CN104466160A - Preparation method of lithium enriched ternary system nanometer material - Google Patents
Preparation method of lithium enriched ternary system nanometer material Download PDFInfo
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- CN104466160A CN104466160A CN201410670027.1A CN201410670027A CN104466160A CN 104466160 A CN104466160 A CN 104466160A CN 201410670027 A CN201410670027 A CN 201410670027A CN 104466160 A CN104466160 A CN 104466160A
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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
- H01M4/48—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- H01M4/48—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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- 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
Abstract
The invention relates to a preparation method of a lithium enriched ternary system nanometer material, and the prepared lithium enriched ternary system Li(Li0.2Mn0.54Ni0.13Co0.13)O2 nanometer material can be used as an anode material for a lithium ion cell. The electrode material is synthesized by a sol-gel method and the preparation method comprises the following steps: weighing complexing agent-ethylenediamine tetraacetic acid (EDTA) according to chemometry and dissolving in ammonia water, and stirring uniformly to form a transparent solution A; weighing corresponding salts according to the ionic molar ratio of Li<+>:Mn<2+>:Co<2+>:Ni<2+> of 1.26:0.54:0.13:0.13 and dissolving in deionized water to form a pink solution B; mixing the solution A and the solution B in 80 DEG C water bath under a stirring condition, carrying out complexing reaction sufficiently, stirring for 2h and adding with a complexing agent-citric acid; evaporating the solvent at 80 DEG C to form wet gel, drying at 100 DEG C for 24h, grinding, presintering, and performing high-temperature heat treatment in a muffle furnace to obtain the lithium enriched ternary system material.
Description
Technical field
The present invention relates to a kind of preparation method of rich lithium ternary system nano material, prepare the rich lithium ternary system Li [Li of gained
0.2mn
0.54ni
0.13co
0.13] O
2nano material can be used as anode material for lithium-ion batteries.
Background technology
Lithium ion battery is the crucial energy storage device of portable consumer electronics product and the New Energy Industry comprising electric automobile, and the principal element limiting its development is positive electrode.At present, business-like anode material for lithium-ion batteries generally adopts LiFePO4, and its theoretical specific capacity only has 170mAh/g, and energy density is lower, limit the further raising of lithium ion battery specific capacity, be difficult to meet future electronic product and electrokinetic cell to the requirement of high capacity lithium ion battery.In order to overcome the shortcoming of this type of material, people find the novel anode material of high power capacity.Ternary system material has higher operating voltage because of it in recent years, has objective specific capacity and be subject to researcher's extensive concern under low range, has broad prospects in following electrokinetic cell application.Relevant Li at present
2mnO
3with LiNi
1/3co
1/3mn
1/3o
2the solid-solution material xLi that Material cladding is formed
2mnO
3(1-x) LiNi
1/3co
1/3mn
1/3o
2there is the focus that higher specific capacity (>250mAh/g) becomes research, compared with the stratified material of routine, containing a certain amount of lithium in transition metal layer, this part of lithium and other transition metal ionss form ordered arrangement, are commonly called rich lithium material.When the value of x gets 0.5, rich lithium material Li [Li
0.2mn
0.54ni
0.13co
0.13] O
2under room temperature 2.0 ~ 4.8V, 20mA/g current density, specific discharge capacity is studied widely up to 280mAh/g.
The rich lithium ternary system Li of current synthesis [Li
0.2mn
0.54ni
0.13co
0.13] O
2material main method has solid phase method, coprecipitation and sol-gal process.Solid phase method is that raw material takes to be placed in ball mill according to stoichiometric proportion and obtains presoma by ball milling, rich lithium ternary system material is obtained in atmosphere after Overheating Treatment, although this method is applicable to large-scale production, but obtain that material granule is comparatively large, pattern is uneven makes electrolyte cannot enter granule interior to cause the high magnification chemical property of material poor, ball-milling method power consumption is higher in addition; Coprecipitation is that the slaine of manganese nickel cobalt is configured to solution, select suitable coprecipitator, rich lithium ternary system material is obtained with lithium salts mixing after-baking after generating precipitation of hydroxide drying, in this method, the adjustment of Ph is difficult to accurate control, cause nucleation rate in coprecipitation process uneven, the material particle size difference of synthesis is larger; In order to overcome the defect existed in above synthetic method, the present invention adopts sol-gal process to synthesize rich lithium ternary system Li [Li
0.2mn
0.54ni
0.13co
0.13] O
2positive electrode.
When synthesizing many metal ion oxide, because complexing agent is different to complexing of metal ion ability, use during single complexing agent and all have impact in various degree to the pattern of material and the chemical property of particle uniformity and material after the presoma homogeneity of ingredients prepared, sintering, and adopt the method for two complexing agent effectively can improve the adverse effect of single complexing agent appearance.Document (Zhao Xueling etc. Chinese Journal of Inorganic Chemistry .2013, the 29th volume fifth phase, 1013-1018) individually adopt citric acid (CA) and ethylenediamine tetra-acetic acid (EDTA) as complexant to synthesize rich lithium binary stratiform Li [Li
0.2ni
0.2mn
0.6] O
2material, when found that using EDTA as complexing agent synthetic material in sintering process material particle size skewness, chemical property is poor, and chemical property preferably binary stratified material can be obtained using CA as complexing agent, but in building-up process, need fine adjustment Ph value to prevent forming gel at evaporating solvent occur deposited phenomenon, and reuniting appears in material granule, particle diameter differs.Therefore the present invention looks for another way, and utilizes the two complexing agent of EDTA and CA to synthesize rich lithium ternary system material, makes certain improvements simultaneously, obtain evengranular electrode material in pre-sinter process.
Summary of the invention
Main thought of the present invention is: first by regulating the even rich lithium ternary system Gel Precursor of ratio synthesis of EDTA and CA, then pass through under an inert atmosphere through carbonization, form evengranular metal oxide, eventually passing sintering in atmosphere, to obtain pattern homogeneous, uniform particles, has the rich lithium ternary system material of good electrical chemical property.
An object of the present invention adopts sol-gal process, the method complexation of metal ions of two complexing agent is utilized growing up of limiting material particle diameter, control granule-morphology, thus improve the high rate capability of material, obtain the rich lithium ternary electrode material of excellent electrochemical performance.
Two of object of the present invention provides that a kind of operation is simple and feasible, the required prices of raw and semifnished materials are cheap, production cost is low, be beneficial to the anode material for lithium-ion batteries of environmental protection.
In order to achieve the above object, the present invention is achieved by the following technical solutions.
The preparation method of rich lithium ternary system nano material, comprises the following steps:
(1) take 0.05mol complexing agent ethylenediamine tetra-acetic acid (EDTA) to be dissolved in 50ml weak aqua ammonia as the first complexing agent, stirring and forming concentration is 1mol/L clear solution A;
(2) by the mol ratio Li of ion
+: Mn
2+: Co
2+: Ni
2+=1.26:0.54:0.13:0.13 takes corresponding salt and is dissolved in deionized water and forms pink colour solution B;
(3) under 80 DEG C of stirring in water bath, mixed solution A and solution B make it fully complex reaction occur, citric acid is added as the second complexing agent after stirring 2h, wherein the mol ratio of ethylenediamine tetra-acetic acid and citric acid is 1:1 ~ 2, and the concentration of citric acid is 0.1 ~ 0.2mol/L;
(4) at 80 DEG C, evaporating solvent forms wet gel, 100 DEG C of dry 24h, and first in atmosphere furnace, calcined temperature is 400 DEG C, and burn-in time is 3 ~ 6h; Then be 700 ~ 900 DEG C in Muffle furnace calcining heat, calcination time is 6 ~ 24h, obtains rich lithium ternary system Li [Li
0.2mn
0.54ni
0.13co
0.13] O
2nano material.
As preferably, soluble manganese source described in step (2) is the one in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride; Described soluble nickel source is the one in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride; Described solubility cobalt source is the one in cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride; Described solubility lithium source is the one in lithium nitrate, lithium acetate, lithium hydroxide, lithium carbonate.
As preferably, the second complexing agent described in step (3) can be replaced tartaric acid or oxalic acid or butanedioic acid.
As preferably, described in step (4), pre-burning atmosphere is Ar or N
2or Ar and N
2gaseous mixture.
As preferably, the heating rate being raised to sintering temperature from room temperature in sintering process described in step (4) is 2 DEG C/min
The invention has the beneficial effects as follows:
1) adopt the rich lithium ternary system material chemical composition of sol-gal process synthesis even, purity is high, and particle is less, is conducive to generation and the growth of crystal in material heat treatment process, can reduce reaction temperature, Reaction time shorten simultaneously;
2) utilize ethylenediamine tetra-acetic acid (EDTA) and citric acid can realize metal ion as two complexing agent to grow in position, the increase of limiting material particle diameter, simultaneously, in heat treatment process, resolve into NH
3and CO
2discharge, effectively can improve the dispersiveness of material granule;
3) granular size and pattern by improving material effectively can improve the chemical property of material under high magnification, increase the life-span of cycle performance of battery and battery.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is further detailed explanation.
Fig. 1 is the rich lithium ternary system Li [Li of preparation method's embodiment of the present invention's rich lithium ternary system nano material
0.2mn
0.54ni
0.13co
0.13] O
2x-ray diffraction (XRD) collection of illustrative plates of nano anode material;
Fig. 2 is the rich lithium ternary system Li [Li of preparation method's embodiment of the present invention's rich lithium ternary system nano material
0.2mn
0.54ni
0.13co
0.13] O
2the ESEM collection of illustrative plates of nano anode material;
Fig. 3 is the rich lithium ternary system Li [Li of preparation method's embodiment of the present invention's rich lithium ternary system nano material
0.2mn
0.54ni
0.13co
0.13] O
2the electrochemistry cyclic curve of nano anode material.
Embodiment
Below rich lithium ternary system Li [Li
0.2mn
0.54ni
0.13co
0.13] O
2the specific experiment process of nano anode material synthesis, to be described in further detail the present invention.
Embodiment 1
take 0.05mol complexing agent ethylenediamine tetra-acetic acid (EDTA) to be dissolved in 50ml weak aqua ammonia, stir and form 1mol/L clear solution A;
by the mol ratio Li of ion
+: Mn
2+: Co
2+: Ni
2+=1.26:0.54:0.13:0.13 takes its 63mmol lithium acetate, 27mmol manganese acetate, 6.5mmol cobalt acetate, 6.5mmol nickel acetate are dissolved in deionized water and form pink colour solution B;
under 80 DEG C of stirring in water bath, mixed solution A and solution B make it fully complex reaction occur, and add 75mmol complexing agent citric acid after stirring 2h, wherein the mol ratio of two complexing agent EDTA and citric acid is 1:1.5, and the concentration of citric acid is 1.5mol/L;
at 80 DEG C, evaporating solvent forms wet gel, 100 DEG C of dry 24h, and first in atmosphere furnace, calcined temperature is 400 DEG C, and burn-in time is 4h; Then be 800 DEG C in Muffle furnace calcining heat, calcination time is 10h, obtains rich lithium ternary system material.
Embodiment 2
(1) take 0.05mol complexing agent ethylenediamine tetra-acetic acid (EDTA) to be dissolved in 50ml weak aqua ammonia, stir and form 1mol/L clear solution A;
(2) press the mol ratio Li of ion
+: Mn
2+: Co
2+: Ni
2+=1.26:0.54:0.13:0.13 takes its 63mmol lithium acetate, 27mmol manganese acetate, 6.5mmol cobalt acetate, 6.5mmol nickel acetate are dissolved in deionized water and form pink colour solution B;
(3) under 80 DEG C of stirring in water bath, mixed solution A and solution B make it fully complex reaction occur, and add 75mmol complexing agent citric acid after stirring 2h, wherein the mol ratio of two complexing agent EDTA and citric acid is 1:2, and the concentration of citric acid is 2mol/L;
(4) at 80 DEG C, evaporating solvent forms wet gel, 100 DEG C of dry 24h, and first in atmosphere furnace, calcined temperature is 400 DEG C, and burn-in time is 4h; Then be 900 DEG C in Muffle furnace calcining heat, calcination time is 10h, obtains rich lithium ternary system material.
Embodiment 3
(1) take 0.05mol complexing agent ethylenediamine tetra-acetic acid (EDTA) to be dissolved in 50ml weak aqua ammonia, stir and form 1mol/L clear solution A;
(2) press the mol ratio Li of ion
+: Mn
2+: Co
2+: Ni
2+=1.26:0.54:0.13:0.13 takes its 63mmol lithium acetate, 27mmol manganese acetate, 6.5mmol cobalt acetate, 6.5mmol nickel acetate are dissolved in deionized water and form pink colour solution B;
(3) under 80 DEG C of stirring in water bath, mixed solution A and solution B make it fully complex reaction occur, and add 75mmol complexing agent citric acid after stirring 2h, wherein the mol ratio of two complexing agent EDTA and citric acid is 1:1, and the concentration of citric acid is 1mol/L;
(4) at 80 DEG C, evaporating solvent forms wet gel, 100 DEG C of dry 24h, and first in atmosphere furnace, calcined temperature is 400 DEG C, and burn-in time is 6h; Then be 800 DEG C in Muffle furnace calcining heat, calcination time is 10h, obtains rich lithium ternary system material.
Embodiment 4
(1) take 0.05mol complexing agent ethylenediamine tetra-acetic acid (EDTA) to be dissolved in 50ml weak aqua ammonia, stir and form 1mol/L clear solution A;
(2) press the mol ratio Li of ion
+: Mn
2+: Co
2+: Ni
2+=1.26:0.54:0.13:0.13 takes its 63mmol lithium acetate, 27mmol manganese acetate, 6.5mmol cobalt acetate, 6.5mmol nickel acetate are dissolved in deionized water and form pink colour solution B;
(3) under 80 DEG C of stirring in water bath, mixed solution A and solution B make it fully complex reaction occur, and add 75mmol complexing agent citric acid after stirring 2h, wherein the mol ratio of two complexing agent EDTA and citric acid is 1:1.5, and the concentration of citric acid is 1.5mol/L;
(4) at 80 DEG C, evaporating solvent forms wet gel, 100 DEG C of dry 24h, and first in atmosphere furnace, calcined temperature is 400 DEG C, and burn-in time is 6h; Then be 800 DEG C in Muffle furnace calcining heat, calcination time is 24h, obtains rich lithium ternary system material.
Embodiment 5
(1) take 0.05mol complexing agent ethylenediamine tetra-acetic acid (EDTA) to be dissolved in 50ml weak aqua ammonia, stir and form 1mol/L clear solution A;
(2) press the mol ratio Li of ion
+: Mn
2+: Co
2+: Ni
2++=1.26:0.54:0.13:0.13 takes its 63mmol lithium acetate, 27mmol manganese acetate, 6.5mmol cobalt acetate, 6.5mmol nickel acetate are dissolved in deionized water and form pink colour solution B;
(3) under 80 DEG C of stirring in water bath, mixed solution A and solution B make it fully complex reaction occur, and add 75mmol complexing agent citric acid after stirring 2h, wherein the mol ratio of two complexing agent EDTA and citric acid is 1:1.5, and the concentration of citric acid is 1.5mol/L;
(4) at 80 DEG C, evaporating solvent forms wet gel, 100 DEG C of dry 24h, and first in atmosphere furnace, calcined temperature is 400 DEG C, and burn-in time is 4h; Then be 900 DEG C in Muffle furnace calcining heat, calcination time is 24h, obtains rich lithium ternary system material.
Embodiment 6
(1) take 0.05mol complexing agent ethylenediamine tetra-acetic acid (EDTA) to be dissolved in 50ml weak aqua ammonia, stir and form 1mol/L clear solution A;
(2) press the mol ratio Li of ion
+: Mn
2+: Co
2+: Ni
2+=1.26:0.54:0.13:0.13 takes its 63mmol lithium acetate, 27mmol manganese acetate, 6.5mmol cobalt acetate, 6.5mmol nickel acetate are dissolved in deionized water and form pink colour solution B;
(3) under 80 DEG C of stirring in water bath, mixed solution A and solution B make it fully complex reaction occur, and add 75mmol complexing agent citric acid after stirring 2h, wherein the mol ratio of two complexing agent EDTA and citric acid is 1:2, and the concentration of citric acid is 2mol/L;
(4) at 80 DEG C, evaporating solvent forms wet gel, 100 DEG C of dry 24h, and first in atmosphere furnace, calcined temperature is 400 DEG C, and burn-in time is 4h; Then be 700 DEG C in Muffle furnace calcining heat, calcination time is 10h, obtains rich lithium ternary system material.
By reference to the accompanying drawings, the chemical property of the rich lithium ternary system material of preparation is described with embodiment 1
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates of rich lithium ternary system material prepared by embodiment 2; Its abscissa is taking measurement of an angle of X-ray diffraction, and ordinate is the diffraction peak intensity when this angle of diffraction of material.Analyzed from profiling results, the material of synthesis is the Li [Li of stratiform
0.2mn
0.54ni
0.13co
0.13] O
2ternary system material, and without other dephasigns, degree of crystallinity and purity are all higher.
Fig. 2 is rich lithium Li [Li prepared by embodiment 1
0.2mn
0.54ni
0.13co
0.13] O
2the SEM collection of illustrative plates of ternary system material, the particle diameter of material is at about 100nm, and pattern is homogeneous.
Fig. 3 is rich lithium Li [Li prepared by embodiment 1
0.2mn
0.54ni
0.13co
0.13] O
2ternary system material circulation curve.As seen from the figure when current density is 40 mA/g, after 40 circulations, the specific capacity of material maintains about 240mAh/g, shows good chemical property.
Above-described embodiment of the present invention, does not form limiting the scope of the present invention.Any amendment done within the spirit and principles in the present invention, equivalent replacement and improvement etc., all should be included within claims of the present invention.
Claims (5)
1. the preparation method of rich lithium ternary system nano material, comprises the following steps:
(1) take 0.05mol complexing agent ethylenediamine tetra-acetic acid (EDTA) to be dissolved in 50ml weak aqua ammonia as the first complexing agent, stirring and forming concentration is 1mol/L clear solution A;
(2) by the mol ratio Li of ion
+: Mn
2+: Co
2+: Ni
2+=1.26:0.54:0.13:0.13 takes corresponding salt and is dissolved in deionized water and forms pink colour solution B;
(3) under 80 DEG C of stirring in water bath, mixed solution A and solution B make it fully complex reaction occur, citric acid is added as the second complexing agent after stirring 2h, wherein the mol ratio of ethylenediamine tetra-acetic acid and citric acid is 1:1 ~ 2, and the concentration of citric acid is 0.1 ~ 0.2mol/L;
(4) at 80 DEG C, evaporating solvent forms wet gel, 100 DEG C of dry 24h, and first in atmosphere furnace, calcined temperature is 400 DEG C, and burn-in time is 3 ~ 6h; Then be 700 ~ 900 DEG C in Muffle furnace calcining heat, calcination time is 6 ~ 24h, obtains rich lithium ternary system Li [Li
0.2mn
0.54ni
0.13co
0.13] O
2nano material.
2. preparation method according to claim 1, is characterized in that: soluble manganese source described in step (2) is the one in manganese nitrate, manganese acetate, manganese sulfate, manganese chloride; Described soluble nickel source is the one in nickel nitrate, nickel acetate, nickelous sulfate, nickel chloride; Described solubility cobalt source is the one in cobalt nitrate, cobalt acetate, cobaltous sulfate, cobalt chloride; Described solubility lithium source is the one in lithium nitrate, lithium acetate, lithium hydroxide, lithium carbonate.
3. preparation method according to claim 1, is characterized in that: the second complexing agent described in step (3) can be replaced tartaric acid or oxalic acid or butanedioic acid.
4. preparation method according to claim 1, is characterized in that: the heating rate being raised to sintering temperature from room temperature in sintering process described in step (4) is 2 DEG C/min.
5. preparation method according to claim 1, is characterized in that: described in step (4), pre-burning atmosphere is Ar or N
2or Ar and N
2gaseous mixture.
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Cited By (10)
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| CN105680034A (en) * | 2016-04-22 | 2016-06-15 | 柳州凯通新材料科技有限公司 | Synthesis process of nickel-cobalt lithium manganate anode material |
| CN105720254A (en) * | 2016-03-02 | 2016-06-29 | 合肥国轩高科动力能源有限公司 | Preparation method for carbon-coated lithium vanadate used as negative electrode material of lithium ion battery |
| CN106450275A (en) * | 2016-10-11 | 2017-02-22 | 苏州大学 | Preparation method of high-capacity ternary positive electrode material of lithium battery |
| CN106450283A (en) * | 2016-11-23 | 2017-02-22 | 昆明理工大学 | Preparing method of lithium-rich ternary anode material with high power capacity |
| CN106602056A (en) * | 2016-12-30 | 2017-04-26 | 绍兴文理学院 | Lithium-rich positive electrode material and preparation method therefor |
| CN107170969A (en) * | 2017-05-17 | 2017-09-15 | 上海电力学院 | A kind of lithium ion battery lithium-rich manganese base of modification and preparation method thereof |
| CN112794376A (en) * | 2021-01-20 | 2021-05-14 | 湖南德景源科技有限公司 | Preparation method of nickel-cobalt-manganese ternary material precursor |
| CN114678522A (en) * | 2022-04-25 | 2022-06-28 | 西安理工大学 | Modification method of lithium-rich manganese-based positive electrode material by regulating manganese vacancy and application of material |
| CN114944488A (en) * | 2022-05-23 | 2022-08-26 | 浙江锂威能源科技有限公司 | Preparation method of coated positive electrode material, product and application thereof |
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| CN105680034A (en) * | 2016-04-22 | 2016-06-15 | 柳州凯通新材料科技有限公司 | Synthesis process of nickel-cobalt lithium manganate anode material |
| CN106450275B (en) * | 2016-10-11 | 2019-08-02 | 苏州大学 | A kind of preparation method of high-capacity lithium battery tertiary cathode material |
| CN106450275A (en) * | 2016-10-11 | 2017-02-22 | 苏州大学 | Preparation method of high-capacity ternary positive electrode material of lithium battery |
| CN106450283A (en) * | 2016-11-23 | 2017-02-22 | 昆明理工大学 | Preparing method of lithium-rich ternary anode material with high power capacity |
| CN106602056A (en) * | 2016-12-30 | 2017-04-26 | 绍兴文理学院 | Lithium-rich positive electrode material and preparation method therefor |
| CN107170969A (en) * | 2017-05-17 | 2017-09-15 | 上海电力学院 | A kind of lithium ion battery lithium-rich manganese base of modification and preparation method thereof |
| CN107170969B (en) * | 2017-05-17 | 2019-12-03 | 上海电力学院 | A kind of lithium ion battery lithium-rich manganese base of modification and preparation method thereof |
| CN112794376A (en) * | 2021-01-20 | 2021-05-14 | 湖南德景源科技有限公司 | Preparation method of nickel-cobalt-manganese ternary material precursor |
| CN115924986A (en) * | 2021-10-19 | 2023-04-07 | 浙江海创锂电科技有限公司 | Preparation method of high-nickel ternary precursor material |
| CN114678522A (en) * | 2022-04-25 | 2022-06-28 | 西安理工大学 | Modification method of lithium-rich manganese-based positive electrode material by regulating manganese vacancy and application of material |
| CN114944488A (en) * | 2022-05-23 | 2022-08-26 | 浙江锂威能源科技有限公司 | Preparation method of coated positive electrode material, product and application thereof |
| CN114944488B (en) * | 2022-05-23 | 2024-02-09 | 浙江锂威能源科技有限公司 | Preparation method of coated positive electrode material, product and application thereof |
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