CN105161705A - Lithium manganese phosphate-coated nickel-cobalt lithium manganate cathode material and preparation method thereof - Google Patents

Lithium manganese phosphate-coated nickel-cobalt lithium manganate cathode material and preparation method thereof Download PDF

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CN105161705A
CN105161705A CN201510365733.XA CN201510365733A CN105161705A CN 105161705 A CN105161705 A CN 105161705A CN 201510365733 A CN201510365733 A CN 201510365733A CN 105161705 A CN105161705 A CN 105161705A
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lithium
manganese phosphate
lithium manganate
cathode material
cobalt
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CN105161705B (en
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乔文灿
宋春华
王瑛
王文阁
赵成龙
冯涛
张智辉
赵艳丽
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Shandong Yuhuang Chemical Co Ltd
Shandong Yuhuang New Energy Technology Co Ltd
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Shandong Yuhuang Chemical Co Ltd
Shandong Yuhuang New Energy Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/362—Composites
    • 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
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • 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
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
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    • 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 lithium manganese phosphate-coated nickel-cobalt lithium manganate cathode material and a preparation method thereof, and belongs to the technical field of electrochemistry. The cathode material comprises nickel-cobalt lithium manganate and lithium manganese phosphate, wherein the lithium manganese phosphate coats the surface of the nickel-cobalt lithium manganate; the chemical formula of the nickel-cobalt lithium manganate is LiNixCoyMnzO2; x+y+z=1; x is less than or equal to 0.6 and greater than or equal to 0.25; y is less than or equal to 0.4 and greater than or equal to 0.1; and z is less than or equal to 0.5 and greater than or equal to 0.2. The cathode material is simple in preparation technology, low in cost and friendly to environment; industrial production is easy to achieve; according to the lithium manganese phosphate-coated nickel-cobalt lithium manganate cathode material prepared by the method, compared with uncoated nickel-cobalt lithium manganate, particularly, the cycling stability of nickel-cobalt manganic acid at high voltage (4.4V) is significantly improved; meanwhile, the lithium manganese phosphate has relatively high voltage (4.4V) as the cathode material; lithium ion conduction on the surface of the nickel-cobalt manganic acid material is promoted after the nickel-cobalt lithium manganate is coated; and the rate capability of the cathode material is improved.

Description

Coated nickel-cobalt lithium manganate cathode material of a kind of lithium manganese phosphate and preparation method thereof
Technical field
The present invention relates to technical field of electrochemistry, particularly anode material for lithium-ion batteries, relate to coated nickel-cobalt lithium manganate cathode material of a kind of lithium manganese phosphate and preparation method thereof further.
Background technology
Along with becoming increasingly conspicuous of the energy and environmental problem, lithium ion battery, as a kind of energy storage of clean and effective and conversion medium, obtains research and the attention of more and more people.Lithium ion battery is widely used in the portable mobile apparatus such as mobile phone, notebook computer, camera; What the New-energy electric vehicle of current the supreme arrogance of a person with great power mainly used is also lithium ion battery.
The anode material for lithium-ion batteries of current commodity mainly contains cobalt acid lithium, LiMn2O4, LiFePO4 and nickle cobalt lithium manganate.Wherein cobalt acid lithium cost is high, and there is potential safety hazard during overcharge; Layered lithium manganate structural stability is poor, and lithium manganate having spinel structure specific capacity is low, and under high temperature, structural stability has much room for improvement.LiFePO4 poor processability, tap density is low, and energy density is low.Compare with above-mentioned material, nickel-cobalt lithium manganate material has that cost low and high temperature performance is good, energy density is high and the advantage such as processing characteristics is excellent, and nickle cobalt lithium manganate combination property is higher than above-mentioned positive electrode.But the cobalt acid lithium that the high rate capability of nickle cobalt lithium manganate and cyclical stability account for rate relative to high market is poor.Carrying out finishing to cobalt nickel lithium manganate ternary material is the effective approach of one improving its chemical property.Application number is 201410250912.4 employing carbon-coating nickel cobalt manganic acid lithiums, improves high rate performance and the cyclical stability of positive electrode after coated.Application number is that 201310312317.4 employing fluorapatite carry out coated to nickle cobalt lithium manganate, and the cyclical stability of material is improved.
The Modified Nickel cobalt lithium manganate material of low, the easy popularization of development cost is to improve cyclical stability and the high rate performance of nickle cobalt lithium manganate, significant in electrochemical field.
Summary of the invention
The object of the present invention is to provide coated nickel-cobalt lithium manganate cathode material of a kind of lithium manganese phosphate and preparation method thereof, to improve cyclical stability and the high rate performance of nickle cobalt lithium manganate.Another object of the present invention is to provide the application of the coated nickel-cobalt lithium manganate cathode material of lithium manganese phosphate in lithium rechargeable battery.The coated nickel-cobalt lithium manganate cathode material of lithium manganese phosphate prepared by the present invention, has cyclical stability and high rate performance is excellent, preparation method's low cost, be easy to the advantages such as suitability for industrialized production.
Technical scheme of the present invention is:
The coated nickel-cobalt lithium manganate cathode material of a kind of lithium manganese phosphate, comprise nickle cobalt lithium manganate and the lithium manganese phosphate being coated on described nickle cobalt lithium manganate surface, the chemical formula of described nickle cobalt lithium manganate is LiNi xco ymn zo 2, wherein x+y+z=1,0.25≤x≤0.6,0.1≤y≤0.4,0.2≤z≤0.5.
Preferably, the mass fraction of described lithium manganese phosphate is 0.5%-1.5%.Lithium manganese phosphate poorly conductive, covering amount too much can cause nickel-cobalt lithium manganate material electric conductivity sharp-decay, covering amount is very few cannot realize the evenly coated of lithium manganese phosphate, the hydrofluoric acid in electrolyte effectively can not be stoped the corrosion of surface of active material, and then cause nickel-cobalt lithium manganate material stable circulation performance to decay.Within the scope of this and avoid the decay of materials conductive performance simultaneously can effectively stop nickel-cobalt lithium manganate material stable circulation performance to decay.
As preferably, described lithium manganese phosphate is amorphous state.The porous state of amorphous state is conducive to carrying out reversible electrochemical reaction.
The coated nickel-cobalt lithium manganate cathode material of described lithium manganese phosphate is preparing the application in lithium ion battery.
The preparation method of the coated nickel-cobalt lithium manganate cathode material of described lithium manganese phosphate, concrete steps are:
1) be 1.1-1.5:1.05:1:1 by complexing agent compound, Li source compound, manganese source compound, P source compound according to mol ratio, obtain solution soluble in water successively, and be 3.7-4.2 by adjust ph;
2) by a certain amount of pressed powder nickle cobalt lithium manganate LiNi xco ymn zo 2join in the obtained solution of step 1), its solid content is for controlling as 25%-30%;
3) by step 2) solution that obtains stirs evaporating liquid to thickness, the still aging 2-4 hour of room temperature at 80-90 DEG C, product is placed in 90 DEG C of dry 3-6 hour of baking oven; Sample comminution crosses 400 eye mesh screens;
4) pressed powder that step 3) obtains is put into tube furnace to heat up with 1-5 DEG C/min programming rate, under being warming up to 350-550 DEG C of air atmosphere, roasting 3-4 hour, Temperature fall, to room temperature, obtains the nickel-cobalt lithium manganate cathode material that lithium manganese phosphate is coated.
Preferably, step 2) in, the mass fraction of lithium manganese phosphate controls as 0.5%-1.5%.
Preferably, described complexing agent compound is at least one in citric acid, ascorbic acid, tartaric acid.Complexing agent controls chemical reaction rate in the course of reaction generating lithium manganese phosphate, and then promotes to realize evenly coated to nickle cobalt lithium manganate, and the use of complexing agent greatly adds modified effect of the present invention.And citric acid, ascorbic acid, tartaric acid are as complexing agent, cost is low and just right to the chemical reaction rate control generating lithium manganese phosphate.
Preferably, described Li source compound is at least one in lithium hydroxide, lithium acetate, lithium nitrate; Described manganese source compound is at least one in manganese acetate, manganese citrate; Described P source compound is at least one in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid.
LiMnPO 4as its Stability Analysis of Structures of transition metal phosphate lithium salts, cheap environmental protection, has higher voltage (4.1V), can promote the conduction of nickle cobalt lithium manganate surface lithium ion as clad material, is conducive to improving high rate performance.LiMnPO 4in PO 4 3-effectively can suppress electrode material dissolving in the electrolytic solution, the hydrofluoric acid in prevention electrolyte, to the corrosion of surface of active material, improves security performance and cyclical stability.Therefore, adopt the coated nickle cobalt lithium manganate of lithium manganese phosphate, cyclical stability and the high rate performance of nickle cobalt lithium manganate can be improved.And the method is easy to operation, be easy to promote.
Beneficial effect of the present invention is:
The surface coated lithium manganese phosphate of nickel-cobalt lithium manganate cathode material prepared by the present invention is amorphous state, favourable to the chemical property of material, simultaneously lithium manganese phosphate can stop hydrofluoric acid in electrolyte to the corrosion on nickle cobalt lithium manganate surface, significantly improve the cyclical stability of nickle cobalt lithium manganate, especially cyclical stability under high voltage (4.4V);
Lithium manganese phosphate itself has higher voltage (4.1V) as positive electrode, can promote nickel-cobalt lithium manganate material surface lithium ionic conduction, improve its high rate performance after coated.
The present invention has actual application prospect at electrokinetic cell and high-energy density type field of batteries.Present invention improves cyclical stability and the high rate performance of nickle cobalt lithium manganate, preparation technology is simple, and consuming time short, and energy consumption is low, with low cost, and environmental friendliness is easy to suitability for industrialized production.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
The scanning electron microscope (SEM) photograph of the coated nickel-cobalt lithium manganate material of the lithium manganese phosphate of Fig. 1 prepared by the present invention, enlargement ratio 2000 times.
The scanning electron microscope (SEM) photograph of the coated nickel-cobalt lithium manganate material of the lithium manganese phosphate of Fig. 2 prepared by the present invention, enlargement ratio 5000 times.
Fig. 3 is the X-ray diffraction spectrogram before and after the coated nickle cobalt lithium manganate of lithium manganese phosphate prepared by the present invention;
Fig. 4 is before and after the coated nickle cobalt lithium manganate of lithium manganese phosphate prepared by the present invention under 1C multiplying power, the specific discharge capacity stable circulation performance figure of 3.0V-4.4V.
Fig. 5 is before and after the coated nickle cobalt lithium manganate of lithium manganese phosphate prepared by the present invention under 0.2C-8C multiplying power, the discharge-rate performance map of 3.0V-4.3V.
Embodiment
Embodiment 1
By 0.1844gC 6h 8o 7h 2o, 0.0351gLiOHH 2o, 0.1955gMn (CH 3cOO) 24H 2o and 0.0917gNH 4h 2pO 4(complexing agent: Li:Mn:P=1.1:1.05:1:1) is dissolved in 60ml deionized water successively, adopts red fuming nitric acid (RFNA) or concentrated ammonia liquor to regulate pH value of solution to be 4.2, by 25gLiNi 0.5mn 0.3co 0.2o 2powder infusion is in above-mentioned solution, and the mass fraction of lithium manganese phosphate controls to be 0.5%; This solution stirs evaporating liquid to thickness at 90 DEG C of lower magnetic forces, still aging 2 hours of room temperature, is then placed in 90 DEG C of baking ovens dry 3 hours, pulverizes 400 eye mesh screens; The 450 DEG C of roastings 4 hours in air atmosphere of gained sample, naturally cool to room temperature, the nickel-cobalt lithium manganate cathode material that finally obtained lithium manganese phosphate is coated.
Embodiment 2:
By 0.7538gC 6h 8o 7h 2o, 0.2563gLi (CH 3cOO) 22H 2o, 0.5864gMn (CH 3cOO) 24H 2o and 0.3160g (NH 4) 2hPO 4(complexing agent: Li:Mn:P=1.5:1.05:1:1) is dissolved in 60ml deionized water successively, adopts red fuming nitric acid (RFNA) or concentrated ammonia liquor to regulate pH value of solution to be 3.7, by 25gLiNi 0.5mn 0.3co 0.2o 2powder infusion is in above-mentioned solution, and the mass fraction of lithium manganese phosphate controls to be 1.5%; This solution stirs evaporating liquid to thickness at 90 DEG C of lower magnetic forces, still aging 2 hours of room temperature, is then placed in 90 DEG C of baking ovens dry 6 hours, pulverizes 400 eye mesh screens; The 550 DEG C of roastings 4 hours in air atmosphere of gained sample, naturally cool to room temperature, the nickel-cobalt lithium manganate cathode material that finally obtained lithium manganese phosphate is coated.
Embodiment 3:
By 0.4355gC 6h 8o 7h 2o, 0.0703gLiOHH 2o, 0.3910gMn (CH 3cOO) 24H 2o and 0.1834gNH 4h 2pO 4(complexing agent: Li:Mn:P=1.3:1.05:1:1) is dissolved in 75ml deionized water successively, adopts red fuming nitric acid (RFNA) or concentrated ammonia liquor to regulate pH value of solution to be 4.2, by 25gLiNi 0.5mn 0.3co 0.2o 2powder infusion is in above-mentioned solution, and the mass fraction of lithium manganese phosphate controls to be 1.0%; This solution stirs evaporating liquid to thickness at 85 DEG C of lower magnetic forces, still aging 4 hours of room temperature, is then placed in 90 DEG C of baking ovens dry 6 hours, pulverizes 400 eye mesh screens; The 450 DEG C of roastings 4 hours in air atmosphere of gained sample, naturally cool to room temperature, the nickel-cobalt lithium manganate cathode material that finally obtained lithium manganese phosphate is coated.
Embodiment 4:
By 0.1844gC 6h 8o 7h 2o, 0.0351gLiOHH 2o, 0.1955gMn (CH 3cOO) 24H 2o and 0.0917gNH 4h 2pO 4(complexing agent: Li:Mn:P=1.1:1.05:1:1) is dissolved in 75ml deionized water successively, adopts red fuming nitric acid (RFNA) or concentrated ammonia liquor to regulate pH value of solution to be 4.0, by 25gLiNi 0.3mn 0.4co 0.3o 2powder infusion is in above-mentioned solution, and the mass fraction of lithium manganese phosphate controls as 0.5wt%; This solution stirs evaporating liquid to thickness at 85 DEG C of lower magnetic forces, still aging 4 hours of room temperature, is then placed in 90 DEG C of baking ovens dry 6 hours, pulverizes 400 eye mesh screens; The 350 DEG C of roastings 4 hours in air atmosphere of gained sample, naturally cool to room temperature, the nickel-cobalt lithium manganate cathode material that finally obtained lithium manganese phosphate is coated.
As shown in Figure 1, the scanning electron microscopic picture of the coated nickel-cobalt lithium manganate material of the lithium manganese phosphate prepared by the embodiment of the present invention 1, enlargement ratio 2000 times.
As shown in Figure 2, the scanning electron microscopic picture of the coated nickel-cobalt lithium manganate material of the lithium manganese phosphate prepared by the embodiment of the present invention 1, enlargement ratio 5000 times, the lithium manganese phosphate of amorphous state obviously can be observed in nickel cobalt manganese lithium surface.
As shown in Figure 3, the X-ray diffraction spectrogram display lithium manganese phosphate of the coated nickel-cobalt lithium manganate material of the lithium manganese phosphate prepared by the embodiment of the present invention 1 is amorphous state.
As shown in Figure 4, the coated LiNi of the lithium manganese phosphate prepared by embodiment 1 0.5mn 0.3co 0.2o 2as positive electrode, lithium is negative material, and assembling button cell, at voltage window 3.0-4.4V, under 1C multiplying power, the material capacity conservation rate of cycle charge discharge after 100 weeks after coated lithium manganese phosphate brings up to 92.6% by 80.1%, and under high voltage (4.4V), cycle performance obviously improves.
As shown in Figure 5, the coated LiNi of the lithium manganese phosphate prepared by embodiment 1 0.5mn 0.3co 0.2o 2as positive electrode, lithium is negative material, and assembling button cell, at voltage window 3.0-4.4V, under large multiplying power, (5C, 8C) discharge performance obviously promotes.

Claims (8)

1. the coated nickel-cobalt lithium manganate cathode material of lithium manganese phosphate, comprise nickle cobalt lithium manganate and the lithium manganese phosphate being coated on described nickle cobalt lithium manganate surface, the chemical formula of described nickle cobalt lithium manganate is LiNi xco ymn zo 2, wherein x+y+z=1,0.25≤x≤0.6,0.1≤y≤0.4,0.2≤z≤0.5.
2. the coated nickel-cobalt lithium manganate cathode material of lithium manganese phosphate as claimed in claim 1, is characterized in that: the mass fraction of described lithium manganese phosphate is 0.5%-1.5%.
3. the coated nickel-cobalt lithium manganate cathode material of lithium manganese phosphate as claimed in claim 1 or 2, is characterized in that: described lithium manganese phosphate is amorphous state.
4. described in an any one of claim 1-3, the coated nickel-cobalt lithium manganate cathode material of lithium manganese phosphate is preparing the application in lithium ion battery.
5. a preparation method for the coated nickel-cobalt lithium manganate cathode material of lithium manganese phosphate described in claim 1, is characterized in that, concrete steps are:
1) be 1.1-1.5:1.05:1:1 by complexing agent compound, Li source compound, manganese source compound, P source compound according to mol ratio, obtain solution soluble in water successively, and be 3.7-4.2 by adjust ph;
2) by a certain amount of pressed powder nickle cobalt lithium manganate LiNi xco ymn zo 2join in the obtained solution of step 1), its solid content is for controlling as 25%-30%;
3) by step 2) solution that obtains stirs evaporating liquid to thickness, the still aging 2-4 hour of room temperature at 80-90 DEG C, product is placed in 90 DEG C of dry 3-6 hour of baking oven; Sample comminution crosses 400 eye mesh screens;
4) pressed powder that step 3) obtains is put into tube furnace to heat up with 1-5 DEG C/min programming rate, under being warming up to 350-550 DEG C of air atmosphere, roasting 3-4 hour, Temperature fall, to room temperature, obtains the nickel-cobalt lithium manganate cathode material that lithium manganese phosphate is coated.
6. the preparation method of the coated nickel-cobalt lithium manganate cathode material of lithium manganese phosphate as claimed in claim 5, is characterized in that: step 2) in, the mass fraction of lithium manganese phosphate controls as 0.5%-1.5%.
7. the preparation method of the coated nickel-cobalt lithium manganate cathode material of lithium manganese phosphate as claimed in claim 5, is characterized in that: described complexing agent compound is at least one in citric acid, ascorbic acid, tartaric acid.
8. the preparation method of the coated nickel-cobalt lithium manganate cathode material of lithium manganese phosphate as described in claim 5 or 7, is characterized in that: described Li source compound is at least one in lithium hydroxide, lithium acetate, lithium nitrate; Described manganese source compound is at least one in manganese acetate, manganese citrate; Described P source compound is at least one in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid.
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CN105552360A (en) * 2016-03-03 2016-05-04 四川浩普瑞新能源材料股份有限公司 Modified lithium nickel cobalt manganese oxide cathode material and preparation method thereof
CN106058221A (en) * 2016-08-12 2016-10-26 合肥国轩高科动力能源有限公司 Preparation method of phosphate polyanion composite manganese salt coated lithium-rich manganese-based positive electrode material
WO2017000741A1 (en) * 2015-06-29 2017-01-05 山东玉皇新能源科技有限公司 Lithium manganese phosphate-coated lithium nickel cobalt manganese oxide cathode material and preparation method thereof
CN107221645A (en) * 2017-07-06 2017-09-29 广州朝锂新能源科技有限公司 Nickelic layered cathode material of surface modification lithium ion battery and preparation method thereof
CN108933242A (en) * 2018-07-10 2018-12-04 邓丽萍 A kind of preparation method of lithium ion battery blended anode
CN109216680A (en) * 2018-09-18 2019-01-15 贵州永合益环保科技有限公司 A kind of method of lithium manganese phosphate, alumina-coated nickel-cobalt lithium manganate cathode material
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