CN106229499A - A kind of preparation method of lithium ion battery MnO/Super P nanometer anode material - Google Patents

A kind of preparation method of lithium ion battery MnO/Super P nanometer anode material Download PDF

Info

Publication number
CN106229499A
CN106229499A CN201610828333.2A CN201610828333A CN106229499A CN 106229499 A CN106229499 A CN 106229499A CN 201610828333 A CN201610828333 A CN 201610828333A CN 106229499 A CN106229499 A CN 106229499A
Authority
CN
China
Prior art keywords
super
ion battery
lithium ion
mno
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
CN201610828333.2A
Other languages
Chinese (zh)
Inventor
曹丽云
王瑞谊
李瑞梓
许占位
黄剑锋
李嘉胤
王彩薇
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.)
Shaanxi University of Science and Technology
Original Assignee
Shaanxi University of Science and Technology
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 Shaanxi University of Science and Technology filed Critical Shaanxi University of Science and Technology
Priority to CN201610828333.2A priority Critical patent/CN106229499A/en
Publication of CN106229499A publication Critical patent/CN106229499A/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
    • 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
    • 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
    • H01M4/62—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 relates to the preparation method of a kind of lithium ion battery MnO/Super P nanometer anode material, comprise the following steps: weigh a certain amount of potassium permanganate and Super P, soluble in water, ultrasonic disperse, in 120 180 DEG C of hydro-thermal reaction 4 12h, by the product of gained 600 800 DEG C of heat treatment 1 4h in tube-type atmosphere furnace, obtain the complex of MnO/Super P；The inventive method technique is simple, environmental friendliness, and the negative material described in MnO/Super P prepared by the method has excellently chemical property.

Description

A kind of preparation method of lithium ion battery MnO/Super P nanometer anode material
Technical field
The invention belongs to field of lithium ion battery material, be specifically related to a kind of lithium ion battery MnO/Super P nanometer and bear The preparation method of pole material.
Background technology
Lithium ion battery owing to having high energy density, long cycle life, the advantage such as memory-less effect, and by extensively Ground is for the aspect such as electric automobile and hybrid vehicle.Along with people are more and more higher to energy seedbed demand, seek high power capacity Electrode material has become as the Hot spots for development of current research.Traditional negative material is material with carbon element, but due to its theoretical specific volume Measuring low, bulk density is little, easily comes off, it is impossible to meet people currently for the jumbo demand of small size, and when battery mistake When filling, there is also safety issue, so, researchers begin to explore another negative pole material that can substitute material with carbon element Material.
Transition metal oxide MnO is due to its ABUNDANT NATUREAL RESOURSES, low toxicity, low cost, high theoretical specific capacity (755.6mA h g-1) etc. feature, be widely used in the research of lithium ion battery negative material.But its maximally shortcoming lead exactly The lowest, and Super P is a kind of granular conductive black of armorphous nano, therefore the present invention uses and is combined with Super P Improve the electric conductivity of MnO, and then improve its chemical property.
Prepare the method for manganese oxide/carbon complex at present and mainly have hydro-thermal and heat treating process and sol-gal process subsequently. The MnO/C nanometer sheet of nucleocapsid structure prepared by manganous hydroxide presoma that Xing Zhang etc. is deposited by heat treatment and acetylene, follows Specific discharge capacity 563mA h g after ring 30 circle-1, when electric current density is 300mA g-1, reversible specific capacity is 550mA h g-1 [Zhang X,Xing Z,Wang L,et al.Synthesis of MnO@C core–shell nanoplates with controllable shell thickness and their electrochemical performance for lithium-ion batteries[J].Journal of Materials Chemistry,2012,22(34):17864- 17869.].The method preparation process is complicated, and the cyclical stability of product is poor.Changju Chae etc. are by with silicon nanometer Granule is that the method for template carbonization resorcinol resin glue cohesion compound prepares mesoporous carbon, then five water manganese nitrates is immersed in Jie Hole carbon is prepared MnO/C complex.At 2A g-1Electric current density under, specific discharge capacity is 320-345mA h g-1, circulate 100 Circle specific discharge capacity is 500mA h g-1。[Chae C,Park H,Kim D,et al.A Li-ion battery using LiMn 2O 4cathode and MnO x/C anode[J].Journal of Power Sources,2013,244:214- 221.].The method is prepared the performance of product and is increased, but preparation process is complicated, is unsuitable for large-scale industrial production.
Summary of the invention
It is an object of the invention to provide that a kind of technique is simple, environmental friendliness, there is the lithium-ion electric of excellent electrochemical performance The preparation method of pond MnO/Super P nanometer anode material.
For achieving the above object, its concrete technical scheme is as follows:
1) potassium permanganate is dissolved in deionized water, is configured to the potassium permanganate solution that mass fraction is 3%-15%；
2) take the Super P of 0.1-0.5g, join in potassium permanganate solution, ultrasonic disperse, obtain homodisperse molten Liquid；
3) by step 2) dispersion liquid of gained is transferred in politef water heating kettle carry out hydro-thermal reaction, by reacted Product washs, centrifugal, dries；
4) product of drying is placed in heat treatment in tube-type atmosphere furnace, i.e. can get end product.
Described step 3) in hydrothermal temperature be 120-180 DEG C, the time is 4-12h.
Described step 3) in washing liquid be deionized water and dehydrated alcohol.
Described step 4) in atmosphere be argon gas atmosphere.
Described step 4) in heat treatment temperature be 600-800 DEG C, the time is 1-4h.
The present invention, with potassium permanganate and Super P as raw material, prepares manganese dioxide and Super initially with hydro-thermal method P, complex, after carried out heat treatment, prepare MnO/Super P lithium ion battery negative material, as lithium-ion electric Pond negative material has the chemical property of excellence.Have that technique is simple, advantages of environment protection.As lithium ion battery negative Material, has the cyclical stability under higher reversible capacity and high current charge-discharge.
MnO/Super P lithium ion battery negative material synthesized by the present invention, owing to which introducing high conductivity Super P so that the electric conductivity of electrode material increases, the transmission speed of electronics is accelerated, so largely improving its Chemical property.
Accompanying drawing explanation
Fig. 1 is that SEM (scanning electron microscope) figure of MnO/Super P lithium ion battery negative material prepared by the present invention (amplifies Multiple 50,000 times).
Fig. 2 is XRD (X-ray diffraction) figure of MnO/Super P lithium ion battery negative material prepared by the present invention.
Fig. 3 is the cyclical stability figure of MnO/Super P lithium ion battery negative material prepared by the present invention.
Fig. 4 is the high rate performance figure of MnO/Super P lithium ion battery negative material prepared by the present invention.
Detailed description of the invention
Embodiment 1:
1) potassium permanganate is dissolved in deionized water, is configured to the potassium permanganate solution that mass fraction is 3%；
2) take the Super P of 0.1g, join in potassium permanganate solution, ultrasonic disperse, obtain homodisperse solution；
3) by step 2) dispersion liquid of gained is transferred to 120 DEG C of hydro-thermal reactions 12h in politef water heating kettle, and will reaction After product deionized water and absolute ethanol washing, centrifugal, dry；
4) product of drying is placed in 600 DEG C of heat treatment 4h in the tube-type atmosphere furnace of argon gas atmosphere, i.e. available final product Thing.
Embodiment 2:
1) potassium permanganate is dissolved in deionized water, is configured to the potassium permanganate solution that mass fraction is 5%；
2) take the Super P of 0.2g, join in potassium permanganate solution, ultrasonic disperse, obtain homodisperse solution；
3) by step 2) dispersion liquid of gained is transferred to 140 DEG C of hydro-thermal reactions 8h in politef water heating kettle, and will reaction After product deionized water and absolute ethanol washing, centrifugal, dry；
4) product of drying is placed in 700 DEG C of heat treatment 2h in the tube-type atmosphere furnace of argon gas atmosphere, i.e. available final product Thing.
Embodiment 3:
1) potassium permanganate is dissolved in deionized water, is configured to the potassium permanganate solution that mass fraction is 8%；
2) take the Super P of 0.3g, join in potassium permanganate solution, ultrasonic disperse, obtain homodisperse solution；
3) by step 2) dispersion liquid of gained is transferred to 160 DEG C of hydro-thermal reactions 6h in politef water heating kettle, and will reaction After product deionized water and absolute ethanol washing, centrifugal, dry；
4) product of drying is placed in 600 DEG C of heat treatment 3h in the tube-type atmosphere furnace of argon gas atmosphere, i.e. available final product Thing.
Embodiment 4:
1) potassium permanganate is dissolved in deionized water, is configured to the potassium permanganate solution that mass fraction is 10%；
2) take the Super P of 0.4g, join in potassium permanganate solution, ultrasonic disperse, obtain homodisperse solution；
3) by step 2) dispersion liquid of gained is transferred to 180 DEG C of hydro-thermal reactions 4h in politef water heating kettle, and will reaction After product deionized water and absolute ethanol washing, centrifugal, dry；
4) product of drying is placed in 800 DEG C of heat treatment 1h in the tube-type atmosphere furnace of argon gas atmosphere, i.e. available final product Thing.
Embodiment 5:
1) potassium permanganate is dissolved in deionized water, is configured to the potassium permanganate solution that mass fraction is 12%；
2) take the Super P of 0.4g, join in potassium permanganate solution, ultrasonic disperse, obtain homodisperse solution；
3) by step 2) dispersion liquid of gained is transferred to 150 DEG C of hydro-thermal reactions 8h in politef water heating kettle, and will reaction After product deionized water and absolute ethanol washing, centrifugal, dry；
4) product of drying is placed in 700 DEG C of heat treatment 3h in the tube-type atmosphere furnace of argon gas atmosphere, i.e. available final product Thing.
Embodiment 6:
1) potassium permanganate is dissolved in deionized water, is configured to the potassium permanganate solution that mass fraction is 15%；
2) take the Super P of 0.5g, join in potassium permanganate solution, ultrasonic disperse, obtain homodisperse solution；
3) by step 2) dispersion liquid of gained is transferred to 140 DEG C of hydro-thermal reactions 10h in politef water heating kettle, and will reaction After product deionized water and absolute ethanol washing, centrifugal, dry；
4) product of drying is placed in 700 DEG C of heat treatment 1h in the tube-type atmosphere furnace of argon gas atmosphere, i.e. available final product Thing.
It will be seen from figure 1 that the MnO/Super P lithium ion battery negative material of preparation presents graininess shape equably Looks, granular size is about 40-50nm.
Figure it is seen that successfully prepared the MnO of Emission in Cubic by the preparation method of the present invention.
From figure 3, it can be seen that prepared MnO/Super P lithium ion battery negative material has excellently cyclicity Can, after circulation 75 circle, capacity is up to 690mA h g-1。
From fig. 4, it can be seen that prepared MnO/Super P lithium ion battery negative material has the most forthright Can, it is 5Ag in electric current density-1Time, it is possible to keep 260mA hg-1Capacity, in the playback circulation under different electric current densities After, capacity can clearly return to initial capacity, and slightly above initial capacity.

Claims (5)

1. the preparation method of a lithium ion battery MnO/Super P nanometer anode material, it is characterised in that include following step Rapid:
1) potassium permanganate is dissolved in deionized water, is configured to the potassium permanganate solution that mass fraction is 3%-15%；
2) take the Super P of 0.1-0.5g, join in potassium permanganate solution, ultrasonic disperse, obtain homodisperse solution；
3) by step 2) dispersion liquid of gained is transferred in politef water heating kettle carry out hydro-thermal reaction, by reacted product Washing, centrifugal, dry；
4) product of drying is placed in heat treatment in tube-type atmosphere furnace, i.e. can get end product.
Its spy of the preparation method of a kind of lithium ion battery MnO/Super P nanometer anode material the most according to claim 1 Levy and be: described step 3) in hydrothermal temperature be 120-180 DEG C, the time is 4-12h.
Its spy of the preparation method of a kind of lithium ion battery MnO/Super P nanometer anode material the most according to claim 1 Levy and be: described step 3) in washing liquid be deionized water and dehydrated alcohol.
Its spy of the preparation method of a kind of lithium ion battery MnO/Super P nanometer anode material the most according to claim 1 Levy and be: described step 4) in atmosphere be argon gas atmosphere.
Its spy of the preparation method of a kind of lithium ion battery MnO/Super P nanometer anode material the most according to claim 1 Levy and be: described step 4) in heat treatment temperature be 600-800 DEG C, the time is 1-4h.
CN201610828333.2A 2016-09-18 2016-09-18 A kind of preparation method of lithium ion battery MnO/Super P nanometer anode material Pending CN106229499A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610828333.2A CN106229499A (en) 2016-09-18 2016-09-18 A kind of preparation method of lithium ion battery MnO/Super P nanometer anode material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610828333.2A CN106229499A (en) 2016-09-18 2016-09-18 A kind of preparation method of lithium ion battery MnO/Super P nanometer anode material

Publications (1)

Publication Number Publication Date
CN106229499A true CN106229499A (en) 2016-12-14

Family

ID=58076439

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610828333.2A Pending CN106229499A (en) 2016-09-18 2016-09-18 A kind of preparation method of lithium ion battery MnO/Super P nanometer anode material

Country Status (1)

Country Link
CN (1) CN106229499A (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115642254A (en) * 2022-09-28 2023-01-24 南方海洋科学与工程广东省实验室(湛江) Conductive composite material, preparation method and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120258367A1 (en) * 2011-04-06 2012-10-11 Industry-Academic Coorperation Foundation, Yonsei University Nanocomposite material, method for preparing the same, and energy storage device including the same
CN102760583A (en) * 2012-07-13 2012-10-31 郑州轻工业学院 Hollow honeycomb MnO2/C micro nanosphere and microrod preparation method
CN102810673A (en) * 2012-08-16 2012-12-05 山东大学 Method for preparing carbon-coated MnO coaxial nanowire cathode material for lithium ion batteries
CN102983321A (en) * 2012-12-24 2013-03-20 福州大学 Carbon-coated MnOx nano energy storage material with one-dimensional core-shell structure and preparation method thereof
CN103022463A (en) * 2012-12-20 2013-04-03 中国东方电气集团有限公司 Manganese-based compound cathode material of lithium battery and preparation method of material
CN105047419A (en) * 2015-08-06 2015-11-11 清华大学 Manganese dioxide/carbon composite electrode material and preparation method thereof, and super capacitor
CN105185977A (en) * 2015-10-13 2015-12-23 陕西科技大学 Method for preparing lithium ion battery cathode material

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120258367A1 (en) * 2011-04-06 2012-10-11 Industry-Academic Coorperation Foundation, Yonsei University Nanocomposite material, method for preparing the same, and energy storage device including the same
CN102760583A (en) * 2012-07-13 2012-10-31 郑州轻工业学院 Hollow honeycomb MnO2/C micro nanosphere and microrod preparation method
CN102810673A (en) * 2012-08-16 2012-12-05 山东大学 Method for preparing carbon-coated MnO coaxial nanowire cathode material for lithium ion batteries
CN103022463A (en) * 2012-12-20 2013-04-03 中国东方电气集团有限公司 Manganese-based compound cathode material of lithium battery and preparation method of material
CN102983321A (en) * 2012-12-24 2013-03-20 福州大学 Carbon-coated MnOx nano energy storage material with one-dimensional core-shell structure and preparation method thereof
CN105047419A (en) * 2015-08-06 2015-11-11 清华大学 Manganese dioxide/carbon composite electrode material and preparation method thereof, and super capacitor
CN105185977A (en) * 2015-10-13 2015-12-23 陕西科技大学 Method for preparing lithium ion battery cathode material

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
RUNG-CHUAN LEE ET AL.: ""Synthesis of high-performance MnOx/carbon composite as lithium-ion battery anode by a facile co-precipitation method: Effects of oxygen stoichiometry and carbon morphology"", 《JOURNAL OF POWER SOURCES》 *
XIANGYANG ZHOU ET AL.: ""Synthesis of three-dimensional cross-linked MnO@C composite as high-performance anode material for lithium-ion batteries"", 《INOICS》 *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115642254A (en) * 2022-09-28 2023-01-24 南方海洋科学与工程广东省实验室(湛江) Conductive composite material, preparation method and application thereof
CN115642254B (en) * 2022-09-28 2023-10-31 南方海洋科学与工程广东省实验室(湛江) Conductive composite material, preparation method and application thereof

Similar Documents

Publication Publication Date Title
CN105895886B (en) A kind of sodium-ion battery transition metal phosphide/porous anode composite and preparation method thereof
CN105355886B (en) A kind of sodium-ion battery positive pole Na2+2xFe2‑x(SO4)3@carbon composites and preparation method thereof
CN106876705B (en) Preparation method of in-situ synthesized carbon/carbon nanotube coated lithium iron phosphate composite material
CN108269982B (en) Composite material, preparation method thereof and application thereof in lithium ion battery
CN105280897B (en) A kind of preparation method of lithium ion battery negative material C/ZnO/Cu composites
CN108545774A (en) Porous vanadic anhydride micron ball electrode material and its preparation method and application
CN103956493B (en) The preparation method of carbon cladding hierarchical organization LiFePO4
CN101901903A (en) Preparation method of high activity lithium ion battery anode material lithium iron phosphate
CN108232167B (en) Carbon @ iron silicate hollow structure compound and preparation method thereof
CN102683649A (en) Method for preparing lithium ion battery carbon silicon anode material
CN104993116B (en) A kind of self assembly anode material for lithium-ion batteries V2O5Preparation method
CN110615480A (en) Method for preparing layered lithium manganate material by dynamic hydrothermal method
CN104466110B (en) Preparation method of high-performance lithium ion battery negative electrode material
CN108039486A (en) The hollow core shell structure vanadic anhydride anode electrode piece of tremelliform and its fastening lithium ionic cell preparation method
CN103413918B (en) A kind of synthetic method of anode material for lithium ion battery cobalt phosphate lithium
CN103928680A (en) Spray drying auxiliary synthesis method for preparing sheet type lithium manganese phosphate/graphene composite material
CN102386408B (en) Preparation method for manganese lithium borate cathode material of lithium ion battery
CN109888236B (en) Preparation method of lithium-sulfur battery positive electrode material
CN103159201B (en) A kind of high pressure, low temperature method preparing carbon-coated LiFePO 4 for lithium ion batteries anode composite material of lithium ion battery
CN105174240B (en) Nanometer rods assembling iron manganese phosphate for lithium microballoon, composite and preparation method thereof
CN105702938A (en) Iron-based oxide lithium ion battery negative electrode material and preparation method and application thereof
CN108270014A (en) A kind of supercritical carbon dioxide fluid prepares method and the application of silica/graphene composite material
CN110707299B (en) Vanadium oxide/carbon/clay composite positive electrode material, preparation method thereof and application thereof in water-based battery
CN107628639A (en) The preparation method of inner porosity spherical lithium titanate ion battery cathode material
CN106784724A (en) A kind of LiFePO4The solvent heat assistant preparation method of@C/rGO multistage composite microballoons

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20161214