CN103943842A - Synthesis of modified lithium-rich layered cathode material co-doped by anion Cl- and cation Cr<3+> - Google Patents

Synthesis of modified lithium-rich layered cathode material co-doped by anion Cl- and cation Cr<3+> Download PDF

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CN103943842A
CN103943842A CN201310023490.2A CN201310023490A CN103943842A CN 103943842 A CN103943842 A CN 103943842A CN 201310023490 A CN201310023490 A CN 201310023490A CN 103943842 A CN103943842 A CN 103943842A
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lithium
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cathode material
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张海朗
臧慧娟
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Jiangnan University
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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
    • 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
    • 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
    • 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

Abstract

The invention relates to a doped modified lithium-rich layered cathode material and a preparation method thereof, and particularly relates to a novel lithium-rich layered cathode material obtained by modification and co-doping with anion Cl- and cation Cr<3+> according to a certain ratio, and belongs to the technical field of lithium ion batteries. The method includes steps of: weighing a lithium salt, nitrate of a metal and a non-metallic lithium salt according to a molar ratio, dissolving the weighed compounds into deionized water, adding citric acid, adjusting the pH value to be 7-8 by utilization of concentrated ammonia liquor, heating, stirring and reacting to obtain wet gel, drying the wet gel to obtain dried gel, pre-sintering to obtain a precursor, and finally calcinating at high temperature and grinding to obtain a lithium-rich cathode material Li[Li<0.2>Ni<0.15>Mn<0.55>Co<0.1-x>Cr<x>]O<2-y>Cl<y> that is the modified lithium-rich layered cathode material, wherein 0<=x<0.1 and 0<=y<0.1. The cathode material has characteristics of fine and uniform particles, smooth surfaces and good crystallization performance, so that the material has high specific discharge capacity and good rate capability. Co-doping can improve the cycle performance of the material, increases the first coulombic efficiency, and reduces loss of irreversible capacity, so that the cathode material has important industrial significance.

Description

A kind of zwitterion Cl -, Cr 3+mix altogether the synthetic of the rich lithium layered cathode material of modification
Technical field
The present invention relates to one and mix altogether modified layered lithium-rich anode material and preparation method thereof, belong to technical field of lithium ion.
Background technology
Anode material for lithium-ion batteries from come out since, traditional leading material LiCoO 2because its voltage is high, steadily, specific capacity is high in electric discharge, good cycle, and preparation process simply enjoys manufacturer's favor, be also suitability for industrialized production positive electrode the earliest, but because its cost is high, cobalt resource rareness, has certain pollution and be subject to certain restrictions environment; Nickel resources is abundanter than cobalt reserves, cheap, but LiNiO 2again because of its synthesis condition harshness, Li +and Ni 2+radius is very nearly the same, easily forms dislocation, and the structure of lithium defect causes that capacity attenuation is very fast, invertibity is poor; And LiMnO 2unsteadiness on thermodynamics makes its preparation difficulty, easily becomes spinel structure in cyclic process laminate structure, makes capacity attenuation serious.LiFePO4 is as the more product of current commercialization, and also because its capacity is low, cryogenic property is bad and enjoy query.
Polynary stratiform lithium-rich anode material system is mainly by Li 2mnO 3and LiMO 2the rich lithium solid solution that (wherein M is one or more in Ni, Co, Mn etc.) forms, belongs to layered system.Make a general survey of this structure, the advantage that it has not only assembled above-mentioned single-phase layered system, has the electrochemical characteristics such as high voltage, high power capacity and good cycle performance.Also, because of the increase of lithium ratio, having reduced the ratio of transition metal, reduced cost, is very likely by the positive electrode of suitability for industrialized production, tool application prospect.
Although lithium-rich anode material has above-mentioned advantage,, its high rate performance and first coulomb efficiency are also lower, are the bottlenecks of its development of restriction.In order to address the above problem, conventionally adopt doping, coated and acid-treated form to improve positive electrode performance, and strive for can be on the basis of guaranteed capacity, solve its high rate performance and coulomb efficiency first, apply thereby obtain on a large scale.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the rich lithium layered cathode material of a kind of novel cation-anion co-doping modification lithium-ion battery and synthetic method thereof are proposed, this positive electrode uniform particles, smooth surface, degree of crystallinity is high, and charging voltage is high, capacity is high, good cycle, high rate performance and first coulomb efficiency improve, and have good high-temperature behavior.
Novel feature of mixing altogether the rich lithium layered cathode material of modification provided by the invention is: the chemical general formula of described positive electrode is Li[Li 0.2ni 0.15mn 0.55co 0.1-xcr x] O 2-ycl y; Wherein 0≤x < 0.1; 0≤y < 0.1.
A kind of novel preparation method who mixes altogether the rich lithium layered cathode material of modification of the present invention, step is as follows:
(1), lithium salts, transition metal nickel salt, manganese salt, cobalt salt, chromic salts and villaumite are weighed and dissolved in deionized water by certain mol proportion, add chelating agent, regulating pH with ammoniacal liquor is 7～8, at 70～90 DEG C, stir reaction in about 8～15 hours with the speed of 300～500 revs/min and generate coloured gel, this gelling material is dried after 12～15 hours at 90～120 DEG C, in 350～500 DEG C of presintering 6～8 hours, cooling rear grinding.850～950 DEG C of calcinings 10～20 hours, cooling rear grinding, obtained described modified layered lithium-rich anode material.
(2), lithium salts described in step (1) can be one or both in lithium nitrate, lithium acetate and lithium carbonate; Described metallic nickel, manganese, cobalt, chromic salts can be one or both in acetate and the nitrate of metal; Described nonmetal villaumite can be one or more in lithium chloride, nickel chloride, manganese chloride; Described chelating agent is one or both in tartaric acid and citric acid.
(3), described in step (1), the mol ratio of lithium salts, nickel salt, manganese salt, cobalt salt, chromic salts, villaumite is: when 1. villaumite is lithium chloride (1.26-y): 0.15: 0.55: (0.1-x): x: y, 2. when villaumite is nickel chloride 1.26: (0.15-y/2): 0.55: (0.1-x): x: (y/2), 3. when villaumite is manganese chloride 1.26: 0.15: (0.55-y/2): (0.1-x): x: (y/2), wherein 0≤x < 0.1; 0≤y < 0.1.The mole of described chelating agent is that the mole addition summation of all slaines is 0.8mol.
(4), described in step (1) at 70～90 DEG C, stir 8～15 hours with 300～500 revs/min of speed, reaction temperature can be specifically 70 DEG C, 80 DEG C, 90 DEG C, reaction revolution can be 350 revs/min, 400 revs/min, 500 revs/min, and the reaction time can be specifically 8 hours, 10 hours, 15 hours.
(5), gelling material is dried 12～15 hours at 90～120 DEG C described in step (1), described bake out temperature can be specifically 90 DEG C, 120 DEG C, and described drying time can be specifically 12 hours, 15 hours.
(6), described in step (1) 350～500 DEG C of presintering 6～8 hours, 850～950 DEG C of calcinings 10～20 hours, pre-sintering temperature can be specifically 350 DEG C, 500 DEG C, the presintering time can be specifically 6 hours, 8 hours; Calcining heat can be specifically 850 DEG C, 900 DEG C, 950 DEG C, and calcination time can be specifically 12 hours, 20 hours.
(7), need be on the basis of theoretical value excessive 5% by the amount of lithium salts described in step (3) because volatile 5% left and right of lithium-rich anode material elemental lithium in the time of high-temperature calcination.
Advantage of the present invention:
(1), the positive electrode smooth surface prepared of the present invention, better crystallinity degree, particle reaches nanoscale, has increased specific area, has improved the stability of material structure.
(2), the positive electrode chemical property prepared of the present invention is superior, high voltage, high power capacity, good cycle, high rate performance and coulomb efficiency have greatly improved, and especially have good high-temperature behavior.
(3), the positive electrode prepared of the present invention is rich lithium layer structure, preparation method's simple possible, raw material reserves are abundant, cheap, be tool application prospect, can suitability for industrialized production product, thereby there is substantial important meaning.
Brief description of the drawings:
Fig. 1 is the rich lithium ion battery positive electrode Li[Li of the embodiment of the present invention six synthesizeds 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.95cl 0.05xRD figure.
Fig. 2 is the rich lithium ion battery positive electrode Li[Li of the embodiment of the present invention one synthesized 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.95cl 0.05sEM figure.
Fig. 3 is the rich lithium ion battery positive electrode Li[Li of the embodiment of the present invention six synthesizeds 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.95cl 0.05at 55 DEG C, ((curve is b) time, the first charge-discharge curve chart under 0.1C for a) He 20 DEG C of curves.
Fig. 4 is the rich lithium ion battery positive electrode Li[Li of the embodiment of the present invention six synthesizeds 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.95cl 0.05at 55 DEG C, ((curve is b) time, the circulation discharge curve under different multiplying for a) He 20 DEG C of curves.
Embodiment
Below in conjunction with concrete drawings and Examples, the invention will be further described.
Case study on implementation one: be 1.26: 0.15: 0.55 in molar ratio by lithium nitrate, nickel nitrate, manganese acetate, cobalt nitrate: 0.1 weighs and is dissolved in deionized water, add the aqueous tartaric acid solution suitable with slaine total mole number (0.8mol), mix, with the pH value of concentrated ammonia liquor regulator solution be 7, in the constant water bath box of 70 DEG C, stir about 14 hours to gel with the speed of 350 revs/min.This gel is dried to 15 hours in 90 DEG C of baking ovens, then be placed in Muffle furnace and be warming up in proper order 350 DEG C of presintering 8 hours, obtain presoma, cooling grinding is placed in Muffle furnace and is warming up to 850 DEG C of calcinings 20 hours, and cooling grinding, obtains end product Li[Li 0.2ni 0.15mn 0.55co 0.1] O 2.
With Li[Li 0.2ni 0.15mn 0.55co 0.1] O 2for positive electrode is assembled into half-cell, at 2～4.8V, under 0.1C, 20 DEG C time, specific discharge capacity is 235.4mAhg -1; 55 DEG C time, specific discharge capacity is 282.7mAhg -1.
Case study on implementation two: be 1.26: 0.15: 0.55 in molar ratio by lithium acetate, nickel acetate, manganese acetate, cobalt nitrate, chromic nitrate: weigh and be dissolved in deionized water at 0.07: 0.03, add the aqueous tartaric acid solution suitable with slaine total mole number (0.8mol), mix, with the pH value of ammoniacal liquor regulator solution be 8, in the constant water bath box of 90 DEG C, stir about 12 hours to gel with the speed of 400 revs/min.This gel is dried to 12 hours in 120 DEG C of baking ovens, then be placed in Muffle furnace and be warming up in proper order 500 DEG C of presintering 6 hours, obtain presoma, cooling grinding is placed in Muffle furnace and is warming up to 850 DEG C of calcinings 12 hours, and cooling grinding, obtains end product Li[Li 0.2ni 0.15mn 0.55co 0.07cr 0.03] O 2.
With Li[Li 0.2ni 0.15mn 0.55co 0.07cr 0.03] O 2for positive electrode is assembled into half-cell, at 2～4.8V, under 0.1C, 20 DEG C time, specific discharge capacity is 218.7mAhg -1; 55 DEG C time, specific discharge capacity is 253.5mAhg -1.
Case study on implementation three: be 1.26: 0.15: 0.55 in molar ratio by lithium nitrate, nickel acetate, manganese nitrate, cobalt acetate, chromium acetate: weigh and be dissolved in deionized water at 0.05: 0.05, add the aqueous citric acid solution suitable with slaine total mole number (0.8mol), mix, with the pH value of ammoniacal liquor regulator solution be 7, in the constant water bath box of 80 DEG C, stir about 10 hours to gel with the speed of 500 revs/min.This gel is dried to 12 hours in 120 DEG C of baking ovens, then be placed in Muffle furnace and be warming up in proper order 500 DEG C of presintering 6 hours, obtain presoma, cooling grinding is placed in Muffle furnace and is warming up to 900 DEG C of calcinings 12 hours, and cooling grinding, obtains end product Li[Li 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 2.
With Li[Li 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 2for positive electrode is assembled into half-cell, at 2～4.8V, under 0.1C, 20 DEG C time, specific discharge capacity is 230.6mAhg -1; 55 DEG C time, specific discharge capacity is 293.1mAhg -1.
Case study on implementation four: be 1.26: 0.15: 0.55 in molar ratio by lithium carbonate, nickel nitrate, manganese nitrate, cobalt acetate, chromic nitrate: weigh and be dissolved in deionized water at 0.02: 0.08, add the aqueous citric acid solution suitable with slaine total mole number (0.8mol), mix, with the pH value of ammoniacal liquor regulator solution be 7, in the constant water bath box of 70 DEG C, stir with the speed of 500 revs/min about hour to gel.This gel is dried to 12 hours in 120 DEG C of baking ovens, then be placed in Muffle furnace and be warming up in proper order 350 DEG C of presintering 8 hours, obtain presoma, cooling grinding is placed in Muffle furnace and is warming up to 900 DEG C of calcinings 20 hours, and cooling grinding, obtains end product Li[Li 0.2ni 0.15mn 0.55co 0.02cr 0.08] O 2.
With Li[Li 0.2ni 0.15mn 0.55co 0.02cr 0.08] O 2for positive electrode is assembled into half-cell, at 2～4.8V, under 0.1C, 20 DEG C time, specific discharge capacity is 227.5mAhg -1; 55 DEG C time, specific discharge capacity is 271.6mAhg -1.
Case study on implementation five: be 1.23: 0.135: 0.55 in molar ratio by lithium nitrate, nickel acetate, manganese nitrate, cobalt nitrate, chromic nitrate, nickel chloride: weigh and be dissolved in deionized water at 0.05: 0.05: 0.015, add the aqueous citric acid solution suitable with slaine total mole number (0.8mol), mix, with the pH value of ammoniacal liquor regulator solution be 8, in the constant water bath box of 90 DEG C, stir about 12 hours to gel with the speed of 400 revs/min.This gel is dried to 15 hours in 90 DEG C of baking ovens, then be placed in Muffle furnace and be warming up in proper order 500 DEG C of presintering 6 hours, obtain presoma, cooling grinding is placed in Muffle furnace and is warming up to 950 DEG C of calcinings 12 hours, and cooling grinding, obtains end product Li[Li 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.97cl 0.03.
With Li[Li 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.97cl 0.03for positive electrode is assembled into half-cell, at 2～4.8V, under 0.1C, 20 DEG C time, specific discharge capacity is 237.8mAhg -1; 55 DEG C time, specific discharge capacity is 275.9mAhg -1.
Case study on implementation six: be 1.21: 0.15: 0.55 in molar ratio by lithium nitrate, nickel nitrate, manganese nitrate, cobalt acetate, chromic nitrate, lithium chloride: weigh and be dissolved in deionized water at 0.05: 0.05: 0.05, add the aqueous citric acid solution suitable with slaine total mole number (0.8mol), mix, with the pH value of ammoniacal liquor regulator solution be 7, in the constant water bath box of 80 DEG C, stir about 10 hours to gel with the speed of 200～500 revs/min.This gel is dried to 12 hours in 120 DEG C of baking ovens, then be placed in Muffle furnace and be warming up in proper order 500 DEG C of calcinings 6 hours, obtain presoma, cooling grinding is placed on and in Muffle furnace, is warming up to 900 DEG C of calcinings 12 hours, and cooling grinding, obtains end product Li[Li 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.95cl 0.05.
As Fig. 1, XRD characterizes and finds positive electrode Li[Li 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.95cl 0.05there is typical a-NaFeO 2stratiform configuration, belongs to R-3m space group, and peak type is sharp-pointed, and swarming is obvious, without other assorted peaks.As Fig. 2, SEM characterizes and finds material granule size evenly, and particle diameter reaches nanometer range, and the specific area of illustrative material increases, and is conducive to expand the deintercalation speed that fully contacts and accelerate lithium ion of electrolyte and material, thereby reaches higher charging and discharging capacity.
With Li[Li 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.95cl 0.05for positive electrode is assembled into half-cell, at 55 DEG C, ((curve is b) time, and under 0.1C, as shown in Figure 3, at 2～4.8V, under 0.1C, 20 DEG C time, specific discharge capacity is 239.8mAhg for concrete first charge-discharge specific capacity curve chart for a) He 20 DEG C of curves -1; 55 DEG C time, specific discharge capacity is 308.3mAhg -1.With Li[Li 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.95cl 0.05for positive electrode is assembled into half-cell, at 55 DEG C, ((curve is b) time for a) He 20 DEG C of curves, specific discharge capacity cyclic curve figure under different current densities as shown in Figure 4, after 40 circulations, electric current reaches 1C, voltage range is 2～4.8V, and 20 DEG C of specific discharge capacities are 173.5mAhg -1, when efficiency is 93.2%, 55 DEG C, specific discharge capacity is 207.7mAhg -1, efficiency is still up to 99.4%.
Case study on implementation seven: be 1.18: 0.15: 0.51 in molar ratio by lithium acetate, nickel acetate, manganese acetate, cobalt nitrate, chromic nitrate, manganese chloride: weigh and be dissolved in deionized water at 0.05: 0.05: 0.04, add the aqueous citric acid solution suitable with slaine total mole number (0.8mol), mix, with the pH value of ammoniacal liquor regulator solution be 8, in the constant water bath box of 80 DEG C, stir about 14 hours to gel with the speed of 350 revs/min.This gel is dried to 12 hours in 120 DEG C of baking ovens, then be placed in Muffle furnace and be warming up in proper order 500 DEG C of presintering 6 hours, obtain presoma, cooling grinding is placed in Muffle furnace and is warming up to 950 DEG C of calcinings 20 hours, and cooling grinding, obtains end product Li[Li 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.92cl 0.08.
With Li[Li 0.2ni 0.15mn 0.55co 0.05cr 0.05] O 1.92cl 0.08for positive electrode is assembled into half-cell, at 2～4.8V, under 0.1C, 20 DEG C time, specific discharge capacity is 232.6mAhg -1; 55 DEG C time, specific discharge capacity is 301.3mAhg -1.

Claims (7)

1. a zwitterion Cl -, Cr 3+mix altogether the synthetic of the rich lithium layered cathode material of modification, it is characterized in that described positive electrode is: Li[Li 0.2ni 0.15mn 0.55co 0.1-xcr x] O 2-ycl y; Wherein 0≤x < 0.1; 0≤y < 0.1.
2. the preparation method of utmost point material described in claim 1: by lithium salts, nickel salt, manganese salt, cobalt salt, chromic salts and villaumite according to after molar ratio weighing, dissolve in deionized water, add chelating agent, with the wet gel that heats stirring reaction system after concentrated ammonia liquor adjusting pH, drying, obtain xerogel, after presintering and high-temperature calcination grinding, obtain product successively and be modified layered lithium-rich anode material.
3. the preparation method of modified layered lithium-rich anode material according to claim 2, it is characterized in that: described lithium salts: one or more in lithium nitrate, lithium acetate and lithium carbonate, described metallic nickel, cobalt, manganese, chromic salts: one or both in acetate, the nitrate of metal.Described nonmetal Cl salt: one or more in lithium chloride, nickel chloride, manganese chloride.
4. the preparation method of modified layered lithium-rich anode material according to claim 2, is characterized in that: described chelating agent be in tartaric acid or citric acid one or both, the integral molar quantity that the mole that adds chelating agent is slaine.
5. the preparation method of modified layered lithium-rich anode material according to claim 2, is characterized in that: described to regulate pH value with concentrated ammonia liquor be 7～8.
6. the preparation method of modified layered lithium-rich anode material according to claim 2, is characterized in that: described reaction temperature: 70～90 DEG C; Described bake out temperature: 90～120 DEG C; Described presoma calcination treatment temperature: 350～500 DEG C; Described calcining heat: 850～950 DEG C.
7. the preparation method of modified layered lithium-rich anode material according to claim 2, is characterized in that: the described reaction time: 8～15 hours; Described drying time: 12～15 hours; Described pretreatment time: 6～8 hours; Described calcination time: 10～20 hours.
CN201310023490.2A 2013-01-23 2013-01-23 Synthesis of modified lithium-rich layered cathode material co-doped by anion Cl- and cation Cr<3+> Pending CN103943842A (en)

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CN105895903A (en) * 2014-12-25 2016-08-24 江南大学 Synthesis of modified lithium-rich layered positive electrode material doped with anions of F<->, Cl<-> and Br<->
CN105895902A (en) * 2014-12-25 2016-08-24 江南大学 Synthesis of novel negative and positive ions Cl and Al-codoped modified rich-lithium layered positive electrode material
CN105914364A (en) * 2016-05-13 2016-08-31 安泰科技股份有限公司 Lithium ion battery ternary positive electrode material with hollow microsphere structure and preparation method thereof
CN106229500A (en) * 2016-09-12 2016-12-14 华南理工大学 A kind of LiMn2O4 base anode material of high-temperature long life type non-stoichiometric and preparation method thereof
CN106602009A (en) * 2016-12-09 2017-04-26 江南大学 Lithium-rich positive electrode modified material of lithium ion battery and preparation method of lithium-rich positive electrode modified material
CN108011144A (en) * 2017-10-31 2018-05-08 合肥国轩高科动力能源有限公司 A kind of recovery processing technique of ternary cathode material of lithium ion battery
CN108091863A (en) * 2017-12-18 2018-05-29 江苏双登富朗特新能源有限公司 Graphene is modified lithium-rich manganese-based anode material and preparation method thereof
CN110289415A (en) * 2019-07-05 2019-09-27 福州大学 A kind of class monocrystalline tertiary cathode material and preparation method thereof that cation-anion co-doping is miscellaneous
CN111463427A (en) * 2020-04-15 2020-07-28 江南大学 Chloride ion doped modified lithium-rich layered cathode material and preparation method thereof
WO2020224020A1 (en) * 2019-05-06 2020-11-12 山东泽石新材料科技有限公司 Method and device for preparing lithium transition metal oxide
WO2024026621A1 (en) * 2022-08-01 2024-02-08 宁德时代新能源科技股份有限公司 Modified lithium-rich manganese-based material, modification method of lithium-rich manganese-based material, secondary battery, and electrical device

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CN105914364A (en) * 2016-05-13 2016-08-31 安泰科技股份有限公司 Lithium ion battery ternary positive electrode material with hollow microsphere structure and preparation method thereof
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CN106229500B (en) * 2016-09-12 2018-10-09 华南理工大学 A kind of LiMn2O4 base anode material of high-temperature long life type non-stoichiometric and preparation method thereof
CN106602009A (en) * 2016-12-09 2017-04-26 江南大学 Lithium-rich positive electrode modified material of lithium ion battery and preparation method of lithium-rich positive electrode modified material
CN108011144A (en) * 2017-10-31 2018-05-08 合肥国轩高科动力能源有限公司 A kind of recovery processing technique of ternary cathode material of lithium ion battery
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CN111463427A (en) * 2020-04-15 2020-07-28 江南大学 Chloride ion doped modified lithium-rich layered cathode material and preparation method thereof
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