CN104282882A - Composite positive electrode material and preparation method thereof - Google Patents

Composite positive electrode material and preparation method thereof Download PDF

Info

Publication number
CN104282882A
CN104282882A CN201410500300.6A CN201410500300A CN104282882A CN 104282882 A CN104282882 A CN 104282882A CN 201410500300 A CN201410500300 A CN 201410500300A CN 104282882 A CN104282882 A CN 104282882A
Authority
CN
China
Prior art keywords
composite material
feof
graphene
anode composite
fef
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.)
Granted
Application number
CN201410500300.6A
Other languages
Chinese (zh)
Other versions
CN104282882B (en
Inventor
张艳丽
王莉
何向明
赵鹏
金玉红
李建军
尚玉明
高剑
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.)
Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery Co Ltd
Original Assignee
Tsinghua University
Jiangsu Huadong Institute of Li-ion Battery 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 Tsinghua University, Jiangsu Huadong Institute of Li-ion Battery Co Ltd filed Critical Tsinghua University
Priority to CN201410500300.6A priority Critical patent/CN104282882B/en
Publication of CN104282882A publication Critical patent/CN104282882A/en
Priority to PCT/CN2015/090103 priority patent/WO2016045558A1/en
Application granted granted Critical
Publication of CN104282882B publication Critical patent/CN104282882B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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
    • H01M4/58—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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • 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)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention provides a composite positive electrode material. The composite positive electrode material is a graphene-FeOF composite material, and comprises FeOF particles and graphene which are combined by virtue of chemical bonds. The invention further provides a preparation method of the composite positive electrode material. The preparation method comprises the following steps: uniformly mixing ferric fluoride and graphene oxide in a liquid-phase solvent to form a solid-liquid mixture; performing hydrothermal/solvothermal reaction on the solid-liquid mixture in a hydrothermal/solvothermal reaction kettle at the temperature of 80-250 DEG C.

Description

Anode composite material and preparation method thereof
Technical field
The present invention relates to a kind of anode composite material based on fluorine iron oxide and preparation method thereof.
Background technology
Fluorine iron oxide (FeOF) can be regarded as and instead of FeF with O 2and the structure formed.With strong ionic FeF 2compare, FeOF contains more chemical bond Fe-O, and this makes the conductivity of FeOF be better than FeF 2(both band gap are 1.5 eV and 3 eV respectively).Meanwhile, the Fe in FeOF is+3 valencys, can three electron reactions in electrochemical process, as follows in the reaction of each voltage range: 2V ~ 4.5V:Fe 3+oF+Li=LiFe 2+oF; 0.7V ~ 2V:LiFe 2+oF+2Li=LiF+Li 2o+Fe 0, theoretical specific capacity is 885 mAh g -1, be expected the positive electrode as a kind of large specific capacity.
In prior art, the synthetic method of FeOF is comparatively limited.The J. G. Thompson of Australia National University and F. J. Brink passes through FeF 3and Fe 2o 3in airtight Pt pipe, under Ar atmosphere, 950 ° of C high temperature generation solid phase reactions synthesize FeOF first.G. G. Amatucci and the N. Pereira of Rutgers university of the U.S. do presoma by Fe metal and fluorine silicic acid aqueous solution, have synthesized FeOF by solwution method.The Shigeto Okada of Kyushu University and Ayuko Kitajou is with FeF 3and Fe 2o 3for raw material, pressure roller quench method is adopted to synthesize FeO 1.1+-1f 0.95, this fast synthesis method is beneficial to and reduces production cost and avoid F atmosphere to discharge the pollution caused.But, after these three kinds of methods synthesize FeOF, all to need with acetylene black ball milling, to increase conductivity, then to prepare electrode slice.
Summary of the invention
In view of this, necessaryly a kind of anode composite material based on fluorine iron oxide newly and preparation method thereof is provided.
A kind of anode composite material, is Graphene-FeOF composite material, comprises the FeOF particle by chemical bonds and Graphene.
A kind of anode composite material, be functionalization graphene, comprise the carbon atomic layer by FeOF particle and Graphene, the carbon atomic layer of this FeOF particle and Graphene passes through chemical bonds.
A preparation method for anode composite material, it comprises the following steps: ferric flouride and graphene oxide are uniformly mixed to form a solidliquid mixture in liquid phase solvent; And by this solidliquid mixture in hydrothermal/solvent thermal response still 80 DEG C ~ 250 DEG C carry out hydrothermal/solvent thermal response.
Compared to prior art, first passage ferric flouride of the present invention and graphene oxide synthesize FeOF, and this graphene oxide both carried out chemical reaction as reaction raw materials and ferric flouride, again as the conductive agent in anode composite material, increase the conductivity of FeOF.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the anode composite material of embodiment of the present invention synthesis.
Fig. 2 is the XRD figure of the anode composite material of embodiment of the present invention synthesis.
Embodiment
Below in conjunction with the accompanying drawings and the specific embodiments anode composite material provided by the invention and preparation method thereof is described in further detail.
The embodiment of the present invention provides a kind of anode composite material, is Graphene-FeOF composite material, comprises the FeOF particle by chemical bonds and Graphene.FeOF particle in-situ is created on graphenic surface.
Particularly, the grain size of FeOF particle is preferably 1 nm ~ 10 μm.
Be appreciated that this Graphene can comprise one or more layers (as 1 ~ 10 layer, being preferably 1 ~ 3 layer) superimposed carbon atomic layer.This Graphene can be graphene oxide, and namely in Graphene, a part of carbon atom is connected by chemical bond with oxygen atom.In this anode composite material, the mass percentage of FeOF can be 2% ~ 98%, is preferably 70% ~ 95%.
A part of carbon atom in this Graphene is connected with Fe, O or the F in FeOF particle by chemical bond, is preferably connected with the O in FeOF particle.
This anode composite material also can be regarded as a kind of functionalization graphene.The carbon atomic layer of Graphene and functional group in traditional functionalization graphene, as the organic groups such as S or Cl are connected by chemical bond.And in the present invention, what serve as functional group in this functionalization graphene is FeOF particle.
This anode composite material may be used in lithium ion battery or other electrochemical cells.
The embodiment of the present invention provides a kind of preparation method of anode composite material, and it comprises the following steps:
S1, by ferric flouride (FeF 3) and graphene oxide in liquid phase solvent, be uniformly mixed to form a solidliquid mixture; And
S2, by this solidliquid mixture in hydrothermal/solvent thermal response still 80 DEG C ~ 250 DEG C carry out hydrothermal/solvent thermal response.
FeF 3can contain or not containing the crystallization water, be preferably containing the crystallization water, as three hydration ferric flouride (FeF 33H 2o), FeF 30.33H 2o, Fe 1.9f 4.750.95H 2o, FeF 2.50.5H 2o, FeF 3h 2o and amorphous FeF 3in at least one.
This graphene oxide under hydrothermal/solvent heat condition with FeF 3reaction, generates FeOF at the carbon atomic layer surface in situ of Graphene, thus passes through chemical bonds with Graphene.When oxygen in graphene oxide all participates in the reaction with FeOF, graphene oxide can be reduced to Graphene completely.
This liquid phase solvent can be water and/or organic solvent, and this organic solvent preferably contains reactive species (as-NO 2,-OH ,-COOH etc.), as one or more in ethanol, propyl alcohol, acetic acid and citric acid.When this liquid phase solvent is the mixed solvent of water and organic solvent, the ratio between water and organic solvent does not limit.That is, the basic role that this liquid phase solvent plays is to provide the liquid phase reactor environment of hydrothermal/solvent heat.When containing water in this liquid phase solvent, FeF can be made 3dissolve, thus form solid-liquid with graphene oxide and mix, reaction is more easily carried out.Preferably, the FeF of small sized particles as far as possible can be adopted 3as raw material, when this liquid phase solvent is only organic solvent, during as ethanol, the FeF of small sized particles 3feOF can be generated with graphite oxide alkene reaction equally under the high-temperature and high-pressure conditions of hydrothermal/solvent heat.When this organic solvent contains reactive species, graphene oxide and FeF can be participated in as reactant 3reaction, promote FeOF generate.The ratio of water and organic solvent can be 1:10 ~ 10:1, is preferably 1:3 ~ 3:1.
This FeF 3, graphene oxide and liquid phase solvent mix by modes such as mechanical agitation, ball milling or sonic oscillations.
This hydrothermal/solvent thermal response still is the autoclave of sealing, by heating, reactor internal liquid phase solvent is gasified, thus provide reaction under high pressure environment in course of reaction.The temperature retention time of this hydrothermal/solvent thermal response can be 2 hours ~ 24 hours.Naturally cool to room temperature after reaction, open reactor and filter the solid product obtained, be described anode composite material, namely Graphene-FeOF composite material.
Refer to Fig. 1, as shown in the figure, nanoscale FeOF particle (40 nm × 100 nm) is dispersed on graphene oxide lamella the pattern of product graphene oxide-FeOF composite material.Refer to Fig. 2, characterized the solid product of synthesis by XRD, the diffraction maximum in spectrogram can be attributed to other diffraction maximums in graphene oxide (peak at 11.8 ° of places, arrow marks) and FeOF(spectrogram respectively).FeF can be proved thus 3with graphene oxide after the mixed solution hydro-thermal reaction of ethanol and deionized water, graphene oxide-FeOF composite material can be converted into completely.This nano composite material can as excellent anode material for lithium-ion batteries.
The raw material FeF that above-mentioned reaction adopts 3and the synthetic method of graphene oxide is not limit, FeF in the present embodiment 33H 2the preparation method of O comprises the following steps;
By surfactant (as CTAB) ultrasonic disperse in deionized water;
Add iron chloride to be dissolved in this deionized water, obtain Fe 3+solution; And
Under agitation by this Fe 3+dropwise instills in hydrofluoric acid solution, continues to be stirred to react completely.
The solid product obtained further by centrifugation, and with ethanol washing to neutral, can obtain FeF after oven dry 33H 2o.
Adopt Hummers method to prepare graphene oxide in the present embodiment, preparation method comprises the following steps:
In ice-water bath, graphite, sodium nitrate, 1 concentrated sulfuric acid are mixed and stir;
Add potassium permanganate, continue to be stirred to graphite and be fully oxidized;
In reactant, add deionized water and hydrogen peroxide, be stirred to and react completely.
The solid product obtained further by centrifugation, can obtain graphene oxide suspension.
Embodiment 1
Three hydration ferric flouride FeF 33H 2the preparation of O: 0.1g CTAB is joined in 30mL deionized water, ultrasonic disperse; Then add 18 g FeCl wherein 36H 2o obtains Fe 3+solution; Under strong stirring, by Fe 3+dropwise instillation HF(38%, 50mL) among, continue to stir 2h to reacting completely.Centrifugal and with ethanol washing to neutral, dry 10h under 60 ° of C will to be deposited in a conventional oven, to obtain three hydration ferric flouride FeF 33H 2o.
The preparation of graphene oxide: adopt Hummers method to prepare graphene oxide, experimentation is: by 5 g graphite, 2.5 g sodium nitrate, 115 mL concentrated sulfuric acid mixing in ice-water bath, strong stirring 30 min; Add 30 g potassium permanganate wherein, after continuing to stir 5h, graphite is fully oxidized; In reactant, adding 200 mL deionized waters continue stirring 20 min, adding 400mL deionized water and 20mL hydrogen peroxide (30%) to reacting completely.Centrifugal 5000 rpm/30 min, lose below precipitation, get upper oxide graphene suspension (4 mg/mL) and save backup.
The preparation of Graphene-FeOF composite material: get prepared graphene oxide suspension (4 mg/mL) 10 mL, with the FeF prepared by 80 mg 33H 2o, 25mL ethanol mixes, ultrasonic disperse 30 min; Then mixed liquor is placed in water heating kettle, is warming up to 120 ° of C, is incubated 10 h.Then naturally cool to room temperature.
The preparation method of anode composite material provided by the invention utilizes graphene oxide both as reaction raw materials and FeF 3carry out chemical reaction, again as the conductive agent in anode composite material, increase the conductivity of FeOF.Because graphene oxide comprises one deck or which floor carbon atomic layer, surface is containing oxygen-containing functional group, and have good dispersiveness in aqueous, FeOF can be created on surface of graphene oxide uniformly.Because Graphene has good conductivity, larger specific area and good mechanical property performance, can as the carrier of FeOF nano particle; After forming composite material with FeOF nano particle, in electrochemical process, Graphene plays and transmits electronics, increases conductivity, prevents the effects such as reunion, buffer volumes change.
In addition, those skilled in the art also can do other changes in spirit of the present invention, and certainly, these changes done according to the present invention's spirit, all should be included within the present invention's scope required for protection.

Claims (10)

1. an anode composite material, is characterized in that, is Graphene-FeOF composite material, comprises the FeOF particle by chemical bonds and Graphene.
2. anode composite material as claimed in claim 1, it is characterized in that, the grain size of this FeOF particle is 1 nm ~ 10 μm.
3. anode composite material as claimed in claim 1, it is characterized in that, in this anode composite material, the mass percentage of FeOF is 2% ~ 98%.
4. anode composite material as claimed in claim 1, it is characterized in that, in this anode composite material, the mass percentage of FeOF is 70% ~ 95%.
5. anode composite material as claimed in claim 1, it is characterized in that, this FeOF particle in-situ is created on this graphenic surface.
6. an anode composite material, is characterized in that, is functionalization graphene, comprises the carbon atomic layer by FeOF particle and Graphene, and the carbon atomic layer of this FeOF particle and Graphene passes through chemical bonds.
7. a preparation method for anode composite material, it comprises the following steps:
Ferric flouride and graphene oxide are uniformly mixed to form a solidliquid mixture in liquid phase solvent; And
By this solidliquid mixture in hydrothermal/solvent thermal response still 80 DEG C ~ 250 DEG C carry out hydrothermal/solvent thermal response.
8. the preparation method of anode composite material as claimed in claim 7, it is characterized in that, this ferric flouride is FeF 33H 2o, FeF 30.33H 2o, Fe 1.9f 4.750.95H 2o, FeF 2.50.5H 2o, FeF 3h 2o and amorphous FeF 3in at least one.
9. the preparation method of anode composite material as claimed in claim 7, it is characterized in that, this liquid phase solvent is the combination of water and ethanol.
10. the preparation method of anode composite material as claimed in claim 7, it is characterized in that, the temperature retention time of this hydrothermal/solvent thermal response is 2 hours ~ 24 hours.
CN201410500300.6A 2014-09-26 2014-09-26 Composite positive electrode material and preparation method thereof Active CN104282882B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201410500300.6A CN104282882B (en) 2014-09-26 2014-09-26 Composite positive electrode material and preparation method thereof
PCT/CN2015/090103 WO2016045558A1 (en) 2014-09-26 2015-09-21 Composite positive electrode material and preparation method therefor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410500300.6A CN104282882B (en) 2014-09-26 2014-09-26 Composite positive electrode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN104282882A true CN104282882A (en) 2015-01-14
CN104282882B CN104282882B (en) 2017-01-11

Family

ID=52257554

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410500300.6A Active CN104282882B (en) 2014-09-26 2014-09-26 Composite positive electrode material and preparation method thereof

Country Status (2)

Country Link
CN (1) CN104282882B (en)
WO (1) WO2016045558A1 (en)

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016045558A1 (en) * 2014-09-26 2016-03-31 江苏华东锂电技术研究院有限公司 Composite positive electrode material and preparation method therefor
CN110060886A (en) * 2019-05-20 2019-07-26 常熟理工学院 A kind of preparation method of fiber/graphene/FeOF/Ag flexible electrode material
CN110136976A (en) * 2019-05-20 2019-08-16 常熟理工学院 A kind of fiber/graphene/carbon quantum dot/FeOF flexible electrode material preparation method
CN111082024A (en) * 2019-12-30 2020-04-28 中科廊坊过程工程研究院 Coating material, preparation method and application thereof
CN112542581A (en) * 2019-09-20 2021-03-23 华中科技大学 Method for preparing pre-lithiation agent in electrochemical process
CN113422028A (en) * 2021-06-29 2021-09-21 沈阳化工大学 Preparation method of battery positive electrode composite material
CN113488623A (en) * 2021-07-08 2021-10-08 西北大学 Thermal battery anode composite material and preparation method and application thereof
CN113871591A (en) * 2021-09-24 2021-12-31 中国科学院过程工程研究所 Iron-based electrode material and preparation method and application thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112563488B (en) * 2020-11-18 2023-02-21 上海空间电源研究所 Mixed-valence iron-based fluoride cathode material and preparation method thereof
CN112687881B (en) * 2020-12-28 2022-03-29 中国科学院过程工程研究所 Ferric oxyfluoride cathode material, preparation method thereof and lithium ion battery
CN115156238B (en) * 2022-07-12 2023-05-30 华南理工大学 Comprehensive recycling method for aluminum electrolysis waste cathode carbon blocks and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101562248A (en) * 2009-06-03 2009-10-21 龚思源 Graphite composite lithium ion battery anode material lithium iron phosphate and preparation method thereof
CN101752561A (en) * 2009-12-11 2010-06-23 中国科学院宁波材料技术与工程研究所 Graphite alkene iron lithium phosphate positive active material, preparing method thereof, and lithium ion twice battery based on the graphite alkene modified iron lithium phosphate positive active material
CN101800310A (en) * 2010-04-02 2010-08-11 中国科学院苏州纳米技术与纳米仿生研究所 Method for preparing graphene-doped anode material for lithium-ion batteries
CN102169987A (en) * 2011-01-14 2011-08-31 南京大学 Graphene-supported porous nickel oxide and preparation method thereof, and application of graphene-supported porous nickel oxide in lithium ion battery anode material
CN103199253A (en) * 2013-03-31 2013-07-10 马军昌 Preparation method of graphene-ferric fluoride composite cathode material
CN103718352A (en) * 2011-06-22 2014-04-09 国立大学法人九州大学 Method for producing iron oxyfluoride positive electrode active substance and iron oxyfluoride positive electrode active substance
CN103730655A (en) * 2014-01-21 2014-04-16 中国计量学院 Preparation method of LiMn2O4-graphene composite positive electrode material

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102583298B (en) * 2012-02-18 2014-03-26 无锡合志科技有限公司 Preparation method of lithium iron phosphate compounded by graphite fluoride as cathode material of secondary lithium battery
CN103022483A (en) * 2012-12-07 2013-04-03 南京工业大学 Preparation method for positive electrode material of power lithium ion battery
KR101817260B1 (en) * 2013-02-22 2018-01-11 삼성전자주식회사 Graphene-nanomaterial composite, electrode and electric device including the graphene-nanomaterial composite, and method of manufacturing the graphene-nanomaterial composite
CN103560231A (en) * 2013-09-27 2014-02-05 江苏华东锂电技术研究院有限公司 Lithium ion battery anode composite material and its preparation method
CN104282882B (en) * 2014-09-26 2017-01-11 江苏华东锂电技术研究院有限公司 Composite positive electrode material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101562248A (en) * 2009-06-03 2009-10-21 龚思源 Graphite composite lithium ion battery anode material lithium iron phosphate and preparation method thereof
CN101752561A (en) * 2009-12-11 2010-06-23 中国科学院宁波材料技术与工程研究所 Graphite alkene iron lithium phosphate positive active material, preparing method thereof, and lithium ion twice battery based on the graphite alkene modified iron lithium phosphate positive active material
CN101800310A (en) * 2010-04-02 2010-08-11 中国科学院苏州纳米技术与纳米仿生研究所 Method for preparing graphene-doped anode material for lithium-ion batteries
CN102169987A (en) * 2011-01-14 2011-08-31 南京大学 Graphene-supported porous nickel oxide and preparation method thereof, and application of graphene-supported porous nickel oxide in lithium ion battery anode material
CN103718352A (en) * 2011-06-22 2014-04-09 国立大学法人九州大学 Method for producing iron oxyfluoride positive electrode active substance and iron oxyfluoride positive electrode active substance
CN103199253A (en) * 2013-03-31 2013-07-10 马军昌 Preparation method of graphene-ferric fluoride composite cathode material
CN103730655A (en) * 2014-01-21 2014-04-16 中国计量学院 Preparation method of LiMn2O4-graphene composite positive electrode material

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016045558A1 (en) * 2014-09-26 2016-03-31 江苏华东锂电技术研究院有限公司 Composite positive electrode material and preparation method therefor
CN110060886A (en) * 2019-05-20 2019-07-26 常熟理工学院 A kind of preparation method of fiber/graphene/FeOF/Ag flexible electrode material
CN110136976A (en) * 2019-05-20 2019-08-16 常熟理工学院 A kind of fiber/graphene/carbon quantum dot/FeOF flexible electrode material preparation method
CN112542581A (en) * 2019-09-20 2021-03-23 华中科技大学 Method for preparing pre-lithiation agent in electrochemical process
CN111082024A (en) * 2019-12-30 2020-04-28 中科廊坊过程工程研究院 Coating material, preparation method and application thereof
CN113422028A (en) * 2021-06-29 2021-09-21 沈阳化工大学 Preparation method of battery positive electrode composite material
CN113488623A (en) * 2021-07-08 2021-10-08 西北大学 Thermal battery anode composite material and preparation method and application thereof
CN113871591A (en) * 2021-09-24 2021-12-31 中国科学院过程工程研究所 Iron-based electrode material and preparation method and application thereof

Also Published As

Publication number Publication date
WO2016045558A1 (en) 2016-03-31
CN104282882B (en) 2017-01-11

Similar Documents

Publication Publication Date Title
CN104282882B (en) Composite positive electrode material and preparation method thereof
Li et al. Electrochemically activated MnO cathodes for high performance aqueous zinc-ion battery
Chen et al. In situ nitrogenated graphene–few-layer WS 2 composites for fast and reversible Li+ storage
CN104051729B (en) NiFe for cathode of lithium battery2o4the preparation method of/graphene composite material
CN101937985B (en) Graphene/titanium dioxide lithium ion battery cathode material and preparation method
WO2019114205A1 (en) Mxene-metal composite material and preparation method therefor
WO2011069348A1 (en) Lithium iron phosphate positive electrode active material modified by graphene, preparation method and lithium ion secondary battery thereof
CN104966812A (en) Three-dimensional porous quasi-graphene loaded molybdenum disulfide composite and preparation method thereof
CN104966824A (en) Nitrogen-doped porous carbon sphere and cobaltous oxide nano-composite anode material based on chitosan and derivatives thereof and preparation method thereof
CN100517812C (en) Production method of lithium secondary battery drop water ferric fluoride anode material
CN102709057A (en) Method for preparing composite of grapheme with different oxidation degrees and manganese dioxide
CN110518228B (en) Inorganic nanoparticle embedded three-dimensional grapheme carbon nanocomposite and application thereof
CN104900858A (en) Preparation method for sodium-ion battery antimony/carbon anode composite material with yolk-shell structure
CN104009212A (en) Preparation method of graphene-based nanosilicon compound electrode material
Liu et al. Solid-state mechanochemistry advancing two dimensional materials for lithium-ion storage applications: A mini review
CN106025241A (en) Graphene aerogel loaded lithium iron phosphate porous composite material and preparation method thereof
CN102244255A (en) Novel cathode material of vanadium oxide nanometer lithium ion battery and preparation method thereof
CN104577126A (en) Method for preparing MWCNT@a-C@Co9S8 composite electrode material with uniform morphology and application of material in lithium electrode
Zhang et al. A large area mesh-like MoS2 with an expanded interlayer distance synthesized by one-pot method and lithium storage performance
Yu et al. Synthesis of zinc-cobalt bimetallic oxide anchored on the surface of rice husk carbon as anode for high-performance lithium ion battery
CN114314673A (en) Preparation method of flaky FeOCl nano material
Wang et al. ZIF-67-derived porous nitrogen-doped carbon shell encapsulates photovoltaic silicon cutting waste as anode in high-performance lithium-ion batteries
Wang et al. High-capacity and cycling-stable anode for sodium ion batteries constructed from SnS2/MWCNTs nanocomposites
Dong et al. Self-activation effect in bimetallic MgMn2O4 and boosting its electrochemical performance using metal-organic framework template for magnesium-ion battery cathodes
CN114094078A (en) Nitrogen-doped carbon-coated metal sulfide heterojunction material, preparation method and battery application

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant