CN103956492B - A kind of preparation method of conducting polymer composite coating beta-LiVOPO4 anode material for lithium-ion batteries - Google Patents

A kind of preparation method of conducting polymer composite coating beta-LiVOPO4 anode material for lithium-ion batteries Download PDF

Info

Publication number
CN103956492B
CN103956492B CN201410206279.9A CN201410206279A CN103956492B CN 103956492 B CN103956492 B CN 103956492B CN 201410206279 A CN201410206279 A CN 201410206279A CN 103956492 B CN103956492 B CN 103956492B
Authority
CN
China
Prior art keywords
livopo
lithium
polymer composite
conducting polymer
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.)
Expired - Fee Related
Application number
CN201410206279.9A
Other languages
Chinese (zh)
Other versions
CN103956492A (en
Inventor
任慢慢
杨铭志
乔从德
刘伟良
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.)
Qilu University of Technology
Original Assignee
Qilu University of 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 Qilu University of Technology filed Critical Qilu University of Technology
Priority to CN201410206279.9A priority Critical patent/CN103956492B/en
Publication of CN103956492A publication Critical patent/CN103956492A/en
Application granted granted Critical
Publication of CN103956492B publication Critical patent/CN103956492B/en
Expired - Fee Related 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
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Composite Materials (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

Disclosure one conducting polymer composite coating beta-LiVOPO4The preparation method of anode material for lithium-ion batteries.It is characterized in that and utilizes conducting polymer composite to β-LiVOPO4It is coated with, thus improving β-LiVOPO4Electronic conductivity and charge/discharge capacity.Comprise the following steps: prepare β-LiVOPO by sol-gel process4, then by prepared β-LiVOPO4After mixing with conducting polymer composite monomer, cause conductive high polymer monomer polymerization by initiator, it is achieved conducting polymer composite is to β-LiVOPO4Cladding.The material that the present invention prepares has good electrical conductivity and charge/discharge capacity.This method has the advantages such as flow process is short, process is simple, energy consumption is low, cost is little.

Description

A kind of preparation method of conducting polymer composite coating beta-LiVOPO4 anode material for lithium-ion batteries
Technical field
The invention belongs to the preparation field of lithium ion battery electrode material, relate to one and utilize conducting polymer composite monomer polymerization to β-LiVOPO4Carry out being coated with the method preparing anode material for lithium-ion batteries.Conducting polymer composite coating beta-the LiVOPO of preparation4Anode material for lithium-ion batteries has good chemical property.
Background technology
LiVOPO4There are two kinds of space structure α-LiVOPO4With β-LiVOPO4。α-LiVOPO4Belong to anorthic system space group.And β-LiVOPO4Belong to rhombic system space group, be by the unlimited VO of shared drift angle6Octahedra chain and PO4 3-Tetrahedron shares summit in plane and is formed.Usual LiVOPO4The preparation of material is all obtained by the wet chemical method such as ion exchange and Electrochemical lithiation.Barker seminar reports at " JournalofTheElectrochemicalSociety " magazine 2004,151 (6): A796 ~ A800 and has synthesized β-LiVOPO by carbothermic method4Material, when charge-discharge magnification is C/50, the reversible capacity of material is 135mAh/g, de-/embedding lithium to lithium current potential at 3.9V.Kerr seminar reports by chemical method by ε-phase VOPO at " ElectrochemicalandSolid-StateLetters " magazine 2000,3 (10): 460 ~ 4624Materials synthesis α-LiVOPO4Material.
β-LiVOPO4During as lithium ion secondary battery anode material, the intercalation/deintercalation of lithium ion depends on V4+/V5+Reduction electricity to reversible transition.The charging platform of material is at 4.05V, and discharge platform is at 3.91V, and theoretical discharge capacity can reach 160mAh/g.Due to β-LiVOPO4Electronic conductivity that material self is relatively low and charge/discharge capacity, therefore, to β-LiVOPO4Carry out the study on the modification of conducting polymer cladding.
Summary of the invention
The present invention seeks to utilize conducting polymer composite coating beta-LiVOPO4Anode material for lithium-ion batteries.The method process is simple, energy consumption is low, cost is little, and the β-LiVOPO of pure phase compared by the material prepared4Material has higher electrical conductivity and discharge capacity, and under 0.1C multiplying power, during discharge and recharge, discharge capacity can reach 130mAh/g.
Conducting polymer composite coating beta-LiVOPO provided by the invention4The preparation method of anode material for lithium-ion batteries comprises the following steps:
(1) vanadium source, phosphoric acid root and lithium source are mixed in the ratio of 1:1:1, mixture is dispersed in a certain amount of deionized water, it is sufficiently stirred for, it is subsequently adding a certain amount of oxalic acid or citric acid, stable colloidal sol is formed after being sufficiently stirred for, evaporating water at 80～160 DEG C, it is thus achieved that dry solid product, wherein vanadium source, oxalic acid or citric acid, deionized water amount of substance than for 1:1～5:100～300；
(2) by solid product presintering 2～10h under 200～400 ° of C dry described in step (1), it is thus achieved that precursors, then by the precursors of acquisition at 400～800 DEG C of roasting 3～8h, β-LiVOPO is prepared4Positive electrode；
(3) by β-LiVOPO described in step (2)4Positive electrode and conducting polymer composite monomer are sufficiently stirred at-10～20 DEG C of temperature, are formed and stablize suspension, are subsequently adding appropriate mineral acid, regulating suspension pH value is 3～5, it is subsequently adding initiator, stirs 5～24h, wherein monomer, initiator and β-LiVOPO4The ratio of amount of substance be 1:1～2:1～5；
(4) after the reaction described in step (3) is sufficiently complete, stirring, filtration washing, it is thus achieved that there is the β-LiVOPO of conducting polymer composite surface coating layer are stopped4Positive electrode.
Further, in described step, vanadium source is at least one in vanadic anhydride, ammonium metavanadate, vanadium dioxide or Vanadium sesquioxide.
Further, in described step, phosphoric acid root is at least one in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate or diammonium phosphate.
Further, in described step, lithium source is at least one in lithium carbonate, Quilonorm (SKB) or lithium nitrate.
Further, in described step, conducting polymer composite monomer is the one in aniline, pyrroles or thiophene.
Further, in described step, mineral acid is at least one in hydrochloric acid, sulphuric acid, phosphoric acid or nitric acid.
Further, in described step, initiator is at least one in acyl class peroxide, hydroperoxides, esters peroxide or inorganic peroxide initiator.
The invention have the characteristics that preparation process technique is simple, flow process is short, production cost is low；Conducting polymer composite coating beta-the LiVOPO prepared4Anode material for lithium-ion batteries, under 0.1C multiplying power, during discharge and recharge, discharge capacity can reach 130mAh/g, has good chemical property.
Accompanying drawing illustrates:
Fig. 1 is the XRD figure spectrum of sample in embodiment 1；
Fig. 2 is the TEM collection of illustrative plates of sample in embodiment 1.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the invention will be further described.Following example are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1: with vanadic anhydride, oxalic acid, ammonium dihydrogen phosphate, lithium carbonate, aniline, hydrochloric acid and Ammonium persulfate. for initial feed.Vanadic anhydride and oxalic acid is weighed in deionized water than 1:4 by amount of substance, 60min is stirred at 60 DEG C, so as to form blue sol, wherein the amount of substance of vanadic anhydride and deionized water is than for 1:270, then in this colloidal sol, vanadium source is pressed: phosphoric acid root: the amount of lithium source substance adds ammonium dihydrogen phosphate and lithium carbonate than 1:2:1, after continuing mixing 30min, fully dry at 100 DEG C, by drying product, first at 300 DEG C, predecomposition 6h prepares precursors, precursors continues roasting 6h at 550 DEG C and prepares β-LiVOPO4；β-LiVOPO is weighed than 2:1 by amount of substance4With aniline monomer in deionized water, so as to be uniformly mixed at 10 DEG C, adding hydrochloric acid adjustment PH in this solution is about 3, continues stirring 2h, then presses aniline in this solution: initiator amount of substance adds Ammonium persulfate. than for 1:1；24h is stirred at 10 DEG C；Namely β-the LiVOPO of polyaniline-coated is obtained after finally being dried by prepared solution sucking filtration4Positive electrode.Material under 0.1C multiplying power first discharge capacity be 130mAh/g.
Embodiment 2: with vanadic anhydride, oxalic acid, ammonium dihydrogen phosphate, lithium carbonate, pyrroles, hydrochloric acid and Ammonium persulfate. for initial feed.Vanadic anhydride and citric acid is weighed in deionized water than 1:5 by amount of substance, 120min is stirred at 90 DEG C, so as to form blue sol, wherein the amount of substance of vanadic anhydride and deionized water is than for 1:400, then in this colloidal sol, vanadium source is pressed: phosphoric acid root: the amount of lithium source substance adds ammonium dihydrogen phosphate and lithium carbonate than 1:2:1, continue mixing 30min, fully dry at 100 DEG C, by drying product, first at 300 DEG C, predecomposition 4h prepares precursors, precursors continues roasting 6h at 500 DEG C and prepares β-LiVOPO4；β-LiVOPO is weighed than 2:1 by amount of substance4With pyrrole monomer in deionized water, so as to be uniformly mixed at 10 DEG C；Then adding hydrochloric acid adjustment PH in this solution is about 3, continues stirring 2h；Then by pyrroles in this solution: initiator amount of substance adds Ammonium persulfate. than for 1:1；24h is stirred at 10 DEG C；Namely β-the LiVOPO of polypyrrole cladding is obtained after finally being dried by prepared solution sucking filtration4Positive electrode.Material under 0.1C multiplying power first discharge capacity be 127mAh/g.
Embodiment 3: with vanadic anhydride, oxalic acid, ammonium dihydrogen phosphate, Quilonorm (SKB), thiophene, hydrochloric acid and Ammonium persulfate. for initial feed.Vanadic anhydride and oxalic acid is weighed in deionized water than 1:3 by amount of substance, 150min is stirred at 30 DEG C, so as to form blue sol, wherein the amount of substance of vanadic anhydride and deionized water is than for 1:350, then in this colloidal sol, vanadium source is pressed: phosphoric acid root: the amount of lithium source substance adds ammonium dihydrogen phosphate and Quilonorm (SKB) than 1:2:2, continue mixing 30min, fully dry at 100 DEG C, by drying product, first under 300 ° of C, predecomposition 5h prepares precursors, precursors continues roasting 4h at 600 DEG C and prepares β-LiVOPO4；β-LiVOPO is weighed than 2:1 by amount of substance4With thiophene monomer in deionized water, so as to be uniformly mixed at 10 DEG C；Then adding hydrochloric acid adjustment PH in this solution is about 3, continues stirring 2h；Then in this solution, thiophene is pressed: initiator amount of substance adds Ammonium persulfate. than for 1:1；24h is stirred at 10 DEG C；Namely β-the LiVOPO of polythiophene cladding is obtained after finally being dried by prepared solution sucking filtration4Positive electrode.Material under 0.1C multiplying power first discharge capacity be 129mAh/g.

Claims (6)

1. a conducting polymer composite coating beta-LiVOPO4The preparation method of anode material for lithium-ion batteries, it is characterised in that comprise the following steps:
(1) vanadium source, phosphoric acid root and lithium source are mixed in the ratio of 1:1:1, mixture is dispersed in a certain amount of deionized water, it is sufficiently stirred for, it is subsequently adding a certain amount of oxalic acid or citric acid, stable colloidal sol is formed after being sufficiently stirred for, evaporating water at 80～160 DEG C, it is thus achieved that dry solid product, wherein vanadium source, oxalic acid or citric acid, deionized water amount of substance than for 1:1～5:100～300；
(2) by solid product presintering 2～10h at 200～400 DEG C dry described in step (1), it is thus achieved that precursors, then by the precursors of acquisition at 400～800 DEG C of roasting 3～8h, β-LiVOPO is prepared4Positive electrode；
(3) by β-LiVOPO described in step (2)4Positive electrode and conducting polymer composite monomer are sufficiently stirred at-10～20 DEG C of temperature, are formed and stablize suspension, are subsequently adding appropriate mineral acid, regulating suspension pH value is 3～5, it is subsequently adding initiator, stirs 5～24h, wherein monomer, initiator and β-LiVOPO4The ratio of amount of substance be 1:1～2:1～5, described monomer is aniline, pyrroles or thiophene；
(4) after the reaction described in step (3) is sufficiently complete, stirring, filtration washing, it is thus achieved that there is the β-LiVOPO of conducting polymer composite surface coating layer are stopped4Positive electrode.
2. a kind of conducting polymer composite coating beta-LiVOPO as claimed in claim 14The preparation method of anode material for lithium-ion batteries, is characterized in that the vanadium source described in step (1) is at least one in vanadic anhydride, ammonium metavanadate, vanadium dioxide or Vanadium sesquioxide.
3. a kind of conducting polymer composite coating beta-LiVOPO as claimed in claim 14The preparation method of anode material for lithium-ion batteries, is characterized in that the phosphoric acid root described in step (1) is at least one in phosphoric acid, ammonium phosphate, ammonium dihydrogen phosphate or diammonium phosphate.
4. a kind of conducting polymer composite coating beta-LiVOPO as claimed in claim 14The preparation method of anode material for lithium-ion batteries, is characterized in that the lithium source described in step (1) is at least one in lithium carbonate, Quilonorm (SKB) or lithium nitrate.
5. a kind of conducting polymer composite coating beta-LiVOPO as claimed in claim 14The preparation method of anode material for lithium-ion batteries, is characterized in that the mineral acid described in step (3) is at least one in hydrochloric acid, sulphuric acid, phosphoric acid or nitric acid.
6. a kind of conducting polymer composite coating beta-LiVOPO as claimed in claim 14The preparation method of anode material for lithium-ion batteries, is characterized in that the initiator described in step (3) is at least one in acyl class peroxide, esters peroxide or inorganic peroxide initiator.
CN201410206279.9A 2014-05-16 2014-05-16 A kind of preparation method of conducting polymer composite coating beta-LiVOPO4 anode material for lithium-ion batteries Expired - Fee Related CN103956492B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410206279.9A CN103956492B (en) 2014-05-16 2014-05-16 A kind of preparation method of conducting polymer composite coating beta-LiVOPO4 anode material for lithium-ion batteries

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410206279.9A CN103956492B (en) 2014-05-16 2014-05-16 A kind of preparation method of conducting polymer composite coating beta-LiVOPO4 anode material for lithium-ion batteries

Publications (2)

Publication Number Publication Date
CN103956492A CN103956492A (en) 2014-07-30
CN103956492B true CN103956492B (en) 2016-07-06

Family

ID=51333741

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410206279.9A Expired - Fee Related CN103956492B (en) 2014-05-16 2014-05-16 A kind of preparation method of conducting polymer composite coating beta-LiVOPO4 anode material for lithium-ion batteries

Country Status (1)

Country Link
CN (1) CN103956492B (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104393292A (en) * 2014-11-12 2015-03-04 齐鲁工业大学 Preparation Method of lithium ion battery positive electrode material alpha-LiVOPO4
CN108155367A (en) * 2017-12-29 2018-06-12 国联汽车动力电池研究院有限责任公司 A kind of positive electrode and its anode pole piece of conducting polymer cladding nickle cobalt lithium manganate

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1674329A (en) * 2005-02-21 2005-09-28 武汉理工大学 Electric catalyst with compound conducing high polymer modification one-dimensional nano carbon as carrier and preparation
CN103227318A (en) * 2013-04-02 2013-07-31 东莞新能源科技有限公司 Silicon-based composite material, preparation method and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101237036B (en) * 2008-01-21 2010-06-02 湘潭大学 Making method for positive material LiFePO4 of poly-aniline coated lithium ion battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1674329A (en) * 2005-02-21 2005-09-28 武汉理工大学 Electric catalyst with compound conducing high polymer modification one-dimensional nano carbon as carrier and preparation
CN103227318A (en) * 2013-04-02 2013-07-31 东莞新能源科技有限公司 Silicon-based composite material, preparation method and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
新型锂离子电池正极材料LiVOPO4 的制备与表征;何则强等;《无机化学学报》;20080228;第24卷(第2期);1.1 LiVOPO4的制备 *

Also Published As

Publication number Publication date
CN103956492A (en) 2014-07-30

Similar Documents

Publication Publication Date Title
US20200328406A1 (en) Layered lithium-rich manganese-based cathode material with olivine structured limpo4 surface modification and preparation method thereof
CN105692576B (en) Method for preparing battery-grade FePO4 from industrial iron-containing waste
CN105140489B (en) A kind of titanium doped carbon coating phosphoric acid ferrisodium material and preparation method thereof
CN103956485B (en) Lithium iron phosphate electrode material of a kind of three-dimensional hierarchical structure and preparation method thereof
CN108878877B (en) Positive electrode active material for aqueous zinc ion secondary battery and aqueous zinc ion secondary battery
CN108046231A (en) A kind of sodium-ion battery positive material and preparation method thereof
CN103078114B (en) A kind of porous calcium phosphate iron lithium/carbon complex microsphere and preparation method thereof
CN104078676B (en) A kind of preparation method of vanadyl phosphate sodium/graphene composite material
CN103762362A (en) Hydrothermal preparation method of nano lithium iron manganese phosphate anode material
CN102244244B (en) Method for improving tap density of composite anode material xLiFePO4.yLi3V2(PO4)3 of lithium ion battery
Gao et al. A gelatin-based sol–gel procedure to synthesize the LiFePO4/C nanocomposite for lithium ion batteries
Huang et al. Design and synthesis of high-rate micron-sized, spherical LiFePO4/C composites containing clusters of nano/microspheres
CN108039458A (en) A kind of sodium-ion battery positive material and its preparation method and application
CN103682276A (en) Preparation method for cathode material LiVOPO4/C adopting sheet structure for lithium ion battery
CN101989653B (en) Spherical anode materials for lithium ion batteries connected by ultramicro particles and preparation method thereof
CN105322145A (en) Lithium ferric manganese phosphate/graphene/ carbon composite material and preparation method and application
CN104810513B (en) A kind of lithium ion battery negative material and preparation method thereof
CN107293723B (en) Binder-free Na3V2(PO4)3/C lithium ion battery composite anode and preparation method thereof
CN103413918A (en) Synthetic method for cathode material lithium cobaltous phosphate used for lithium ion batteries
CN103413940B (en) A kind of synthetic method of positive material nano lithium manganese phosphate of lithium ion battery
CN103956492B (en) A kind of preparation method of conducting polymer composite coating beta-LiVOPO4 anode material for lithium-ion batteries
CN102983332A (en) Preparation method for lithium iron phosphate material of positive electrode of lithium ion secondary battery
CN104779393A (en) Method for preparing lithium-vanadium-phosphate lithium ion battery positive material by means of liquid phase reduction
CN104332612B (en) P Modification carbon-coated lithium ion battery anode composite material and Preparation method and use
CN106169568A (en) A kind of preparation method of anode material for lithium-ion batteries carbon cladding phosphoric acid vanadium lithium

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160706

Termination date: 20170516

CF01 Termination of patent right due to non-payment of annual fee