CN107359316A - A kind of anode material of lithium battery and preparation method thereof - Google Patents

A kind of anode material of lithium battery and preparation method thereof Download PDF

Info

Publication number
CN107359316A
CN107359316A CN201710342171.6A CN201710342171A CN107359316A CN 107359316 A CN107359316 A CN 107359316A CN 201710342171 A CN201710342171 A CN 201710342171A CN 107359316 A CN107359316 A CN 107359316A
Authority
CN
China
Prior art keywords
lithium battery
anode material
fluorinated graphene
manganese dioxide
lithium
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
CN201710342171.6A
Other languages
Chinese (zh)
Other versions
CN107359316B (en
Inventor
燕绍九
彭思侃
南文争
陈翔
王楠
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.)
Beijing Graphene Technology Research Institute Co Ltd
Original Assignee
AECC Beijing Institute of Aeronautical Materials
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 AECC Beijing Institute of Aeronautical Materials filed Critical AECC Beijing Institute of Aeronautical Materials
Priority to CN201710342171.6A priority Critical patent/CN107359316B/en
Publication of CN107359316A publication Critical patent/CN107359316A/en
Application granted granted Critical
Publication of CN107359316B publication Critical patent/CN107359316B/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
    • H01M4/362—Composites
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

Abstract

The present invention is a kind of anode material of lithium battery and preparation method thereof, and the positive electrode is the compound of manganese dioxide and fluorinated graphene, and preparation process comprises the following steps：Prepare single dispersing fluorinated graphene solution, prepare fluorinated graphene and manganese dioxide composite granule, heat treatment, grinding, sieving.Fluorinated graphene can form uniform three-dimensional composite system with manganese bioxide material in the present invention, be advantageous to improve the utilization rate of positive electrode applied to lithium primary battery, hence it is evident that improve the ratio energy of battery.Operation is simple for present invention process, is produced suitable for engineering, using the teaching of the invention it is possible to provide a kind of high power lithium battery positive electrode, have very big industry and commercial value.

Description

A kind of anode material of lithium battery and preparation method thereof
Technical field
The present invention is a kind of anode material of lithium battery and preparation method thereof, belongs to energy-storage composite material technical field.
Background technology
The development of social economy, people are to the performance requirement more and more higher of portable power source, various portable type electronic products The direction of supporting power supply to high-energy-density, high-power, long storage life, high security is developed.Lithium primary battery is due to excellent Different performance, is widely used in that sensor, camera, pacemaker, aircraft etc. be a variety of civilian and military field.Often at present The lithium primary battery seen includes, lithium manganese dioxide cell, lithium thionyl chloride cell, lithium-sulfur dioxide cell, lithium fluorine cell, lithium iron Battery etc..Wherein, lithium manganese dioxide cell is most widely used, and has discharge voltage high, and electric discharge is steady, active material cost is low Etc. advantage, but it is more relatively low than energy；And fluorocarbons is that theory is more electric than energy highest, lithium fluorine in lithium primary battery positive electrode Pond utiliztion ratio energy may be up to 250~800Wh/kg, but because fluorinated carbon material is costly, battery cryogenic property and high current Service behaviour is undesirable to be limited lithium fluorine cell practicality.
Graphene is a kind of New Two Dimensional nano material, has superpower electric conductivity, is the best material of current electric conductivity Material.Single-layer graphene has high-specific surface area (2630m2/ g), the electron mobility (200000cm of superelevation2/ VS) and thermal conductivity (5000W/m·K).New function material of the fluorinated graphene as graphene, had both maintained the bigger serface of graphene, Again because the introducing of fluorine atom brings the novel interface such as surface energy reduction, hydrophobicity enhancing and physical and chemical performance.It is fluorinated stone Black alkene is applied to lithium primary battery positive electrode, is advantageous to improve the infiltration of electrolyte and increases positive electrode reactivity face Product, material conductivity is improved, so as to effectively lift positive material utilization ratio, this has important for the ratio energy of raising lithium battery Meaning.Therefore above reason is based on, we have proposed following invention.
The content of the invention
The present invention is exactly to design for above-mentioned prior art situation and provide a kind of anode material of lithium battery and its preparation Method, its object is to for existing commercial lithium primary battery positive electrode capacity utilization it is low the defects of, utilize fluorographite The unique two-dimensional structure of alkene and excellent surface and interface property, modified manganese bioxide material commercial at present, make composite positive pole Capacity utilization and battery specific energy be improved significantly.
To achieve the above object, present invention employs following technical scheme：
Technical solution of the present invention proposes a kind of anode material of lithium battery, it is characterised in that：The chemical composition of the material and Percentage by weight is：Fluorinated graphene 5%~30%, manganese dioxide 70%~95%.
Technical solution of the present invention also proposes the method for preparing this kind of anode material of lithium battery, it is characterised in that：This method Step is as follows：
Step 1: the preparation of single dispersing fluorinated graphene solution
Fluorinated graphene is added in organic solvent, preparing uniform single dispersing using sonic oscillation mode is fluorinated stone Black alkene solution；
Step 2: manganese dioxide powder is added in the single dispersing fluorinated graphene solution that step 1 obtains, mixed Close solution；
Step 3: the mixed solution that step 2 is obtained is heated to 40~60 DEG C of constant temperature and synchronously carries out mechanical agitation, directly To drying；
Step 4: the powder after drying is placed in baking oven, carries out 300~320 DEG C of constant temperature, be heat-treated within 20~30 hours；
Step 5: the powder after step 4 is heat-treated is ground, sieving obtains the anode material of lithium battery.
The weight of the organic solvent is 19~199 times of fluorinated graphene weight.
The organic solvent is in absolute ethyl alcohol, isopropanol, ethylene glycol, 1-METHYLPYRROLIDONE or dimethylformamide It is a kind of.
Fluorinated graphene is fluorinated graphene nanometer sheet, and its maximum outside diameter size is 5~20 μm, and fluorine carbon atomic ratio is 0.6 ~1.1.
The sonic oscillation time in step 1 was more than 30 minutes.
The particle diameter of the manganese dioxide powder is 20~40 μm.
The particle diameter for the anode material of lithium battery that step 5 obtains is 10~30 μm.
By adopting the above-described technical solution, compared with prior art, beneficial effects of the present invention include：
1. the inventive method by ultrasonic disperse mode, solve the problems, such as fluorinated graphene easily reunite, be not easy it is scattered, Fluorinated graphene is realized to mix with the uniform of manganese dioxide powder.
2. the inventive method makes manganese dioxide powder equal by way of mechanical agitation is synchronously carried out with heating dry out solvent It is even to be dispersed in around fluorinated graphene, realize being uniformly distributed for fluorinated graphene and manganese dioxide interface.
3. the inventive method is favourable in 300~320 DEG C of constant temperature heat treatments by fluorinated graphene and manganese dioxide mixed powder In the specific surface area, the electrical conductivity that further improve composite positive pole, increase specific discharge capacity.
Embodiment
With reference to embodiment, the present invention will be described in detail.
Embodiment 1：
The step of preparing the method for anode material of lithium battery of the present invention is as follows：
Step 1: the preparation of single dispersing fluorinated graphene solution
It it is 15 μm by maximum outside diameter size, the 1g fluorinated graphene nanometer sheets that fluorine carbon ratio is 0.9 dissolve in 19g absolute ethyl alcohols In, glass bar is put into ultrasonic oscillation device ultrasound after stirring to prepare within 30 minutes uniform single dispersing fluorinated graphene molten Liquid；
Step 2: it is the single dispersing fluorinated graphene that 30 μm of manganese dioxide powder is added to that step 1 obtains by 5g particle diameters In solution, mixed solution is obtained；
Dried Step 3: the mixed solution that step 2 is obtained is put into baking oven, drying temperature be 50 DEG C, drying it is same Shi Jinhang mechanical agitations, until drying；
Step 4: the powder after drying is divided in baking oven, 300 DEG C of constant temperature of progress are heat-treated 20 hours；
Step 5: the powder after step 4 is heat-treated is ground, sieving obtains the lithium that particle diameter distribution is 10~30 μm Cell positive material.

Claims (8)

  1. A kind of 1. anode material of lithium battery, it is characterised in that：The chemical composition and percentage by weight of the material be：Fluorinated graphene 5%~30%, manganese dioxide 70%~95%.
  2. 2. prepare the method for the anode material of lithium battery described in claim 1, it is characterised in that：The step of this method, is as follows：
    Step 1: the preparation of single dispersing fluorinated graphene solution
    Fluorinated graphene is added in organic solvent, uniform single dispersing fluorinated graphene is prepared using sonic oscillation mode Solution；
    Step 2: manganese dioxide powder is added in the single dispersing fluorinated graphene solution that step 1 obtains, obtain mixing molten Liquid；
    Step 3: the mixed solution that step 2 is obtained is heated to 40~60 DEG C of constant temperature and synchronously carries out mechanical agitation, until drying It is dry；
    Step 4: the powder after drying is placed in baking oven, carries out 300~320 DEG C of constant temperature, be heat-treated within 20~30 hours；
    Step 5: the powder after step 4 is heat-treated is ground, sieving obtains the anode material of lithium battery.
  3. 3. the method according to claim 2 for preparing anode material of lithium battery, it is characterised in that：The weight of the organic solvent Measure as 19~199 times of fluorinated graphene weight.
  4. 4. the method according to claim 2 for preparing anode material of lithium battery, it is characterised in that：The organic solvent is nothing One kind in water-ethanol, isopropanol, ethylene glycol, 1-METHYLPYRROLIDONE or dimethylformamide.
  5. 5. the method according to claim 2 for preparing anode material of lithium battery, it is characterised in that：Fluorinated graphene is fluorination Graphene nanometer sheet, its maximum outside diameter size are 5~20 μm, and fluorine carbon atomic ratio is 0.6~1.1.
  6. 6. the method according to claim 2 for preparing anode material of lithium battery, it is characterised in that：Ultrasound in step 1 is shaken The time is swung more than 30 minutes.
  7. 7. the method according to claim 2 for preparing anode material of lithium battery, it is characterised in that：The manganese dioxide powder Particle diameter be 20~40 μm.
  8. 8. the method according to claim 2 for preparing anode material of lithium battery, it is characterised in that：The lithium electricity that step 5 obtains The particle diameter of pond positive electrode is 10~30 μm.
CN201710342171.6A 2017-05-16 2017-05-16 Lithium battery positive electrode material and preparation method thereof Active CN107359316B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201710342171.6A CN107359316B (en) 2017-05-16 2017-05-16 Lithium battery positive electrode material and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201710342171.6A CN107359316B (en) 2017-05-16 2017-05-16 Lithium battery positive electrode material and preparation method thereof

Publications (2)

Publication Number Publication Date
CN107359316A true CN107359316A (en) 2017-11-17
CN107359316B CN107359316B (en) 2020-08-11

Family

ID=60271133

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201710342171.6A Active CN107359316B (en) 2017-05-16 2017-05-16 Lithium battery positive electrode material and preparation method thereof

Country Status (1)

Country Link
CN (1) CN107359316B (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108054352A (en) * 2017-11-23 2018-05-18 中国航发北京航空材料研究院 A kind of high power lithium battery positive electrode and preparation method thereof
CN109755501A (en) * 2018-12-07 2019-05-14 上海汉行科技有限公司 Artificial gold quantum dot/fluorinated graphene combination electrode for sodium-ion battery
CN111952584A (en) * 2020-07-13 2020-11-17 深圳市秸川材料科技有限公司 Lithium battery
CN116365062A (en) * 2023-02-20 2023-06-30 惠州锂威新能源科技有限公司 Lithium phosphide-based composite material and preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102931408A (en) * 2012-11-21 2013-02-13 大连海洋大学 Graphene composite transition metal oxide nanofiber lithium ion battery electrode material and preparation method thereof
CN103956271A (en) * 2014-05-09 2014-07-30 天津工业大学 Manganese oxide/graphene porous microspheres, preparation method and energy storage application thereof
CN104538650A (en) * 2014-12-25 2015-04-22 贵州梅岭电源有限公司 Modified lithium/carbon fluoride battery
CN104900864A (en) * 2015-04-10 2015-09-09 武汉大学 Manganese dioxide/graphene lithium ion battery cathode material and preparation method thereof
CN106115787A (en) * 2016-06-21 2016-11-16 衡阳师范学院 A kind of MnO2/ graphene nanocomposite material and the electrode prepared thereof
CN106340633A (en) * 2016-11-24 2017-01-18 杭州启澄科技有限公司 Composite nano material for high performance lithium ion battery and preparation method thereof
CN106410181A (en) * 2016-11-10 2017-02-15 无锡市明盛强力风机有限公司 Preparation method of graphene composite containing MnO2 nanowires

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102931408A (en) * 2012-11-21 2013-02-13 大连海洋大学 Graphene composite transition metal oxide nanofiber lithium ion battery electrode material and preparation method thereof
CN103956271A (en) * 2014-05-09 2014-07-30 天津工业大学 Manganese oxide/graphene porous microspheres, preparation method and energy storage application thereof
CN104538650A (en) * 2014-12-25 2015-04-22 贵州梅岭电源有限公司 Modified lithium/carbon fluoride battery
CN104900864A (en) * 2015-04-10 2015-09-09 武汉大学 Manganese dioxide/graphene lithium ion battery cathode material and preparation method thereof
CN106115787A (en) * 2016-06-21 2016-11-16 衡阳师范学院 A kind of MnO2/ graphene nanocomposite material and the electrode prepared thereof
CN106410181A (en) * 2016-11-10 2017-02-15 无锡市明盛强力风机有限公司 Preparation method of graphene composite containing MnO2 nanowires
CN106340633A (en) * 2016-11-24 2017-01-18 杭州启澄科技有限公司 Composite nano material for high performance lithium ion battery and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YU LI等: "the tunable electrochemical performances of carbon fluorides/manganese dioxide hybrid cathodes by their arrangements", 《JOURNAL OF POWER SOURCES》 *
许耀 等: "氟化石墨烯用作一次锂电池正极材料的性能", 《新型碳材料》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108054352A (en) * 2017-11-23 2018-05-18 中国航发北京航空材料研究院 A kind of high power lithium battery positive electrode and preparation method thereof
CN109755501A (en) * 2018-12-07 2019-05-14 上海汉行科技有限公司 Artificial gold quantum dot/fluorinated graphene combination electrode for sodium-ion battery
CN111952584A (en) * 2020-07-13 2020-11-17 深圳市秸川材料科技有限公司 Lithium battery
CN116365062A (en) * 2023-02-20 2023-06-30 惠州锂威新能源科技有限公司 Lithium phosphide-based composite material and preparation method and application thereof

Also Published As

Publication number Publication date
CN107359316B (en) 2020-08-11

Similar Documents

Publication Publication Date Title
CN107316988B (en) A kind of composite positive pole and preparation method thereof for lithium fluorocarbon battery
CN107359316A (en) A kind of anode material of lithium battery and preparation method thereof
AU2015100978A4 (en) Dispersion method of composite conductive agent in li-ion capacitor electrode slurry
CN104716321B (en) A kind of silicon-nitrogen-doped carbon-nitrogen-doped graphene composite material and its preparation and application
CN106744857A (en) 3D printing Graphene metallic composite, preparation method and application
CN102376937A (en) Nanometer lithium titanate/graphene composite negative electrode material and preparation process thereof
CN104993138B (en) A kind of preparation method and applications of graphene composite material aeroge
CN106410199B (en) A kind of lithium ion battery graphene/ferro-tin alloy composite negative pole material preparation method
CN103078087B (en) A kind of preparation method of lithium titanate/carbon nano tube composite cathode material
CN105460917A (en) Nitrogen-doped carbon nanotube adopting hierarchical structure and preparation method
Wang et al. A facile route for PbO@ C nanocomposites: An electrode candidate for lead-acid batteries with enhanced capacitance
CN102891282A (en) Cathode preparation technique of lithium ion battery
CN107946553A (en) High graphitization three dimensional carbon nanotubes graphene composite material and its preparation and application
CN105870430A (en) Method for preparing three-dimensional graphene-phosphotungstate
CN103682277B (en) Hollow porous nickel oxide composite material of N doping carbon-coating parcel and preparation method thereof
CN107240720A (en) A kind of preparation method of modified carbon nano-tube doping solid polymer electrolyte
CN103545494B (en) The liquid-phase synthesis process of secondary lithium battery sub-micron bismuth-anode composite
CN109830668A (en) The method that lithium ion battery silicon-carbon cathode material is prepared using carbon nanotube
CN104393275A (en) Preparation method of carbon-coated lithium titanate battery material
CN107482196A (en) A kind of lithium ion battery composite nano materials and preparation method thereof
CN103647072B (en) A kind of nickel oxide surfaces carbon/nitrogen content is than the preparation method of adjustable nitrogen-doped carbon integument
CN105924963A (en) Preparation method of graphene/ ferric oxide/ polyaniline composite material
CN106549146B (en) A kind of method that In-situ reaction prepares graphene-based lithium-rich manganic acid lithium electrode material
CN105800613A (en) Preparation method for activated carbon based on graphene composite modification and used for supercapacitor
CN107611376A (en) A kind of preparation method of graphene parcel silicon particle composite

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
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20211206

Address after: No. 108, 1f, building 1, yard 3, Fengzhi East Road, Haidian District, Beijing 100094

Patentee after: BEIJING GRAPHENE TECHNOLOGY RESEARCH INSTITUTE Co.,Ltd.

Address before: 100095 Beijing 81 mailbox in Haidian District, Beijing

Patentee before: AECC BEIJING INSTITUTE OF AERONAUTICAL MATERIALS