CN106374106A - Preparing method of lithium cobalt phosphate cathode material - Google Patents

Preparing method of lithium cobalt phosphate cathode material Download PDF

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Publication number
CN106374106A
CN106374106A CN201611005490.XA CN201611005490A CN106374106A CN 106374106 A CN106374106 A CN 106374106A CN 201611005490 A CN201611005490 A CN 201611005490A CN 106374106 A CN106374106 A CN 106374106A
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China
Prior art keywords
cobalt
lithium
phosphate
positive electrode
mixture
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CN201611005490.XA
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Chinese (zh)
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陈厚勇
徐冬明
树荣亮
陈荣华
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Shuangdeng Group Co Ltd
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Shuangdeng Group Co Ltd
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Priority to CN201611005490.XA priority Critical patent/CN106374106A/en
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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
    • H01M4/58—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
    • 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
    • H01M4/362—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
    • H01M4/62—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

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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 provides a preparing method of a lithium cobalt phosphate cathode material, and relates to the technical field of lithium ion battery. The material simultaneously covers carbon and graphene, wherein the carbon and the graphene both contain specific contents. The preparing method comprises the steps of carrying out ball-milling mixing and ultrasonic treatment, and conducting reasonable restrictions on burning temperature and time. The obtained cathode material has uniform structure refinement, improves both specific surface area and conductivity, effectively promotes electrochemical performance and satisfies operating requirements of lithium batteries in the field of high power application.

Description

A kind of preparation method of cobalt phosphate lithium positive electrode
Technical field
The present invention relates to technical field of lithium ion, more particularly to a kind of preparation side of cobalt phosphate lithium positive electrode Method.
Background technology
There is the cobalt phosphate lithium positive electrode of olivine structural, because it has higher theoretical specific capacity (167mah/g), And there is higher discharge platform (4.8v), and it is described as " 5v " material, in the field higher to high power requirements, such as aviation boat My god, the field such as electric motor car can be more exposed to welcome.
The chemical property of cobalt phosphate lithium positive electrode is limited by many-sided reason: the electronics of cobalt phosphate lithium material is led Electric rate is relatively low；Cycle performance has much room for improvement；Higher voltage platform makes electrolyte decomposition serious.Mainly pass through at present to improve it Preparation method, metal ion elements doping, synthesize composite material and work out more stable electrolyte and to lift C.I. Pigment Violet 14 The performance of lithium material, but still fail to solve that cobalt phosphate lithium positive electrode electronic conductivity is low, and it is few to put a capacity, cycle performance The problem limiting its application of difference.
Content of the invention
It is an object of the invention to overcoming the deficiencies in the prior art, just providing a kind of cobalt phosphate lithium of excellent electrochemical performance The preparation method of pole material.
The present invention is achieved through the following technical solutions:
A kind of preparation method of cobalt phosphate lithium positive electrode, thes improvement is that, li:co:p=1:1:1 weighs respectively in molar ratio Lithium salts, cobalt salt and phosphate, add ethanol, the gross weight of salt and the ratio of ethanol are 1g:1ml-1g:2ml, ball milling in ball grinder Vacuum drying after mixing, then be placed in 300-450 DEG C of calcination 5h-6h under inert atmosphere in Muffle furnace and obtain mixture；Again will be above-mentioned Mixture with account for licopo4The carbon source of the 2wt%-10wt% carbon content of/c/g quality of materials is mixed and is incorporated in ball grinder plus ethanol, The ratio of the gross weight of mixture and carbon source and ethanol be 1g:1ml-1g:2ml, after ball milling mixing with account for licopo4/ c/g material The graphene film of the 0.5wt%-10wt% of material quality is dissolved in solvent jointly, and solvent is ethanol or pure water, the weight of mixture Ratio with solvent is 1g:25ml-1g:50ml, and 80～85 DEG C of heating of water-bath after sonicated 0.5-10h remove solvent and obtain Mixture；Then said mixture is put in 600-800 DEG C of Muffle furnace, after calcination 6-24 hour under reducing atmosphere Obtain described cobalt phosphate lithium positive electrode.
Described lithium salts is Lithium hydrate, lithium carbonate, lithium oxalate, Quilonorm (SKB), at least one reason device in lithium chloride lithium nitrate； Described cobalt salt is cobalt acetate, cobalt oxalate, cobalt nitrate, cobalt oxide, at least one in cobaltous chloride；Described phosphate is biphosphate At least one in ammonium, diammonium phosphate, ammonium phosphate；Described carbon source is white carbon black, sucrose, glucose, at least one in graphite； Described reducing atmosphere adopts hydrogen/hydrogen-argon-mixed.
In prior art, traditional high-temperature solid phase reaction method due to can not be fully contacted between raw material, and for a long time Under the conditions of high-temperature heat treatment, the crystalline phase eventually resulting in the material obtaining differs, the unordered irregular, size of the pattern of crystal Have a very wide distribution, and the Nomenclature Composition and Structure of Complexes ultimately generating product would generally present non-metering ratio and inhomogeneities, is unfavorable for The raising of the chemical property of material.The present invention can make sufficiently to contact between raw material by mechanical ball milling, but also permissible Reduce the particle diameter of material, and then improve the overall specific surface area of material and electrical conductivity.Calcination temperature to mixture and calcination Time proposes scientific and reasonable scope, is conducive to material electrical property to improve.
The present invention mainly coats cobalt phosphate lithium material with carbon and Graphene simultaneously.Its role is to: cobalt phosphate lithium table Face carbon coated can lift its electric conductivity, have the Graphene material of ultra-high conductivity on this basis again in one layer of Surface coating Material, can lift the electric conductivity of cobalt phosphate lithium further, and then lift its chemical property.
The invention has the beneficial effects as follows:
Carbon and graphene coated do not affect on the crystal formation of cobalt phosphate lithium material, remain as olivine structural.
Carbon and graphene coated can lift the electric conductivity of cobalt phosphate lithium material well, and then lift its electrochemistry Energy.
The present invention uses ball milling solid phase method it is easy to operation, makes sufficiently to contact between raw material, but also can reduce material Particle diameter, and then improve the overall specific surface area of material and electrical conductivity.
Brief description
Fig. 1 is the scanning electron microscope (SEM) photograph (sem) of cobalt phosphate lithium material in the technology of the present invention.
Fig. 2 is the X-ray diffraction pattern (xrd) of cobalt phosphate lithium material in the technology of the present invention.
Fig. 3 is the blank sample licopo of uncoated Graphene4Discharge performance curve under/c different multiplying.
Fig. 4 is the licopo of graphene coated4Discharge performance curve under/c/g sample different multiplying.
Specific embodiment
With reference to specific embodiment, the present invention is described in further detail, to help those skilled in the art's reason The solution present invention.
Embodiment 1:
First li:co:p=1:1:1 weighs lithium carbonate, cobalt acetate and the ammonium phosphate of 0.012mol respectively in molar ratio, in ball grinder Plus vacuum drying after 10ml ethanol ball milling mixing, then it is placed in the lower 350 DEG C of calcination 5h of nitrogen inert atmosphere in Muffle furnace and is mixed Thing；
Again the white carbon black of said mixture and the 5wt% carbon content accounting for active substance quality is mixed and be incorporated in ball grinder plus 10ml second Jointly it is dissolved in 100ml alcohol solvent, supersound process with the graphene film of the 0.5wt% accounting for active substance quality after alcohol ball milling mixing After 5h, 80 DEG C of heating removing solvents of water-bath obtain mixture；
Then said mixture is put in 650 DEG C of Muffle furnace, calcination under hydrogen argon mixing reducing atmosphere obtained institute after 8 hours State cobalt phosphate lithium positive electrode.
Embodiment 2:
First li:co:p=1:1:1 weighs 0.012mol lithium oxalate, cobalt nitrate and ammonium dihydrogen phosphate, respectively in ball grinder in molar ratio In plus 10ml ethanol ball milling mixing after vacuum drying, then be placed in the lower 400 DEG C of calcination 5h of inert atmosphere in Muffle furnace and obtain mixture ⅰ；
Again the graphite of said mixture and the 5wt% carbon content accounting for active substance quality is mixed and be incorporated in ball grinder plus 10ml second Jointly it is dissolved in 100ml etoh solvent solvent, ultrasonic place with the graphene film of the 1wt% accounting for active substance quality after alcohol ball milling mixing After reason 5h, 80 DEG C of heating removing solvents of water-bath obtain mixture；
Then said mixture is put in 750 DEG C of Muffle furnace, calcination under hydrogen argon mixing reducing atmosphere obtained institute after 8 hours State cobalt phosphate lithium positive electrode.
Embodiment 3:
First li:co:p=1:1:1 weighs 0.012mol Quilonorm (SKB), cobalt oxide and ammonium phosphate respectively in molar ratio, adds in ball grinder Vacuum drying after 10ml ethanol ball milling mixing, then be placed in the lower 450 DEG C of calcination 5h of inert atmosphere in Muffle furnace and obtain mixture；
Again the sucrose of said mixture and the 5wt% carbon content accounting for active substance quality is mixed and be incorporated in ball grinder plus 10ml second Jointly it is dissolved in 100ml etoh solvent solvent, ultrasonic place with the graphene film of the 2wt% accounting for active substance quality after alcohol ball milling mixing After reason 5h, 80 DEG C of heating removing solvents of water-bath obtain mixture；
Then said mixture is put in 650 DEG C of Muffle furnace, calcination under mixing reducing atmosphere obtained described phosphorus after 8 hours Sour cobalt lithium anode material.
Embodiment 4:
First li:co:p=1:1:1 weighs 0.012mol Lithium hydrate, cobalt oxide and diammonium phosphate, respectively in ball milling in molar ratio Add vacuum drying after 10ml ethanol ball milling mixing in tank, then be placed in the lower 350 DEG C of calcination 5h of inert atmosphere in Muffle furnace and mixed Thing；
Again the white carbon black of said mixture and the 5wt% carbon content accounting for active substance quality is mixed and be incorporated in ball grinder plus 10ml second Jointly it is dissolved in 100ml alcohol solvent, supersound process 5h with the graphene film of the 5wt% accounting for active substance quality after alcohol ball milling mixing 80 DEG C of heating removing solvents of water-bath obtain mixture afterwards；
Then said mixture is put in 650 DEG C of Muffle furnace, calcination under mixing reducing atmosphere obtained described phosphorus after 8 hours Sour cobalt lithium anode material.
Embodiment 5:
First li:co:p=1:1:1 claims 0.012mol amount lithium carbonate, cobaltous chloride and ammonium phosphate respectively in molar ratio, adds in ball grinder Vacuum drying after 10ml ethanol ball milling mixing, then be placed in the lower 400 DEG C of calcination 5h of inert atmosphere in Muffle furnace and obtain mixture；
Again the graphite of said mixture and the 5wt% carbon content accounting for active substance quality is mixed and be incorporated in ball grinder plus 10ml second Jointly it is dissolved in 100ml alcohol solvent, supersound process 5h with the graphene film of the 10wt% accounting for active substance quality after alcohol ball milling mixing 80 DEG C of heating removing solvents of water-bath obtain mixture afterwards；
Then said mixture is put in 700 DEG C of Muffle furnace, calcination under mixing reducing atmosphere obtained described phosphorus after 8 hours Sour cobalt lithium anode material.
Above-described embodiment be presently preferred embodiments of the present invention, be not used for limiting the scope of the present invention, thus all with this Equivalence changes or modification that feature described in bright claim and principle are done, all should include scope of the invention as claimed it Interior.
Fig. 1 is licopo4The sem figure of/c/g sample, as can be seen from the figure licopo4The pattern of nano-particle do not advise Then, cobalt phosphate lithium sample particle is attached on Graphene, is combined togather well therewith.
Fig. 2 is licopo4/ c and licopo4The xrd figure of/c/g, the as can be seen from the figure diffraction maximum of all samples and mark Quasi- pdf card #32-0552 corresponds, and there is no miscellaneous peak, illustrates that the sample obtaining is the licopo of pure phase4Material, does not have Impurity is had to generate.
Fig. 3 and Fig. 4 is respectively licopo4/ c and licopo4Discharge performance curve under/c/g sample different multiplying, from figure In as can be seen that licopo4Discharge capacity under the conditions of 0.1c, 0.5c, 1c, 2c multiplying power for/c sample is respectively 129.1mah/ G, 96.8 mah/g, 84.7 mah/g, 60.1 mah/g, the licopo of graphene coated4/ c/g sample 0.1c, 0.5c, 1c, Discharge capacity under the conditions of 2c multiplying power is respectively 148.6mah/g, 121.9mah/g, 110.1mah/g, 93.4 mah/g.Graphite The sample of alkene cladding either all shows higher specific discharge capacity under low range or under high magnification, and Graphene bag is described It is covered with the chemical property helping lift cobalt phosphate lithium positive electrode.

Claims (6)

1. a kind of preparation method of cobalt phosphate lithium positive electrode it is characterised in that in molar ratio li:co:p=1:1:1 weigh respectively Lithium salts, cobalt salt and phosphate, add ethanol, the gross weight of salt and the ratio of ethanol are 1g:1ml-1g:2ml, ball milling in ball grinder Vacuum drying after mixing, then be placed in 300-450 DEG C of calcination 5h-6h under inert atmosphere in Muffle furnace and obtain mixture；Again will be above-mentioned Mixture with account for licopo4The carbon source of the 2wt%-10wt% carbon content of/c/g quality of materials is mixed and is incorporated in ball grinder plus ethanol, The ratio of the gross weight of mixture and carbon source and ethanol be 1g:1ml-1g:2ml, after ball milling mixing with account for licopo4/ c/g material The graphene film of the 0.5wt%-10wt% of material quality is dissolved in solvent jointly, and solvent is ethanol or pure water, the weight of mixture Ratio with solvent is 1g:25ml-1g:50ml, and 80～85 DEG C of heating of water-bath after sonicated 0.5-10h remove solvent and obtain Mixture；Then said mixture is put in 600-800 DEG C of Muffle furnace, after calcination 6-24 hour under reducing atmosphere Obtain described cobalt phosphate lithium positive electrode.
2. the preparation method of cobalt phosphate lithium positive electrode as claimed in claim 1 is it is characterised in that described lithium salts is hydroxide At least one in lithium, lithium carbonate, lithium oxalate, Quilonorm (SKB), lithium chloride lithium nitrate.
3. the preparation method of cobalt phosphate lithium positive electrode as claimed in claim 1 is it is characterised in that described cobalt salt is cobalt acetate, grass At least one in sour cobalt, cobalt nitrate, cobalt oxide, cobaltous chloride.
4. the preparation method of cobalt phosphate lithium positive electrode as claimed in claim 1 is it is characterised in that described phosphate is di(2-ethylhexyl)phosphate At least one in hydrogen ammonium, diammonium phosphate, ammonium phosphate.
5. the preparation method of cobalt phosphate lithium positive electrode as claimed in claim 1 is it is characterised in that described carbon source is white carbon black, sugarcane At least one in sugar, glucose, graphite.
6. the preparation method of cobalt phosphate lithium positive electrode as claimed in claim 1 is it is characterised in that described reducing atmosphere adopts Hydrogen/hydrogen-argon-mixed.
CN201611005490.XA 2016-11-16 2016-11-16 Preparing method of lithium cobalt phosphate cathode material Pending CN106374106A (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103754856A (en) * 2014-01-24 2014-04-30 南京工业大学 Preparation method of positive electrode material lithium cobalt phosphate for lithium ion battery
CN105576204A (en) * 2015-12-23 2016-05-11 厦门大学 Graphene composite carbon-coated cobalt-lithium phosphate material and preparation methods and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103754856A (en) * 2014-01-24 2014-04-30 南京工业大学 Preparation method of positive electrode material lithium cobalt phosphate for lithium ion battery
CN105576204A (en) * 2015-12-23 2016-05-11 厦门大学 Graphene composite carbon-coated cobalt-lithium phosphate material and preparation methods and application thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
陈厚勇: ""锂离子电池正极材料磷酸钴锂的制备与改性"", 《（哈尔滨工业大学硕士毕业论文）万方数据库》 *

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