CN103560243A - Preparation method for synthesizing LiNi1/3Co1/3Mn1/3O2 nanometer fiber by using electro-spinning technique - Google Patents

Preparation method for synthesizing LiNi1/3Co1/3Mn1/3O2 nanometer fiber by using electro-spinning technique Download PDF

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CN103560243A
CN103560243A CN201310556823.8A CN201310556823A CN103560243A CN 103560243 A CN103560243 A CN 103560243A CN 201310556823 A CN201310556823 A CN 201310556823A CN 103560243 A CN103560243 A CN 103560243A
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preparation
lini
nanofiber
spinning technique
electrostatic spinning
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梁小平
毛新钰
刘凯
周倩倩
王欢
李冬梅
左蕊
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Tianjin Polytechnic 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/12—Manganates manganites or permanganates
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/40—Nickelates
    • C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
    • C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
    • 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
    • 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
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention discloses a preparation method for synthesizing a LiNi1/3Co1/3Mn1/3O2 nanometer fiber by using an electro-spinning technique, and belongs to the technical field of lithium ion battery electrode materials and preparation of the materials. The preparation method comprises the steps: preparing a precursor solution by using raw materials of lithium nitrate, nickel nitrate, cobalt nitrate, manganese acetate, deionized water, polyacrylic acid and polyvinylpyrrolidone (PVP) as raw materials, preparing a PVP/LiNi1/3Co1/3Mn1/3O2 composite fiber through using an electro-spinning technique, insulating, sintering, and cooling to a room temperature to obtain the LiNi1/3Co1/3Mn1/3O2 nanometer fiber. The preparation method is simple in process, convenient to operate, low in cost and slight in pollution. An anode material of the LiNi1/3Co1/3Mn1/3O2 nanometer fiber prepared by using the preparation method provided by the invention has a good electrochemical performance.

Description

A kind of electrostatic spinning technique synthesizes LiNi 1/3co 1/3mn 1/3o 2the preparation method of nanofiber
Technical field
The invention belongs to lithium ion battery electrode material and preparing technical field thereof, electrostatic spinning technique synthesis of anode material of lithium-ion battery and preparation method thereof is particularly provided.
Background technology
Lithium ion battery has that energy density is high, power density is high, operating voltage is high, has extended cycle life, security performance is good, memory-less effect, the advantage such as pollution-free, is state-of-the-art a kind of green secondary cell at present.Lithium ion battery generally comprises positive pole, negative pole, barrier film, and electrolyte.Its operation principle is that lithium ion is deviate between positive and negative pole material by electrolyte and embeds, so the structure of electrolyte and electrode material and performance are the key factors that affects battery performance and price thereof.Common anode material for lithium-ion batteries mainly contains at present: LiCoO 2, LiNiO 2, LiMn 2o 4, LiFePO 4and LiNi xco ymn 1-x-yo 2deng.But above-mentioned positive electrode has shortcoming separately: LiCoO 2structural instability under high potential, actual capacity is only half of theoretical capacity; LiNiO 2crystal stability is poor, cycle performance wretched insufficiency; LiMn 2o 4middle Mn 2+easily being dissolved in electrolyte causes capacity attenuation very fast; LiFePO 4electric conductivity difference cause the de-embedding difficulty of lithium ion, and the ternary LiNi of layer structure xco ymn 1-x-yo 2anode material for lithium-ion batteries, comprehensive LiCoO 2, LiNiO 2and LiMnO 2the advantage of three kinds of stratified materials, will, significantly better than above arbitrary one-component positive electrode, there is obvious cooperative compensating effect in its performance: introduce Co, can reduce the generation of cation mixing occupy-place situation, effectively the layer structure of stabilizing material; Introduce Ni, can improve the capacity of material; Introduce Mn, can reduce the safety and stability of material cost, raising material.LiNi 1/3co 1/3mn 1/3o 2tertiary cathode material structural change under different temperatures and multiplying power is less, so material has good stability, is to study at present and apply maximum ternary materials.In the patent documentation of having delivered at present, synthetic LiNi 1/3co 1/3mn 1/3o 2the method of lithium ion anode material is high temperature solid-state method, sol-gal process, coprecipitation, hydro thermal method, template, microwave method etc.By electrostatic spinning technique, can obtain the diameter controllable nano fiber of big L/D ratio, and specific area is large, quantum confined effect is obvious, can be widely used in and prepare metal, inorganic oxide and high polymer nanometer fiber.The relevant electrostatic spinning technique that adopts synthesizes LiNi at present 1/3co 1/3mn 1/3o 2the report of lithium ion anode material does not almost have.
Summary of the invention
The object of the present invention is to provide a kind of electrostatic spinning technique to synthesize LiNi 1/3co 1/3mn 1/3o 2the preparation method of nanofiber.
A kind of electrostatic spinning technique synthesizes LiNi 1/3co 1/3mn 1/3o 2the preparation method of nanofiber, is characterized in that, the method step is as follows,
(1) by lithium nitrate, nickel nitrate, cobalt nitrate and manganese acetate in molar ratio 3:1:1:1 be dissolved in deionized water, add again complexing agent polyacrylic acid, the mixed solution of preparation is added to thermal agitation 2～3h under the water bath condition of 60 ℃～70 ℃ and obtain transparent red solution, then add polyvinylpyrrolidone to stir 10～12h it is sufficiently uniformly dissolved, then the precursor solution that obtains of static 3～4h;
(2) in ambient temperature, be 15 ℃～25 ℃, ambient humidity is 35%～65%, and solidifying distance is 14cm～19cm, and polytetrafluoroethylene needle tubing and syringe needle horizontal cross angle of inclination are under the condition of 14～16 °, to carry out electrostatic spinning to prepare PVP/LiNi 1/3co 1/3mn 1/3o 2composite fibre, the contact rod with stainless steel electrode as spinning solution, negative pole receiving system is aluminium foil;
(3) by PVP/LiNi 1/3co 1/3mn 1/3o 2composite fibre is 300～350 ℃ of pre-burnings under air atmosphere in tube furnace, naturally cooling after insulation 5～7h, then in vacuum tube furnace, under Ar atmosphere, at 600 ℃～800 ℃, carry out calcination processing 2h, be naturally cooled to room temperature after cooling to 250 ℃～200 ℃, obtain LiNi 1/3co 1/3mn 1/3o 2the anode material for lithium-ion batteries of nanofiber.
Described complexing agent polyacrylic acid relative molecular mass is 800～1000, and solids content is 30%.
Polyacrylic addition is with polyacrylic acid and metal cation (Li ++ Ni 2++ Co 2++ Mn 2+) the molar ratio R of total amount of material weighs, R is 0.25-1.25.
The solution cation total concentration (Li+Ni+Co+Mn) of described configuration is 0.6～0.8mol/L.
Before being used, described polyvinylpyrrolidone grinds 5～15min.Polyvinylpyrrolidone consumption is the 5-12% of lithium nitrate, nickel nitrate, cobalt nitrate and manganese acetate quality sum.
The invention has the beneficial effects as follows:
This preparation method is simple, easy to operate, and cost is low, pollution is few, LiNi prepared by the method 1/3co 1/3mn 1/3o 2nanofiber specific area is high, and diameter is controlled.LiNi prepared according to the methods of the invention 1/3co 1/3mn 1/3O 2the lithium ion anode material of nanofiber can significantly improve the chemical property of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the LiNi of embodiment 1 preparation 1/3co 1/3mn 1/3o 2the XRD collection of illustrative plates of nanofiber positive electrode;
Fig. 2 is the LiNi of embodiment 1 preparation 1/3co 1/3mn 1/3o 2the SEM picture of nanofiber positive electrode;
Fig. 3 is the LiNi of embodiment 1 preparation 1/3co 1/3mn 1/3o 2first charge-discharge curve under the different multiplying of nanofiber positive electrode;
Fig. 4 is the LiNi of embodiment 1 preparation 1/3co 1/3mn 1/3o 2cycle performance under the different current densities of nanofiber positive electrode.
Embodiment
Take lithium nitrate, nickel nitrate, cobalt nitrate, manganese acetate, deionized water, polyacrylic acid, polyvinylpyrrolidone is raw material, adopts the synthetic LiNi of electrostatic spinning technique 1/3co 1/3mn 1/3o 2nanofiber positive electrode.
Below in conjunction with drawings and Examples, the invention will be further described:
Embodiment 1
A kind of electrostatic spinning technique synthesizes LiNi 1/3co 1/3mn 1/3o 2the preparation method of nanofiber, the method step is as follows,
By lithium nitrate, nickel nitrate, cobalt nitrate and manganese acetate by being dissolved in deionized water than mol ratio 3:1:1:1, (relative molecular mass is 1000 to add complexing agent polyacrylic acid again, solids content is 30%), be configured to cation total concentration (Li+Ni+Co+Mn) for 0.6mol/L mixed solution, polyacrylic addition is with polyacrylic acid and metal cation (Li ++ Ni 2++ Co 2++ Mn 2+) the molar ratio R of total amount of material weighs, R is 0.75, mixed solution is added under the water bath condition of 60 ℃ to thermal agitation 2h and obtains transparent red solution.Then the polyvinylpyrrolidone (PVPK90) that adds levigate (polyvinylpyrrolidone grinds 10min before using), its content is 5% (percentage by weight) of slaine (lithium nitrate, nickel nitrate, cobalt nitrate and manganese acetate) content sum, stir 10h it is sufficiently uniformly dissolved, more standing 3h obtains precursor solution.20 ℃ of temperature, wet 40%, solidify apart from 15cm, polytetrafluoroethylene needle tubing and syringe needle horizontal cross angle of inclination are under 15 ° of conditions, to carry out spinning to prepare PVP/LiNi 1/3co 1/3mn 1/3o 2composite fibre, the contact rod with stainless steel electrode as spinning solution, negative pole receiving system is aluminium foil.By PVP/LiNi 1/3co 1/3mn 1/3o 2composite fibre is 350 ℃ of pre-burnings under air atmosphere in tube furnace, after insulation 5h, naturally lower the temperature, then in vacuum tube furnace under Ar atmosphere at 600 ℃ of calcination processing 2h, be naturally cooled to room temperature after cooling to 200 ℃, intensification rate of temperature fall is all 1 ℃/min, takes out sample and obtains LiNi 1/3co 1/3mn 1/3o 2the anode material for lithium-ion batteries of nanofiber.
By the LiNi of preparation 1/3co 1/3mn 1/3o 2the positive electrode of the button-shaped simulation lithium ion battery of conduct of the positive electrode of nanofiber is for electrochemical property test, concrete steps are: positive electrode, conductive agent carbon black, binding agent PVDF is according to the ratio of mass ratio 80:10:10, with 1-METHYLPYRROLIDONE (NMP), making solvent is applied on Al paper tinsel after evenly, after 120 ℃ of dry 12h, on particulate tablet press machine with 15MPa pressure compressing tablet, die-cut with particular manufacturing craft, obtain the electrode slice that diameter is 18mm, after weighing, put into vacuum drying chamber and dry 10h at 80 ℃, simulated battery is assembled in the glove box of argon shield and carries out, negative pole is that metal buries sheet, electrolyte is for containing 1mol/L LiPF 6eC+DEC mixed system (volume ratio is 1:1), barrier film is microporous polypropylene membrane.Charge and discharge process is: first constant current charge (20mA/g) is after voltage 4.4V, when constant voltage charge to current density is reduced to constant current charge again 1/10, standing 5min, then constant current discharge (20mA/g) is till voltage 2.8V tests first charge-discharge curve, the cycle performance under different current density and AC impedance curve under different multiplying.
Fig. 1 is the LiNi of embodiment 1 preparation 1/3co 1/3mn 1/3o 2the XRD collection of illustrative plates of nanofiber positive electrode.As can be seen from the figure, LiNi 1/3co 1/3mn 1/3o 2for typical a-NaFeO 2structure, belongs to hexagonal crystal system.Fig. 2 be embodiment 1 preparation LiNi 1/3co 1/3mn 1/3o 2the SEM picture of nanofiber positive electrode.Fibre diameter is 200～300nm, and fiber surface is smooth.Fig. 3 is product first charge-discharge curve chart under different current densities of embodiment 1 preparation.As seen from Figure 3, along with the increase of current density, the charging and discharging capacity of material is on a declining curve.When current density is respectively 20,40,60 and 80mAhg -1time, corresponding first charge-discharge capacity is respectively 208.1/169.2,192.7/160.1,183.1/150.4,174.3/141.8mAhg -1.Fig. 4 is the product of the embodiment 1 preparation cycle performance figure under different current densities discharge and recharge.First with 10mAg -1current density carry out charge and discharge cycles 5 times, subsequently more successively with 40,60,80mAg -1current density respectively carry out charge and discharge cycles 5 times, finally return to 10mAg -1current density charge and discharge cycles 5 times again, in Fig. 4, can find the increase along with cycle-index and current density, the discharge capacity of material reduces gradually, each time the increase of current density, the discharge capacity of material all can have individual great-jump-forward to reduce, yet ought again return to 10mAg -1current density time, the discharge capacity of material returns to again 153.1mAhg -1, illustrate that the prepared material of the present invention has good high rate performance.
The foregoing is only preferred embodiment of the present invention, in order to limit the present invention, within the spirit and principles in the present invention not all, any modification of doing, be equal to replacement, improvement etc., within all should being included in protection scope of the present invention.

Claims (6)

1. an electrostatic spinning technique synthesizes LiNi 1/3co 1/3mn 1/3o 2the method of nanofiber,
It is characterized in that, the method step is as follows,
(1) by lithium nitrate, nickel nitrate, cobalt nitrate and manganese acetate in molar ratio 3:1:1:1 be dissolved in deionized water, add again complexing agent polyacrylic acid, the mixed solution of preparation is added to thermal agitation 2～3h under the water bath condition of 60 ℃～70 ℃ and obtain transparent red solution, then add polyvinylpyrrolidone to stir 10～12h it is sufficiently uniformly dissolved, more standing 3～4h obtains precursor solution;
(2) in ambient temperature, be 15 ℃～25 ℃, ambient humidity is 35%～65%, and solidifying distance is 14cm～19cm, and polytetrafluoroethylene needle tubing and syringe needle horizontal cross angle of inclination are under the condition of 14～16 °, to carry out electrostatic spinning to prepare PVP/LiNi 1/3co 1/3mn 1/3o 2composite fibre, the contact rod with stainless steel electrode as spinning solution, negative pole receiving system is aluminium foil;
(3) by PVP/LiNi 1/3co 1/3mn 1/3o 2composite fibre is 300～350 ℃ of pre-burnings under air atmosphere in tube furnace, naturally cooling after insulation 5～7h, then in vacuum tube furnace, under Ar atmosphere, at 600 ℃～800 ℃, carry out calcination processing 2h, after cooling to 250 ℃～200 ℃, be naturally cooled to room temperature, obtain can be used as the LiNi of anode material for lithium-ion batteries 1/3co 1/3mn 1/3o 2nanofiber.
2. a kind of electrostatic spinning technique according to claim 1 synthesizes LiNi 1/3co 1/3mn 1/3o 2the preparation method of nanofiber, is characterized in that: in step (1), described complexing agent polyacrylic acid relative molecular mass is 800～1000, and solids content is 30%.
3. a kind of electrostatic spinning technique according to claim 1 synthesizes LiNi 1/3co 1/3mn 1/3o 2the preparation method of nanofiber, is characterized in that: polyacrylic addition is with polyacrylic acid and metal cation (Li ++ Ni 2++ Co 2++ Mn 2+) the molar ratio R of total amount of material weighs, R is 0.25-1.25.
4. a kind of electrostatic spinning technique according to claim 1 synthesizes LiNi 1/3co 1/3mn 1/3o 2the preparation method of nanofiber, is characterized in that: in step (1), the solution cation total concentration (Li+Ni+Co+Mn) of described configuration is 0.6～0.8mol/L.
5. a kind of electrostatic spinning technique according to claim 1 synthesizes LiNi 1/3co 1/3mn 1/3o 2the preparation method of nanofiber, is characterized in that: in step (1), before described polyvinylpyrrolidone is used, grind 5～15min.
6. a kind of electrostatic spinning technique according to claim 1 synthesizes LiNi 1/3co 1/3mn 1/3o 2the preparation method of nanofiber, is characterized in that: polyvinylpyrrolidone consumption is the 5-12% of lithium nitrate, nickel nitrate, cobalt nitrate and manganese acetate quality sum.
CN201310556823.8A 2013-11-08 2013-11-08 Preparation method for synthesizing LiNi1/3Co1/3Mn1/3O2 nanometer fiber by using electro-spinning technique Pending CN103560243A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
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CN103811747A (en) * 2014-03-04 2014-05-21 广东邦普循环科技有限公司 Power-type nickel cobalt manganese acid lithium material as well as preparation method and application thereof
CN104178929A (en) * 2014-08-19 2014-12-03 中信大锰矿业有限责任公司 Method for preparing LiNi1/3Co1/3Mn1/3O2 fibrous material by electrostatic spinning
CN107437620A (en) * 2017-07-19 2017-12-05 广东迈纳科技有限公司 The preparation method of nickelic ternary NCM622 nano-materials
CN107689451A (en) * 2016-08-04 2018-02-13 中信国安盟固利动力科技有限公司 A kind of ternary material and preparation method thereof of synthesized-power type, nanofiber
CN107805858A (en) * 2017-10-26 2018-03-16 湘潭大学 A kind of electrostatic spinning preparation method of flexible SnS C nanos fiber
CN108251918A (en) * 2018-01-09 2018-07-06 哈尔滨理工大学 A kind of MgMn2O4Nano-fiber electrode material and preparation method thereof
CN110416489A (en) * 2019-07-01 2019-11-05 北京科技大学 The nanofiber storage sodium positive electrode preparation of nano particle assembling and application method
CN114497474A (en) * 2021-12-24 2022-05-13 江苏华峰超纤材料有限公司 Preparation method of nickel-rich NCM811 nanoparticles
CN114883567A (en) * 2022-06-30 2022-08-09 河南科隆新能源股份有限公司 Lithium ion battery cathode material with hollow tubular structure and preparation method and application thereof
WO2023010972A1 (en) * 2021-08-03 2023-02-09 广东邦普循环科技有限公司 Preparation method and application of high-performance nickel 55-type modified nickel cobalt lithium manganate material

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103811747A (en) * 2014-03-04 2014-05-21 广东邦普循环科技有限公司 Power-type nickel cobalt manganese acid lithium material as well as preparation method and application thereof
CN103811747B (en) * 2014-03-04 2016-01-20 广东邦普循环科技有限公司 A kind of power type nickel-cobalt lithium manganate material and its preparation method and application
CN104178929A (en) * 2014-08-19 2014-12-03 中信大锰矿业有限责任公司 Method for preparing LiNi1/3Co1/3Mn1/3O2 fibrous material by electrostatic spinning
CN107689451A (en) * 2016-08-04 2018-02-13 中信国安盟固利动力科技有限公司 A kind of ternary material and preparation method thereof of synthesized-power type, nanofiber
CN107437620A (en) * 2017-07-19 2017-12-05 广东迈纳科技有限公司 The preparation method of nickelic ternary NCM622 nano-materials
CN107805858A (en) * 2017-10-26 2018-03-16 湘潭大学 A kind of electrostatic spinning preparation method of flexible SnS C nanos fiber
CN108251918A (en) * 2018-01-09 2018-07-06 哈尔滨理工大学 A kind of MgMn2O4Nano-fiber electrode material and preparation method thereof
CN108251918B (en) * 2018-01-09 2020-05-12 哈尔滨理工大学 MgMn2O4Nanofiber electrode material and preparation method thereof
CN110416489A (en) * 2019-07-01 2019-11-05 北京科技大学 The nanofiber storage sodium positive electrode preparation of nano particle assembling and application method
WO2023010972A1 (en) * 2021-08-03 2023-02-09 广东邦普循环科技有限公司 Preparation method and application of high-performance nickel 55-type modified nickel cobalt lithium manganate material
GB2618685A (en) * 2021-08-03 2023-11-15 Guangdong Brunp Recycling Technology Co Ltd Preparation method and application of high-performance nickel 55-type modified nickel cobalt lithium manganate material
CN114497474A (en) * 2021-12-24 2022-05-13 江苏华峰超纤材料有限公司 Preparation method of nickel-rich NCM811 nanoparticles
CN114883567A (en) * 2022-06-30 2022-08-09 河南科隆新能源股份有限公司 Lithium ion battery cathode material with hollow tubular structure and preparation method and application thereof
CN114883567B (en) * 2022-06-30 2022-09-30 河南科隆新能源股份有限公司 Lithium ion battery cathode material with hollow tubular structure and preparation method and application thereof

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Application publication date: 20140205