CN104022276A - Clad modified layered cathode material of lithium-ion battery and preparation method of layered cathode material - Google Patents

Clad modified layered cathode material of lithium-ion battery and preparation method of layered cathode material Download PDF

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CN104022276A
CN104022276A CN201410252599.8A CN201410252599A CN104022276A CN 104022276 A CN104022276 A CN 104022276A CN 201410252599 A CN201410252599 A CN 201410252599A CN 104022276 A CN104022276 A CN 104022276A
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cathode material
lithium
layered cathode
ion battery
solution
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周飞
任崇
孔继周
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Nanjing University of Aeronautics and Astronautics
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Nanjing University of Aeronautics and Astronautics
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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
    • 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
    • H01M4/50—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
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The invention discloses a clad modified layered cathode material of a lithium-ion battery and a preparation method of the layered cathode material. The material is obtained by evenly covering the layered cathode material of the lithium-ion battery by a Li2TiO3 thin film. The preparation method comprises the following steps: (1) dissolving a titanium source in an ethanol solution, and dropwise adding glycol to form a solution A; dissolving a lithium salt and a complexing agent in deionized water to form a solution B; (2) mixing the two solutions and regulating the pH value of the mixed solution to the range of 5-7 by use of a weakly alkaline liquor or a weakly acidic liquor; (3) adding the layered cathode material of the lithium-ion battery to a suspension, and heating and stirring to obtain a sol; drying the sol to obtain a precursor; grinding and annealing the precursor to obtain the target product. The method is used for modifying the layered cathode material of the lithium-ion battery by covering the layered cathode material with the Li2TiO3 thin film; the surface thin film covering the cathode material by use of the method is clad evenly, and the method is mature and reliable.

Description

Coated modification lithium-ion battery layered cathode material and preparation method thereof
Technical field
The present invention relates to layered cathode material of lithium ion battery preparation field, particularly relate to surface coating modification of layered cathode material of lithium ion battery and preparation method thereof.
Background technology
Because lithium battery has that energy density is high, lightweight, memory-less effect, good rate capability, a series of outstanding advantages such as have extended cycle life, therefore, it is acknowledged as the desirable energy of electric automobile of future generation, mixed power electric car.And the energy density of lithium ion battery depends primarily on the energy density of positive electrode, so the positive electrode that research and development have high-energy-density becomes the focus that people pay close attention to.
Due to layered cathode material and electrolyte react (as redox reaction), can cause the problem such as metallic element dissolving (as Mn), the increase of solid electrolyte interface film in layered cathode material, thereby cause the capacity attenuation of battery, and cause fail safe to decline.Therefore need to adopt surface coating modification technology to improve the chemical property of layered cathode material of lithium ion battery.At present, the coated mode in surface can be divided into coated two kinds of dry method and wet method substantially.Compare, wet method is evenly coated, and the chemical property of the positive electrode obtaining is more excellent.Regrettably, the synthetic insulated by oxide coating layer of wet method can increase Li +diffusion length, be unfavorable for Li in positive electrode +conduction and interface charge shift, thereby affect the chemical property of positive electrode.
Monoclinic phase Li 2tiO 3with Li 2mnO 3there is identical structure, and Li 2tiO 3material keeps electrochemistry inertia in wider voltage range, and in organic electrolyte, its structural stability is better; In addition, this material also shows higher lithium ion migration rate 2.5 × 10 -7scm -1.The more important thing is, as stratified material, Li 2tiO 3material has three-dimensional Li +migrating channels.And adopt wet method to synthesize Li 2tiO 3the research of coated modification lithium-ion battery layered cathode material have not been reported.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of modification lithium-ion battery layered cathode material and preparation method thereof, and the method is at the coated Li in the surface of layered cathode material of lithium ion battery 2tiO 3film carries out modification, adopts coated even, the method mature and reliable of the coated positive electrode surface film of the method.
One of the present invention is coated modification lithium-ion battery layered cathode material, is evenly coated Li outside layered cathode material of lithium ion battery 2tiO 3film.
The preparation method of above-mentioned coated modification lithium-ion battery layered cathode material, comprises the following steps:
1) first a certain amount of titanium source is dissolved in ethanolic solution, the volume ratio of titanium source and ethanol is 1～5:10, and splashes into ethylene glycol formation solution A in solution; Lithium salts and complexing agent are dissolved in and in deionized water, form solution B; In above-mentioned two kinds of solution, the mol ratio of Li and Ti is 2:1, and complexing agent is 1:0.5～2 with mol ratio (Li+Ti), and the mol ratio of complexing agent and ethylene glycol is 1:1～2;
2) above-mentioned two kinds of solution that configure are slowly mixed under the condition constantly stirring, then with the pH value that weak lye or weak acid liquid are carried out regulator solution be 5～7, stir formation suspension-turbid liquid;
3) layered cathode material of lithium ion battery is joined in above-mentioned suspension-turbid liquid, under 50～80 DEG C of conditions, add thermal agitation, along with the evaporation of solvent obtains colloidal sol;
4) dry colloidal sol is placed in to air dry oven/vacuum drying chamber in 90～120 DEG C of dry 12～24h, obtains the presoma after being coated; Presoma is ground and is placed in tube furnace, and annealing in process 2～5h at 500～700 DEG C of temperature, obtains the coated 1wt%～8wt%Li in surface 2tiO 3target product.
Above-mentioned steps 1) described in titanium source be butyl titanate (C 16h 36o 4ti), the one in isopropyl titanate, titanium tetrachloride, tetraisopropyl titanate or tetraethyl titanate.
Above-mentioned steps 1) described in Li salt be one or more the mixture in lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate.
Above-mentioned steps 1) described in complexing agent be one or more the mixture in citric acid, polyvinylpyrrolidone PVP, polyethylene glycol PEG.
Above-mentioned steps 2) described in weak lye be the aqueous solution of one or more mixtures in ammoniacal liquor, sal volatile, ammonium bicarbonate soln, weak acid liquid is acetic acid.
Above-mentioned steps 3) described in layered cathode material comprise: monobasic layered cathode material LiCoO 2; Binary layered cathode material Li[Ni 0.5mn 0.5] O 2; Ternary layered positive electrode is as Li[Ni 0.5co 0.2mn 0.3] O 2, Li[Ni 1/3co 1/3mn 1/3] O 2, Li 1.2[Mn 0.51ni 0.19co 0.1] O 2, Li 1.2[Mn 0.54ni 0.13co 0.13] O 2.
Surface of the present invention is coated Li 2tiO 3the wet chemical methods of layered cathode material of lithium ion battery there is following distinguishing feature:
1) the present invention adopts wet-chemical to synthesize Li 2tiO 3coating layer, has accelerated the diffusion rate of annealing process intermediate ion, has shortened annealing time;
2) the coating layer Li of synthesized of the present invention 2tiO 3material keeps electrochemistry inertia in wider voltage range, and its structural stability is better in organic electrolyte; Meanwhile, this material also has higher lithium ion migration rate 2.5 × 10 -7scm -1with three-dimensional Li +migrating channels.
3) the present invention is simple to operate, and technique is easy to control, and manufacturing cycle is short, and cost is low, is easy to the features such as large-scale industrial production.
Brief description of the drawings
Fig. 1 is the 2wt%Li of the embodiment of the present invention 1 2tiO 3coated Li 1.2[Mn 0.51ni 0.19co 0.1] O 2the XRD figure of/Li button cell,
Fig. 2 is the 2wt%Li of the embodiment of the present invention 1 2tiO 3coated Li 1.2[Mn 0.51ni 0.19co 0.1] O 2the cyclic curve of/Li button cell,
Fig. 3 is the SEM figure of the embodiment of the present invention 1.Wherein, A is not for coated, and B is for after coated.
Embodiment
Below in conjunction with embodiment, the present invention is specifically described.
Embodiment 1
With lithium nitrate (LiNO 3), butyl titanate (C 16h 36o 4ti), citric acid (C 6h 8o 7) be raw material.First appropriate butyl titanate is dissolved in ethanolic solution, the volume ratio of titanium source and ethanol is 1～5, and splash into appropriate ethylene glycol (promoting the more stable formation of gel) in solution, lithium nitrate and complexing agent citric acid are dissolved in deionized water simultaneously.Then two solution that configure are slowly mixed under the condition constantly stirring, making complexing agent and mol ratio (Li+Ti) is 1:2, and the mol ratio of complexing agent and ethylene glycol is 1:1.Using NH 3h 2the pH value of O regulator solution is 5, stirs and forms suspension-turbid liquid.
By Li 1.2[Mn 0.51ni 0.19co 0.1] O 2positive electrode joins in above-mentioned solution, under 60 DEG C of conditions, adds thermal agitation, along with the evaporation of solvent obtains colloidal sol.Be placed in vacuum drying chamber in 110 DEG C of dry 20h, obtain the presoma after being coated.Presoma is ground and is placed in tube furnace, and 600～700 DEG C of sintering 3h at different temperature, obtain the coated Li in surface 2tiO 3target product, Li 2tiO 3covering amount is 2wt%.
Fig. 1 is the 2wt%Li of embodiment 1 2tiO 3coated Li 1.2[Mn 0.51ni 0.19co 0.1] O 2the XRD figure of/Li button cell.From scheming, compared with not coated sample, the layered cathode material Li obtaining after 600～700 DEG C of sintering 3h 1.2[Mn 0.51ni 0.19co 0.1] O 2crystal structure do not change.And there is not monoclinic phase Li 2tiO 3, may be due to coated Li 2tiO 3amount fewer.
Fig. 2 is the 2wt%Li of embodiment 1 2tiO 3coated Li 1.2[Mn 0.51ni 0.19co 0.1] O 2the cyclic curve of/Li button cell.From scheming, the cycle performance optimum of the sample obtaining after 650 DEG C of sintering 3h.
Fig. 3 is the SEM figure of the embodiment of the present invention 1.Wherein, A is not for coated, and B is for after coated.
Embodiment 2
With lithium hydroxide (LiOH), isopropyl titanate (Ti[OCH (CH 3) 2] 4), PVP (M.W.30000) is raw material.First appropriate isopropyl titanate is dissolved in ethanolic solution, the volume ratio of titanium source and ethanol is 1～10, and splashes into appropriate ethylene glycol in solution, lithium hydroxide and complexing agent PVP is dissolved in deionized water simultaneously.Then two solution that configure are slowly mixed under the condition constantly stirring, complexing agent is 1:0.5 with mol ratio (Li+Ti), and the mol ratio of complexing agent and ethylene glycol is 1:2.Be 6 by the pH value of acetum regulator solution again, stir and form suspension-turbid liquid.
By Li[Ni 0.5co 0.2mn 0.3] O 2positive electrode joins in above-mentioned solution, under 50 DEG C of conditions, adds thermal agitation, along with the evaporation of solvent obtains colloidal sol.Be placed in air dry oven in 90 DEG C of dry 24h, obtain the presoma after being coated.Presoma is ground and is placed in tube furnace, and 500～600 DEG C of sintering 5h at different temperature, obtain the coated Li in surface 2tiO 3target product, Li 2tiO 3covering amount is 1wt%.
Embodiment 3
With lithium carbonate (Li 2cO 3), titanium tetrachloride (TiCl 4), PEG2000 is raw material.First appropriate titanium tetrachloride is dissolved in ethanolic solution, the volume ratio of titanium source and ethanol is 1～6, and splashes into appropriate ethylene glycol in solution, lithium carbonate and complexing agent PEG2000 is dissolved in deionized water simultaneously.Then two solution that configure are slowly mixed under the condition constantly stirring, making complexing agent and mol ratio (Li+Ti) is 1:1, and the mol ratio of complexing agent and ethylene glycol is 1:1.5.Be 7 in the pH value with acetum regulator solution, stir and form suspension-turbid liquid.
By LiCoO 2positive electrode joins in above-mentioned solution, under 80 DEG C of conditions, adds thermal agitation, along with the evaporation of solvent obtains colloidal sol.Be placed in vacuum drying chamber in 120 DEG C of dry 12h, obtain the presoma after being coated.Presoma is ground and is placed in tube furnace, and 600～700 DEG C of sintering 2h at different temperature, obtain the coated Li in surface 2tiO 3target product, Li 2tiO 3covering amount is 6wt%.
Embodiment 4
With lithium nitrate (LiNO 3), tetraethyl titanate (Ti (OCH 2cH 3) 4), citric acid (C 6h 8o 7) be raw material.First appropriate tetraethyl titanate is dissolved in ethanolic solution, the volume ratio of titanium source and ethanol is 1～6, and splashes into appropriate ethylene glycol in solution, lithium nitrate and complexing agent citric acid is dissolved in deionized water simultaneously.Then two solution that configure are slowly mixed under the condition constantly stirring, making complexing agent and mol ratio (Li+Ti) is 1:1, and the mol ratio of complexing agent and ethylene glycol is 1:2.Be 6 in the pH value with ammonium bicarbonate soln regulator solution, stir and form suspension-turbid liquid.
By Li (Ni 0.5mn 0.5) O 2positive electrode joins in above-mentioned solution, under 70 DEG C of conditions, adds thermal agitation, along with the evaporation of solvent obtains colloidal sol.Be placed in vacuum drying chamber in 110 DEG C of dry 12h, obtain the presoma after being coated.Presoma is ground and is placed in tube furnace, and 600～700 DEG C of sintering 3h at different temperature, obtain the coated Li in surface 2tiO 3target product, Li 2tiO 3covering amount is 3wt%.
Embodiment 5
With lithium acetate (Li (CH 3cOO) 2), tetraisopropyl titanate (C 12h 28o 4ti), citric acid (C 6h 8o 7) be raw material.First appropriate tetraisopropyl titanate is dissolved in ethanolic solution, the volume ratio of titanium source and ethanol is 1～10, and splashes into appropriate ethylene glycol in solution, lithium acetate and complexing agent citric acid is dissolved in deionized water simultaneously.Then two solution that configure are slowly mixed under the condition constantly stirring, making complexing agent and mol ratio (Li+Ti) is 1:1, and the mol ratio of complexing agent and ethylene glycol is 1:1.Be 5 in the pH value with ammonium bicarbonate soln regulator solution, stir and form suspension-turbid liquid.
By Li[Ni 1/3co 1/3mn 1/3] O 2positive electrode joins in above-mentioned solution, under 80 DEG C of conditions, adds thermal agitation, along with the evaporation of solvent obtains colloidal sol.Be placed in vacuum drying chamber in 120 DEG C of dry 12h, obtain the presoma after being coated.Presoma is ground and is placed in tube furnace, and 500～600 DEG C of sintering 4h at different temperature, obtain the coated Li in surface 2tiO 3target product, Li 2tiO 3covering amount is 8wt%.
Embodiment 6
With lithium nitrate (LiNO 3), lithium acetate (Li (CH 3cOO) 2), butyl titanate (C 16h 36o 4ti), titanium tetrachloride (TiCl 4), citric acid (C 6h 8o 7), PEG2000 is raw material.First by appropriate butyl titanate, titanium tetrachloride (TiCl 4) (mol ratio 1:1) be dissolved in ethanolic solution, the volume ratio of titanium source and ethanol is 1～5, and splash into appropriate ethylene glycol (promoting the more stable formation of gel) in solution, lithium nitrate, lithium acetate (mol ratio 1:1) and complexing agent citric acid, PEG2000 (mol ratio 1:1) are dissolved in deionized water simultaneously.Then two solution that configure are slowly mixed under the condition constantly stirring, making complexing agent and mol ratio (Li+Ti) is 1:2, and the mol ratio of complexing agent and ethylene glycol is 1:1.Using NH 3h 2the pH value of O regulator solution is 5, stirs and forms suspension-turbid liquid.
By Li 1.2[Mn 0.54ni 0.13co 0.13] O 2positive electrode joins in above-mentioned solution, under 60 DEG C of conditions, adds thermal agitation, along with the evaporation of solvent obtains colloidal sol.Be placed in vacuum drying chamber in 110 DEG C of dry 12h, obtain the presoma after being coated.Presoma is ground and is placed in tube furnace, and 600～650 DEG C of sintering 3h at different temperature, obtain the coated Li in surface 2tiO 3target product, Li 2tiO 3covering amount is 3wt%.
Embodiment 7
With lithium carbonate (Li 2cO 3), lithium hydroxide (LiOH), titanium tetrachloride (TiCl 4), tetraisopropyl titanate (C 12h 28o 4ti), PEG2000, PVP (M.W.30000) are raw material.First appropriate titanium tetrachloride, tetraisopropyl titanate (mol ratio 1:1) are dissolved in ethanolic solution, the volume ratio of titanium source and ethanol is 1～6, and splash into appropriate ethylene glycol in solution, lithium carbonate, lithium hydroxide (mol ratio 2:1) and complexing agent PEG2000, PVP (mol ratio 1:2) are dissolved in deionized water simultaneously.Then two solution that configure are slowly mixed under the condition constantly stirring, making complexing agent and mol ratio (Li+Ti) is 1:1, and the mol ratio of complexing agent and ethylene glycol is 1:1.5.Be 7 in the pH value with acetum regulator solution, stir and form suspension-turbid liquid.
By LiCoO 2positive electrode joins in above-mentioned solution, under 80 DEG C of conditions, adds thermal agitation, along with the evaporation of solvent obtains colloidal sol.Be placed in vacuum drying chamber in 120 DEG C of dry 12h, obtain the presoma after being coated.Presoma is ground and is placed in tube furnace, and 600～700 DEG C of sintering 2h at different temperature, obtain the coated Li in surface 2tiO 3target product, Li 2tiO 3covering amount is 6wt%.
The concrete application approach of the present invention is a lot, and the above is only the preferred embodiment of the present invention, should be understood that; for those skilled in the art; under the premise without departing from the principles of the invention, can also make some improvement, these improve and also should be considered as protection scope of the present invention.

Claims (7)

1. a coated modification lithium-ion battery layered cathode material, is characterized in that, evenly coated Li outside layered cathode material of lithium ion battery 2tiO 3film.
2. the preparation method of coated modification lithium-ion battery layered cathode material described in claim 1, is characterized in that comprising the following steps:
1) first a certain amount of titanium source is dissolved in ethanolic solution, the volume ratio of titanium source and ethanol is 1～5:10, and splashes into ethylene glycol formation solution A in solution; Lithium salts and complexing agent are dissolved in and in deionized water, form solution B; In above-mentioned two kinds of solution, the mol ratio of Li and Ti is 2:1, and complexing agent is 1:0.5～2 with mol ratio (Li+Ti), and the mol ratio of complexing agent and ethylene glycol is 1:1～2;
2) above-mentioned two kinds of solution that configure are slowly mixed under the condition constantly stirring, then with the pH value that weak lye or weak acid liquid are carried out regulator solution be 5～7, stir formation suspension-turbid liquid;
3) layered cathode material of lithium ion battery is joined in above-mentioned suspension-turbid liquid, under 50～80 DEG C of conditions, add thermal agitation, along with the evaporation of solvent obtains colloidal sol;
4) dry colloidal sol is placed in to air dry oven/vacuum drying chamber in 90～120 DEG C of dry 12～24h, obtains the presoma after being coated; Presoma is ground and is placed in tube furnace, and annealing in process 2～5h at 500～700 DEG C of temperature, obtains the coated 1wt%～8wt%Li in surface 2tiO 3target product.
3. the preparation method of modification lithium-ion battery layered cathode material according to claim 2, is characterized in that, above-mentioned steps 1) described in titanium source be butyl titanate (C 16h 36o 4ti), the one in isopropyl titanate, titanium tetrachloride, tetraisopropyl titanate or tetraethyl titanate.
4. according to the preparation method of the modification lithium-ion battery layered cathode material described in claim 2 or 3, it is characterized in that above-mentioned steps 1) described in Li salt be one or more the mixture in lithium hydroxide, lithium carbonate, lithium nitrate, lithium acetate.
5. according to the preparation method of the modification lithium-ion battery layered cathode material described in claim 2 or 3, it is characterized in that above-mentioned steps 1) described in complexing agent be one or more the mixture in citric acid, polyvinylpyrrolidone PVP, polyethylene glycol PEG.
6. according to the preparation method of the modification lithium-ion battery layered cathode material described in claim 2 or 3, it is characterized in that above-mentioned steps 2) described in weak lye be the aqueous solution of one or more mixtures in ammoniacal liquor, sal volatile, ammonium bicarbonate soln; Described weak acid liquid is acetic acid.
7. according to the preparation method of the modification lithium-ion battery layered cathode material described in claim 2 or 3, it is characterized in that above-mentioned steps 3) described in layered cathode material comprise: monobasic layered cathode material, as LiCoO 2; Binary layered cathode material, as Li[Ni 0.5mn 0.5] O 2; Ternary layered positive electrode, as Li[Ni 0.5co 0.2mn 0.3] O 2, Li[Ni 1/3co 1/3mn 1/3] O 2, Li 1.2[Mn 0.51ni 0.19co 0.1] O 2, Li 1.2[Mn 0.54ni 0.13co 0.13] O 2.
CN201410252599.8A 2014-06-09 2014-06-09 Clad modified layered cathode material of lithium-ion battery and preparation method of layered cathode material Pending CN104022276A (en)

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CN115678033A (en) * 2022-12-29 2023-02-03 河南科隆电源材料有限公司 Cobalt-free cathode material with inner gap outer cladding structure and preparation method thereof
EP4213244A4 (en) * 2021-11-29 2024-06-19 Hengdian Group DMEGC Magnetics Co., Ltd. Sodium ion positive electrode material and preparation method therefor, and sodium ion battery

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CN115678033A (en) * 2022-12-29 2023-02-03 河南科隆电源材料有限公司 Cobalt-free cathode material with inner gap outer cladding structure and preparation method thereof

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