CN107887599A - Preparation method of MOF surface-modified nano chip architecture tertiary cathode materials and products thereof and application - Google Patents

Preparation method of MOF surface-modified nano chip architecture tertiary cathode materials and products thereof and application Download PDF

Info

Publication number
CN107887599A
CN107887599A CN201711056868.3A CN201711056868A CN107887599A CN 107887599 A CN107887599 A CN 107887599A CN 201711056868 A CN201711056868 A CN 201711056868A CN 107887599 A CN107887599 A CN 107887599A
Authority
CN
China
Prior art keywords
chip architecture
lithium
mof
tertiary cathode
preparation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201711056868.3A
Other languages
Chinese (zh)
Inventor
何丹农
吴晓燕
张芳
段磊
李敏
金彩虹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Original Assignee
Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai National Engineering Research Center for Nanotechnology Co Ltd filed Critical Shanghai National Engineering Research Center for Nanotechnology Co Ltd
Priority to CN201711056868.3A priority Critical patent/CN107887599A/en
Publication of CN107887599A publication Critical patent/CN107887599A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • H01M4/52—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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Composite Materials (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The present invention provides a kind of preparation method of MOF surface-modified nanos chip architecture tertiary cathode material and products thereof and application, the present invention prepares the nanometer chip architecture ternary material of MOF surfaces modification by two step solvent-thermal methods, pass through solvent hot preparation nanometer sheet structure ternary material first, then the surface for carrying out MOF by solvent heat again is modified, nanometer chip architecture and MOF surface modification can improve the chemical property of material, 0.1C specific discharge capacities are 170 mAh/g or so, and 10C specific discharge capacities are 50 mAh/g or so.

Description

Preparation method of MOF surface-modified nano chip architecture tertiary cathode materials and products thereof And application
Technical field
The present invention relates to a kind of preparation method of anode material for lithium-ion batteries, is modified more particularly to a kind of MOF surfaces Preparation method of nanometer chip architecture tertiary cathode material and products thereof and application.
Background technology
Lithium rechargeable battery as high-energy-density electrochmical power source have been widely used for mobile communication, notebook computer, The fields such as video camera, camera, portable instrument, develop rapidly as one of currently the most important ones secondary cell.Lithium from Green high-capacity battery of the sub- battery as latest generation, is developed rapidly in early 1990s, lithium ion battery because Its voltage is high, energy density is high, have extended cycle life, the advantages that environmental pollution is small gains great popularity.
Due to ternary material LiNi1-x-yCoxMnyO2（Abbreviation NCM, wherein 0<x<1, 0<y<1）With better than ferrous phosphate The characteristic of lithium and cobalt acid lithium, and according to regulation nickel, cobalt, manganese ratio, the ternary electrode material of different performance can be prepared. NCM improves the structural stability of material, improves the charge and discharge cycles stability and high-temperature stability of material, to the full extent Its excellent chemical property is played.
The organic framework materials of metal one (MOF) are a kind of coordination polymers quickly grown in the last few years, have three-dimensional Pore structure, typically using metal ion as tie point, organic ligand support Special composition 3D extension, be zeolite and CNT it The important novel porous materials of outer another class, all it is widely used in catalysis, energy storage and separation.At present, MOF turns into nothing The important research direction of multiple chemical branches such as chemical machine, organic chemistry.
The content of the invention
For overcome the deficiencies in the prior art, present invention aims at：A kind of MOF surface-modified nanos chip architecture ternary is provided The preparation method of positive electrode.
Another object of the present invention is：MOF surface-modified nano chip architecture tertiary cathodes prepared by the above method are provided Material product.
A further object of the present invention is：The application of the said goods is provided.
The object of the invention is realized by following proposal：A kind of system of MOF surface-modified nanos chip architecture tertiary cathode material Preparation Method, comprise the following steps：
（1）By 0.2 ~ 0.4 g polyvinylpyrrolidones（PVP）It is dissolved in 60 ~ 120 mL organic solvents, forms clear solution, will The solution magnetic agitation 2 ~ 4 h, is well mixed to solution；
（2）Then by 1 mmol lithium salts,（1-x-y）Mmol nickel salts, x mmol cobalt salts and y mmol manganese salts are added in above-mentioned solution, The solution magnetic agitation 30 ~ 60 min is transferred in reactor, 160 ~ 180 DEG C of 12 ~ 15 h of reaction, natural cooling；
（3）The centrifugation of above-mentioned sediment, ethanol are washed 3 ~ 5 times, 20 ~ 24 h are dried at 60 ~ 80 DEG C, then by the precipitation after drying Thing calcines 5 ~ 10 h with 1 ~ 2 DEG C/min heating rate at 600 ~ 800 DEG C, obtains a nanometer chip architecture ternary material product A；
（4）Nano-sheet ternary material and tetrahydrate manganese chloride and 2,5- dihydroxy are dissolved in dimethylformamide to stupid dioctyl phthalate （DMF）In-EtOH-DI water, wherein, three's volume ratio is 15：1：0.5 ~ 1, the solution is transferred to reactor, 60 ~ 80 DEG C 2 ~ 4 h of reaction, filter after being cooled to room temperature, 3 times washs with DMF, 50 DEG C are dried in vacuo 12 ~ 15 h, then forge for 180 ~ 200 DEG C 5 ~ 8 h are burnt, obtain final product MOF surface-modified nano chip architecture tertiary cathode materials.
The present invention prepares the nanometer chip architecture ternary material of MOF surfaces modification by two step solvent-thermal methods.First by molten Agent hot preparation nanometer chip architecture ternary material, the surface for then carrying out MOF by solvent heat again are modified, nanometer chip architecture and MOF Surface modification can improve the chemical property of material.
Described organic solvent is one kind or its combination in ethylene glycol or glycerine.
Described lithium salts is one kind or its combination in lithium nitrate, lithium acetate, lithium citrate, lithium formate or lithium lactate.
Described nickel salt is one kind or its combination in nickel nitrate, nickel acetate or nickel oxalate.
Described cobalt salt is one kind or its combination in cobalt nitrate, cobalt acetate or cobalt oxalate.
The present invention also provides a kind of MOF surface-modified nanos chip architecture tertiary cathode material, according to any of the above-described side Method is prepared.
The present invention provides a kind of MOF surface-modified nanos chip architecture tertiary cathode material as lithium ion cell positive material again The application of material.
The present invention is advantageous in that：The nanometer chip architecture ternary material of MOF surfaces modification is prepared by two step solvent-thermal methods. First by solvent hot preparation nanometer sheet structure ternary material, the surface for then carrying out MOF by solvent heat again is modified, nanometer sheet Structure and MOF surface modification can improve the chemical property of material.
Brief description of the drawings
Fig. 1 is embodiment 1MOF surface-modified nano sheets LiNi1/3Co1/3Mn1/3O2The XRD of material；
Fig. 2 is embodiment 2MOF surface-modified nano sheets LiNi1/3Co1/3Mn1/3O2The high rate performance figure of material.
Embodiment
The present invention is described in detail by following instantiation, but protection scope of the present invention is not only restricted to these Examples of implementation.
Embodiment 1：
By 0.2 g polyvinylpyrrolidones（PVP）It is dissolved in 60 mL ethylene glycol, clear solution is formed, by the solution magnetic agitation 2 h, are well mixed to solution；Then by 1 mmol lithium acetates, 0.3333 mmol nickel acetates, 0.3333 mmol cobalt acetates and 0.3333 mmol manganese acetates are added in above-mentioned solution, and the solution magnetic agitation 60 min is transferred in reactor, 160 DEG C reaction 15 h, natural cooling；The centrifugation of above-mentioned sediment, ethanol are washed 3 times, 24 h are dried at 60 DEG C.Then after drying Sediment with 1 DEG C/min heating rate 600 DEG C calcine 10 h, obtain the LiNi of product nano sheet structure1/3Co1/ 3Mn1/3O2；Nano-sheet ternary material and tetrahydrate manganese chloride and 2,5- dihydroxy are dissolved in dimethylformamide to stupid dioctyl phthalate （DMF）In-EtOH-DI water, wherein three's volume ratio is 15：1：0.5, the solution is transferred to reactor, 60 DEG C of reactions 4 h, filter, washed 3 times with DMF, 50 DEG C of 12 h of vacuum drying, then 200 DEG C of 5 h of calcining, are obtained finally after being cooled to room temperature The LiNi for the flaky nanometer structure that product MOF surfaces are modified1/3Co1/3Mn1/3O2.Fig. 1 is MOF surface-modified nano laminated structures LiNi1/3Co1/3Mn1/3O2The XRD of material, through being contrasted with document, the material is pure phase, and R(003)/(104)=1.7, more than 1.2, Illustrate no Li+With Ni2+Ion mix phenomenon,（006）/ (102) with（108）/（110）Division peak illustrates that material is stratiform Knot.
Embodiment 2：
By 0.2 g polyvinylpyrrolidones（PVP）It is dissolved in 60 mL glycerine, clear solution is formed, by the solution magnetic agitation 2 h, are well mixed to solution；Then by 1 mmol lithium nitrates, 0.5 mmol nickel nitrates, 0.3 mmol cobalt nitrates and 0.2 mmol Manganese nitrate is added in above-mentioned solution, and the solution magnetic agitation 30 min is transferred in reactor, 180 DEG C of 12 h of reaction, Natural cooling；The centrifugation of above-mentioned sediment, ethanol are washed 3 times, 20 h are dried at 80 DEG C.Then by the sediment after drying with 1 DEG C/min heating rate calcines 8 h at 750 DEG C, obtain target product nanometer chip architecture LiNi0.5Co0.3Mn0.2O2；By nanometer Sheet ternary material is dissolved in dimethylformamide with tetrahydrate manganese chloride and 2,5- dihydroxy to stupid dioctyl phthalate（DMF）- ethanol-go from In sub- water, wherein three's volume ratio is 15：1：0.5, the solution is transferred to reactor, 60 DEG C of 4 h of reaction, is cooled to room temperature After filter, wash 3 times with DMF, 50 DEG C of 12 h of vacuum drying, then 200 DEG C of 5 h of calcining, obtain the modification of final product MOF surfaces Flaky nanometer structure LiNi0.5Co0.3Mn0.2O2, Fig. 2 is MOF surface-modified nano sheets LiN0.5Co0.3Mn0.2O2Material High rate performance figure, 0.1C specific discharge capacities are 170 mAh/g or so, and 10C specific discharge capacities are 50 mAh/g or so.
Embodiment 3：
By 0.4 g polyvinylpyrrolidones（PVP）It is dissolved in 120 mL glycerine, and adds 1 mL deionized waters, shape thereto Into clear solution, the solution magnetic agitation 4 h is well mixed to solution；Then by 1 mmol lithium nitrates, 0.8 mmol acetic acid Nickel, 0.1 mmol cobalt acetates and 0.1 mmol manganese acetates are added in above-mentioned solution, by the solution magnetic agitation 60 min, by its turn Enter in reactor, 180 DEG C of 12 h of reaction, natural cooling；The centrifugation of above-mentioned sediment, ethanol are washed 3 times, 20 are dried at 80 DEG C h.Then the sediment after drying is calcined into 5 h at 800 DEG C with 2 DEG C/min heating rate, it is hollow micro- obtains target product The LiNi of spherical structure0.8Co0.1Mn0.1O2；By nano-sheet ternary material and tetrahydrate manganese chloride and 2,5- dihydroxy to stupid dioctyl phthalate It is dissolved in dimethylformamide（DMF）In-EtOH-DI water, wherein three's volume ratio is 15：1：0.5, the solution is transferred to Reactor, 60 DEG C of 4 h of reaction, is filtered after being cooled to room temperature, and 3 times washs with DMF, and 50 DEG C are dried in vacuo 12 h, and then 200 DEG C calcining 5 h, obtain final product MOF surfaces modification flaky nanometer structure LiNi0.8Co0.1Mn0.1O2。

Claims (7)

  1. A kind of 1. preparation method of MOF surface-modified nanos chip architecture tertiary cathode material, it is characterised in that this method it is specific Step is：
    （1）By 0.2 ~ 0.4 g polyvinylpyrrolidones（PVP）It is dissolved in 60 ~ 120 mL organic solvents, forms clear solution, will The solution magnetic agitation 2 ~ 4 h, is well mixed to solution；
    （2）Then by 1 mmol lithium salts,（1-x-y）Mmol nickel salts, x mmol cobalt salts and y mmol manganese salts are added in above-mentioned solution, The solution magnetic agitation 30 ~ 60 min is transferred in reactor, 160 ~ 180 DEG C of 12 ~ 15 h of reaction, natural cooling；
    （3）The centrifugation of above-mentioned sediment, ethanol are washed 3 ~ 5 times, 20 ~ 24 h are dried at 60 ~ 80 DEG C, then by the precipitation after drying Thing calcines 5 ~ 10 h with 1 ~ 2 DEG C/min heating rate at 600 ~ 800 DEG C, obtains product A nanometer chip architecture ternary materials；
    （4）Nanometer sheet chip architecture ternary material and tetrahydrate manganese chloride and 2,5- dihydroxy are dissolved in dimethyl formyl to stupid dioctyl phthalate Amine（DMF）In-EtOH-DI water, wherein three's volume ratio is 15：1：0.5 ~ 1, the solution is transferred to reactor, 60 ~ 80 DEG C 2 ~ 4 h of reaction, filter after being cooled to room temperature, 3 times washs with DMF, 50 DEG C are dried in vacuo 12 ~ 15 h, then forge for 180 ~ 200 DEG C 5 ~ 8 h are burnt, obtain final product.
  2. 2. the preparation method of MOF surface-modified nanos chip architecture tertiary cathode material according to claim 1, it is characterised in that It is described（1）In organic solvent be one kind in ethylene glycol or glycerine or its combination.
  3. 3. the preparation method of MOF surface-modified nanos chip architecture tertiary cathode material according to claim 1, it is characterised in that It is described（2）In lithium salts be lithium nitrate, lithium acetate, lithium citrate, lithium formate or lithium lactate in one kind or its combination.
  4. 4. the preparation method of MOF surface-modified nanos chip architecture tertiary cathode material according to claim 1, it is characterised in that It is described（2）In nickel salt be nickel nitrate, nickel acetate or nickel oxalate in one kind or its combination.
  5. 5. the preparation method of MOF surface-modified nanos chip architecture tertiary cathode material according to claim 1, it is characterised in that It is described（2）In cobalt salt be cobalt nitrate, cobalt acetate or cobalt oxalate in one kind or its combination.
  6. 6. a kind of MOF surface-modified nanos chip architecture tertiary cathode material, it is characterised in that according to claim 1-5 is any Method is prepared.
  7. 7. MOF surface-modified nanos chip architecture tertiary cathode material is as lithium ion cell positive material according to claim 6 The application of material.
CN201711056868.3A 2017-11-01 2017-11-01 Preparation method of MOF surface-modified nano chip architecture tertiary cathode materials and products thereof and application Pending CN107887599A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201711056868.3A CN107887599A (en) 2017-11-01 2017-11-01 Preparation method of MOF surface-modified nano chip architecture tertiary cathode materials and products thereof and application

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201711056868.3A CN107887599A (en) 2017-11-01 2017-11-01 Preparation method of MOF surface-modified nano chip architecture tertiary cathode materials and products thereof and application

Publications (1)

Publication Number Publication Date
CN107887599A true CN107887599A (en) 2018-04-06

Family

ID=61783510

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201711056868.3A Pending CN107887599A (en) 2017-11-01 2017-11-01 Preparation method of MOF surface-modified nano chip architecture tertiary cathode materials and products thereof and application

Country Status (1)

Country Link
CN (1) CN107887599A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109546146A (en) * 2018-12-18 2019-03-29 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of rich lithium ternary electrode material and products thereof and application
CN110165196A (en) * 2019-06-13 2019-08-23 吉林大学 A kind of NCM333With ZIF-8 composite positive pole and preparation method
CN110429254A (en) * 2019-07-30 2019-11-08 哈尔滨工业大学（深圳） A kind of preparation method of anode material for lithium-ion batteries
CN110669474A (en) * 2019-10-22 2020-01-10 陕西科技大学 NiCo/C @ CNT double-conductive-network hierarchical structure material and preparation method and application thereof
WO2020215601A1 (en) * 2019-04-26 2020-10-29 浙江大学 Metal-organic framework material-coated ternary positive electrode material and preparation method therefor

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102893434A (en) * 2010-04-21 2013-01-23 巴斯夫欧洲公司 Novel metal-organic frameworks as electrode material for lithium ion accumulators
CN106410184A (en) * 2016-11-01 2017-02-15 上海纳米技术及应用国家工程研究中心有限公司 Hollow microsphere flowerlike-structured ternary positive electrode material, and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102893434A (en) * 2010-04-21 2013-01-23 巴斯夫欧洲公司 Novel metal-organic frameworks as electrode material for lithium ion accumulators
CN106410184A (en) * 2016-11-01 2017-02-15 上海纳米技术及应用国家工程研究中心有限公司 Hollow microsphere flowerlike-structured ternary positive electrode material, and preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
QI-QI QIAO等: "To enhance the capacity of Li-rich layered oxides by surface modification with metal-organic frameworks(MOFs) as cathodes for advanced lithium ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109546146A (en) * 2018-12-18 2019-03-29 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of rich lithium ternary electrode material and products thereof and application
WO2020215601A1 (en) * 2019-04-26 2020-10-29 浙江大学 Metal-organic framework material-coated ternary positive electrode material and preparation method therefor
CN110165196A (en) * 2019-06-13 2019-08-23 吉林大学 A kind of NCM333With ZIF-8 composite positive pole and preparation method
CN110165196B (en) * 2019-06-13 2022-06-14 吉林大学 NCM333ZIF-8 composite anode material and preparation method thereof
CN110429254A (en) * 2019-07-30 2019-11-08 哈尔滨工业大学（深圳） A kind of preparation method of anode material for lithium-ion batteries
CN110669474A (en) * 2019-10-22 2020-01-10 陕西科技大学 NiCo/C @ CNT double-conductive-network hierarchical structure material and preparation method and application thereof
CN110669474B (en) * 2019-10-22 2022-05-20 陕西科技大学 NiCo/C @ CNT double-conductive-network hierarchical structure material as well as preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN107887599A (en) Preparation method of MOF surface-modified nano chip architecture tertiary cathode materials and products thereof and application
JP7321225B2 (en) Positive electrode active material for lithium secondary batteries
Guo et al. Carbon-coated MnO microparticulate porous nanocomposites serving as anode materials with enhanced electrochemical performances
JP2020109772A (en) Positive-electrode active material for lithium secondary battery and lithium secondary battery having the same
US11108037B2 (en) Method for preparing graphene/ternary material composite for use in lithium ion batteries and product thereof
CN102583292B (en) Ferric phosphate having micro-nano structure and preparation method thereof as well as lithium iron phosphate material
CN113488646A (en) Prussian blue type sodium ion battery positive electrode material and preparation method thereof
CN104362343B (en) One-dimensional rod-like CuFeS2The preparation method of compound and application
CN103311505B (en) A kind of preparation method of graphene-ternary composite positive electrode material for lithium ion battery
CN106410184B (en) A kind of tiny balloon flower-like structure tertiary cathode material and preparation and application
CN105870438B (en) A kind of lithium secondary battery lithium-rich anode composite material and preparation method
CN108933237B (en) Preparation method and application of lithium ion battery positive electrode material
CN103151510A (en) Lithium ion battery cathode material and preparation method thereof
WO2015007169A1 (en) Preparation method for positive electrode material of lithium-ion battery
CN107628650A (en) With MnO2Nanotube is that template prepares ternary nano pipe positive electrode method
CN106025208A (en) Preparation method for carbon-coated ternary positive electrode material
CN109319845B (en) Spherical porous lithium manganate and preparation method and application thereof
CN109509874A (en) A kind of preparation method of molybdenum trioxide cladding lithium-rich manganese-based anode material
CN103996852A (en) Preparation method of novel nano lithium vanadium phosphate positive electrode material
CN109950523A (en) Lithium ion battery negative material transition metal oxide/carbon preparation method
CN107381656B (en) Preparation method of lithium ion battery negative electrode material
WO2023245949A1 (en) Metal-organic coordination polymer m2cax, preparation method therefor and use thereof
CN103441239A (en) Synthetic method for nanoscale ternary cathode material
CN104600283A (en) Lithium-enriched electrode material as well as preparation method and application thereof
CN102456882B (en) Lithium-ion battery cathode material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20180406

RJ01 Rejection of invention patent application after publication