CN107946584A - A kind of preparation method for the iron phosphate lithium positive pole composite material that carbon coating Fluorin doped is modified - Google Patents

A kind of preparation method for the iron phosphate lithium positive pole composite material that carbon coating Fluorin doped is modified Download PDF

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Publication number
CN107946584A
CN107946584A CN201711389881.0A CN201711389881A CN107946584A CN 107946584 A CN107946584 A CN 107946584A CN 201711389881 A CN201711389881 A CN 201711389881A CN 107946584 A CN107946584 A CN 107946584A
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lithium fluoride
lifepo
hydrogen phosphate
anode composite
ammonium hydrogen
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李蓓
刘天辉
袁波
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Luoyang Mingli Science and Technology Development Co Ltd
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Luoyang Mingli Science and Technology Development Co Ltd
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    • 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
    • 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
    • H01M4/58—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
    • H01M4/625—Carbon or graphite
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
    • 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

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

Abstract

The invention discloses the LiFePO4 (LiFePO that a kind of carbon coating Fluorin doped is modified4‑xFx/ C) anode composite material preparation method, using lithium fluoride, ferrous acetate, ammonium hydrogen phosphate, lithium fluoride as raw material, add absolute ethyl alcohol and DEXTROSE ANHYDROUS, it is dry after being ultrasonically treated；Grinding, then carries out double sintering, obtains LiFePO after desciccate is once sintered4‑xFx/ C anode composite materials, after which circulates 30 times under 0.1C, specific capacity conservation rate is more than 90%.

Description

A kind of preparation method for the iron phosphate lithium positive pole composite material that carbon coating Fluorin doped is modified
Technical field
The present invention relates to technical field of lithium batteries, and in particular to the LiFePO4 that a kind of carbon coating Fluorin doped is modified (LiFePO4-xFx/ C) anode composite material preparation method.
Background technology
With the development of electric automobile, the requirement for electrode material is higher and higher, especially positive electrode, positive electrode As the important component of lithium ion battery, its price accounts for 1/3rd of lithium ion battery cost, its be not only lithium from The carrier of sub- deintercalation, and provide lithium source for whole battery system.
The LiFePO of olivine structural4Abundance, cheap, nontoxic, the steady voltage platform of 3.5V are higher Specific capacity (about 170mAh/g), good stable circulation performance and security performance have attracted more and more researchers to pay close attention to And research.LiFePO4Material is also considered as the positive electrode of power-type lithium ion battery first choice.
Although LiFePO4 has the advantages that very much, its own intrinsic electricity as lithium ion secondary battery anode material The problem of subconductivity rate and relatively low lithium ion diffusion rate, has seriously affected its large-scale production and application.At present, asked for this Topic, can be solved using doping vario-property.
The content of the invention
A kind of the present invention is intended to provide LiFePO4 (LiFePO that carbon coating Fluorin doped is modified4-xFx/ C) cathode composite wood The preparation method of material, adds DEXTROSE ANHYDROUS, through ultrasound using lithium fluoride, ferrous acetate, ammonium hydrogen phosphate, lithium fluoride as raw material After handling and sintering, the iron phosphate lithium positive pole composite material of F doping vario-properties is made, after being circulated 30 times under 0.1C, specific capacity is protected Holdup is more than 90%, improves the chemical property of LiFePO4.
The object of the invention to solve the technical problems is realized using following technical scheme.Itd is proposed according to the present invention A kind of LiFePO4-xFxThe preparation method of/C anode composite materials, comprises the following steps：
(1) a certain amount of lithium fluoride, ferrous acetate, ammonium hydrogen phosphate are weighed, is put into beaker, absolute ethyl alcohol is added in beaker And DEXTROSE ANHYDROUS, after stirring evenly, a certain amount of lithium fluoride is added, is ultrasonically treated at 50 DEG C, supersonic frequency is 15KHz, ultrasonic time 30min；
(2) mixed solution after gained ultrasound is transferred to 80 DEG C of vacuum drying chamber to be dried；Desciccate shifts Into electron tubes type resistance furnace, the cooled to room temperature after 350 DEG C of sintering 3h, sintering, is fully ground under nitrogen protection；
(3) product after grinding is re-fed into electron tubes type resistance furnace and sinters 6h again in 500 DEG C, obtained LiFePO4-xFx/ C anode composite materials；
Lithium fluoride, ferrous acetate, ammonium hydrogen phosphate, the molar ratio of lithium fluoride are (1-x) in above-mentioned steps (1)：1:1：X, its In, x=0.05-0.1.
The object of the invention to solve the technical problems can be also applied to the following technical measures to achieve further.
A kind of foregoing LiFePO4-xFxThe preparation method of/C anode composite materials, wherein, anhydrous grape in step (1) The addition of sugar accounts for lithium fluoride, ferrous acetate, the 6-10% of ammonium hydrogen phosphate gross mass.
In F ion doping vario-property, F-Its cycle performance can be effectively improved in the Layered Structural Positive Electrode Materials doping of O, Suppress the phase transformation in its charge and discharge process, and can also further promote the growth of first stage particles, improve the volume specific volume of material Amount and tap density.
The present invention adds DEXTROSE ANHYDROUS using lithium fluoride, ferrous acetate, ammonium hydrogen phosphate, lithium fluoride as raw material, through ultrasound After handling and sintering, the iron phosphate lithium positive pole composite material of F doping vario-properties is made, after being circulated 30 times under 0.1C, specific capacity is protected Holdup is more than 90%, has excellent chemical property.
Embodiment
Illustrate the present invention referring to specific embodiment.These embodiments are merely to illustrate the present invention, its not with appoint Where formula limits the scope of the invention.
Embodiment 1
(1) a certain amount of lithium fluoride, ferrous acetate, ammonium hydrogen phosphate are weighed, is put into beaker, absolute ethyl alcohol is added in beaker And DEXTROSE ANHYDROUS, the addition of DEXTROSE ANHYDROUS account for lithium fluoride, ferrous acetate, the 8% of ammonium hydrogen phosphate gross mass.Stir evenly Afterwards, a certain amount of lithium fluoride is added, is ultrasonically treated at 50 DEG C, supersonic frequency 15KHz, ultrasonic time 30min；
Wherein, lithium fluoride, ferrous acetate, ammonium hydrogen phosphate, the molar ratio of lithium fluoride are (0.95)： 1:1：0.05；
(2) mixed solution after gained ultrasound is transferred to 80 DEG C of vacuum drying chamber to be dried；Desciccate shifts Into electron tubes type resistance furnace, the cooled to room temperature after 350 DEG C of sintering 3h, sintering, is fully ground under nitrogen protection；
(3) product after grinding is re-fed into electron tubes type resistance furnace and sinters 6h again in 500 DEG C, obtained LiFePO3.95F0.05/ C anode composite materials；
By the carbon-coated LiFePO4 (LiFePO of gained4/ C) anode composite material carries out circulation 30 times under 0.1C, and it is multiple The discharge capacity of condensation material is 130mAh/g, for the 92% of discharge capacity first.Illustrate the method preparation of the present invention LiFePO4-xFx/ C anode composite materials have excellent chemical property.
Embodiment 2
(1) a certain amount of lithium fluoride, ferrous acetate, ammonium hydrogen phosphate are weighed, is put into beaker, absolute ethyl alcohol is added in beaker And DEXTROSE ANHYDROUS, the addition of DEXTROSE ANHYDROUS account for lithium fluoride, ferrous acetate, the 7% of ammonium hydrogen phosphate gross mass.Stir evenly Afterwards, a certain amount of lithium fluoride is added, is ultrasonically treated at 50 DEG C, supersonic frequency 15KHz, ultrasonic time 30min；
Wherein, lithium fluoride, ferrous acetate, ammonium hydrogen phosphate, the molar ratio of lithium fluoride are 3.94： 1:1：0.06；
(2) mixed solution after gained ultrasound is transferred to 80 DEG C of vacuum drying chamber to be dried；Desciccate shifts Into electron tubes type resistance furnace, the cooled to room temperature after 350 DEG C of sintering 3h, sintering, is fully ground under nitrogen protection；
(3) product after grinding is re-fed into electron tubes type resistance furnace and sinters 6h again in 500 DEG C, obtained LiFePO3.95F0.05/ C anode composite materials；
By the carbon-coated LiFePO4 (LiFePO of gained4/ C) anode composite material carries out circulation 30 times under 0.1C, and it is multiple The discharge capacity of condensation material is 130mAh/g, for the 90% of discharge capacity first.Illustrate the method preparation of the present invention LiFePO4-xFx/ C anode composite materials have excellent chemical property.
Embodiment 3
(1) a certain amount of lithium fluoride, ferrous acetate, ammonium hydrogen phosphate are weighed, is put into beaker, absolute ethyl alcohol is added in beaker And DEXTROSE ANHYDROUS, the addition of DEXTROSE ANHYDROUS account for lithium fluoride, ferrous acetate, the 6% of ammonium hydrogen phosphate gross mass.Stir evenly Afterwards, a certain amount of lithium fluoride is added, is ultrasonically treated at 50 DEG C, supersonic frequency 15KHz, ultrasonic time 30min；
Wherein, lithium fluoride, ferrous acetate, ammonium hydrogen phosphate, the molar ratio of lithium fluoride are 3.92： 1:1：0.08；
(2) mixed solution after gained ultrasound is transferred to 80 DEG C of vacuum drying chamber to be dried；Desciccate shifts Into electron tubes type resistance furnace, the cooled to room temperature after 350 DEG C of sintering 3h, sintering, is fully ground under nitrogen protection；
(3) product after grinding is re-fed into electron tubes type resistance furnace and sinters 6h again in 500 DEG C, obtained LiFePO3.95F0.05/ C anode composite materials；
By the carbon-coated LiFePO4 (LiFePO of gained4/ C) anode composite material carries out circulation 30 times under 0.1C, and it is multiple The discharge capacity of condensation material is 130mAh/g, for the 93% of discharge capacity first.Illustrate the method preparation of the present invention LiFePO4-xFx/ C anode composite materials have excellent chemical property.
Embodiment 4
(1) a certain amount of lithium fluoride, ferrous acetate, ammonium hydrogen phosphate are weighed, is put into beaker, absolute ethyl alcohol is added in beaker And DEXTROSE ANHYDROUS, the addition of DEXTROSE ANHYDROUS account for lithium fluoride, ferrous acetate, the 10% of ammonium hydrogen phosphate gross mass.Stirring is equal After even, a certain amount of lithium fluoride is added, is ultrasonically treated at 50 DEG C, supersonic frequency 15KHz, ultrasonic time is 30min；
Wherein, lithium fluoride, ferrous acetate, ammonium hydrogen phosphate, the molar ratio of lithium fluoride are 3.9： 1:1：0.1；
(2) mixed solution after gained ultrasound is transferred to 80 DEG C of vacuum drying chamber to be dried；Desciccate shifts Into electron tubes type resistance furnace, the cooled to room temperature after 350 DEG C of sintering 3h, sintering, is fully ground under nitrogen protection；
(3) product after grinding is re-fed into electron tubes type resistance furnace and sinters 6h again in 500 DEG C, obtained LiFePO3.95F0.05/ C anode composite materials；
By the carbon-coated LiFePO4 (LiFePO of gained4/ C) anode composite material carries out circulation 30 times under 0.1C, and it is multiple The discharge capacity of condensation material is 130mAh/g, for the 96% of discharge capacity first.Illustrate the method preparation of the present invention LiFePO4-xFx/ C anode composite materials have excellent chemical property.
The above described is only a preferred embodiment of the present invention, limitation in any form is not done to the present invention, though So the present invention is disclosed above with preferred embodiment, but is not limited to the present invention, any to be familiar with this professional technology people Member, without departing from the scope of the present invention, when the technology contents using the disclosure above make a little change or modification For the equivalent embodiment of equivalent variations, as long as being the content without departing from technical solution of the present invention, the technical spirit according to the present invention To any simple modification, equivalent change and modification made for any of the above embodiments, in the range of still falling within technical solution of the present invention.

Claims (2)

  1. A kind of 1. LiFePO4-xFxThe preparation method of/C anode composite materials, it is characterised in that comprise the following steps：
    (1) a certain amount of lithium fluoride, ferrous acetate, ammonium hydrogen phosphate are weighed, is put into beaker, absolute ethyl alcohol and nothing are added in beaker Water glucose, after stirring evenly, adds a certain amount of lithium fluoride, is ultrasonically treated at 50 DEG C, supersonic frequency is 15KHz, ultrasonic time 30min；
    (2) mixed solution after gained ultrasound is transferred to 80 DEG C of vacuum drying chamber to be dried；Desciccate is transferred to very In empty tube type resistance furnace, the cooled to room temperature after 350 DEG C of sintering 3h, sintering, is fully ground under nitrogen protection；
    (3) product after grinding is re-fed into electron tubes type resistance furnace and sinters 6h again in 500 DEG C, obtain LiFePO4-xFx/C Anode composite material；
    Lithium fluoride, ferrous acetate, ammonium hydrogen phosphate, the molar ratio of lithium fluoride are (1-x) in above-mentioned steps (1)：1:1：X, wherein, x =0.05-0.1.
  2. 2. LiFePO as claimed in claim 14-xFxThe preparation method of/C anode composite materials, it is characterised in that in step (1) The addition of DEXTROSE ANHYDROUS accounts for lithium fluoride, ferrous acetate, the 6-10% of ammonium hydrogen phosphate gross mass.
CN201711389881.0A 2017-12-21 2017-12-21 A kind of preparation method for the iron phosphate lithium positive pole composite material that carbon coating Fluorin doped is modified Pending CN107946584A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103855393A (en) * 2014-03-12 2014-06-11 桂林理工大学 Preparation method of lithium iron phosphate with excellent rate performance and cycling performance
CN103855391A (en) * 2012-11-30 2014-06-11 海洋王照明科技股份有限公司 Fluorine lithium iron phosphate/graphene composite and preparation method and application thereof
CN104617293A (en) * 2013-11-04 2015-05-13 北京有色金属研究总院 Preparation method of fluorine-modified carbon-cladded lithium iron phosphate composite material

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103855391A (en) * 2012-11-30 2014-06-11 海洋王照明科技股份有限公司 Fluorine lithium iron phosphate/graphene composite and preparation method and application thereof
CN104617293A (en) * 2013-11-04 2015-05-13 北京有色金属研究总院 Preparation method of fluorine-modified carbon-cladded lithium iron phosphate composite material
CN103855393A (en) * 2014-03-12 2014-06-11 桂林理工大学 Preparation method of lithium iron phosphate with excellent rate performance and cycling performance

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