjected to constant current discharge at room temperature of 1C, the specific capacity can still be kept at 139mAh/g after 100 times of circulation, the voltage is kept at 4.5V, and good circulation performance is shown.

Claims (6)

1. A preparation method of a fast ion conductor coated modified lithium ion battery anode material is characterized by comprising the following steps: after ball milling and mixing the nano-scale aluminum powder and the anode material, stirring and reacting the mixture with a lithium-containing solution at the temperature of 40-80 ℃ to obtain an aluminum hydroxide colloid-coated anode material precursor; calcining the precursor of the aluminum hydroxide colloid-coated positive electrode material at the temperature of 500-900 ℃ to obtain the aluminum hydroxide colloid-coated positive electrode material;
the nano-scale aluminum powder is subjected to pre-activation treatment by an acid corrosion method;
the acid corrosion method is to perform soaking treatment by hydrochloric acid, sulfuric acid or nitric acid with the concentration of 0.1-1.0 mol/L;
the ball milling is realized by a planetary ball mill or a roller ball mill, the rotating speed of the ball mill is 400-800 p/min, and the ball milling time is 1-8 h.
2. The preparation method of the fast ion conductor coated modified lithium ion battery positive electrode material according to claim 1, characterized in that: the mass of the nano-scale aluminum powder is 0.5-10.0% of that of the anode material.
3. The preparation method of the fast ion conductor coated modified lithium ion battery positive electrode material according to claim 1 or 2, characterized in that: the anode material is as follows: LiM having spinel structure2O4LiMO having a layered structure2Lithium-rich manganese cathode material xLi2MnO3·(1-x)LiMO2At least one of:
wherein,
LiM having spinel structure2O4Wherein M is at least one of Ni and Mn;
LiMO having a layered structure2Wherein M is at least one of Ni, Co, and Mn;
lithium-manganese-rich cathode material xLi2MnO3·(1-x)LiMO2Middle, 0.1<x<0.9, M ═ at least one of Ni, Co, and Mn.
4. The preparation method of the fast ion conductor coated modified lithium ion battery positive electrode material according to claim 1, characterized in that: the concentration of the lithium-containing solution is between 0.1mol/L and 10 mol/L.
5. The preparation method of the fast ion conductor coated modified lithium ion battery positive electrode material according to claim 4, characterized in that: the lithium-containing solution comprises LiCl and LiNO3、LiOH、Li2CO3、CH3At least one lithium salt of COOLi.
6. The preparation method of the fast ion conductor coated modified lithium ion battery positive electrode material according to any one of claims 1, 2, 4 and 5, characterized in that: the calcination time is 5-20 h.
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