CN105514429A - Technology for preparing composite electrode material with ball milling-high temperature calcination method - Google Patents

Technology for preparing composite electrode material with ball milling-high temperature calcination method Download PDF

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Publication number
CN105514429A
CN105514429A CN201510972828.8A CN201510972828A CN105514429A CN 105514429 A CN105514429 A CN 105514429A CN 201510972828 A CN201510972828 A CN 201510972828A CN 105514429 A CN105514429 A CN 105514429A
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ball milling
temperature calcination
electrode material
ball
high temperature
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邬石根
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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
    • 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)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

The invention provides a technology for preparing a composite electrode material with a ball milling-high temperature calcination method. For a high temperature solid phase method, the mixing uniformity is limited, the particle size is not uniform, and the material performance is affected. According to the technology, before high temperature calcination of the lithium iron phosphate composite electrode material, synthesis raw materials are subjected to ball milling, so that metal particles are fully powdered and completely react in the high temperature solid phase process, and the technology has bright application prospect in the preparation technology of the electrode material.

Description

A kind of ball milling-high-temperature calcination prepares the technique of combination electrode material
Technical field
The present invention relates to a kind of electrode material, particularly a kind of LiFePO utilizing ball milling-high-temperature calcination preparation to add Co 4the technique of combination electrode material, belongs to field of batteries.
Background technology
Within 1912, lithium metal battery is proposed by GilbertN.Lewis the earliest and studies, and because the chemical characteristic of lithium metal is very active, makes environmental requirement very high, so lithium battery is not applied for a long time.Along with the development of science and technology, present lithium battery becomes main flow.But lithium battery majority is secondary cell, also once property battery.Life-span and the fail safe of the secondary cell of minority are poor.Afterwards, it took Carbon Materials as negative pole that Sony corporation of Japan has been invented, and to make the lithium battery of positive pole containing the compound of lithium, in charge and discharge process, did not have lithium metal, only had lithium ion, Here it is lithium ion battery.When charging to battery, the positive pole of battery has lithium ion to generate, the lithium ion of generation through electrolyte movement to negative pole.And be layer structure as the carbon of negative pole, it has a lot of micropore, and the lithium ion reaching negative pole is just embedded in the micropore of carbon-coating, and the lithium ion of embedding is more, and charging capacity is higher.
In the composition of lithium ion battery, positive electrode plays decisive role to its chemical property, security performance and even the developing direction in future.Anode material for lithium-ion batteries common at present mainly contains the cobalt acid lithium of layer structure and the LiFePO4 etc. of olivine structural.Wherein, LiCoO 2structure comparison is stablized, electrochemical performance, be the positive electrode of commercialization comparative maturity at present, but the overcharge resistant ability of this material is poor, declines rapidly in higher charging voltage specific capacity, LiFePO 4belong to newer positive electrode, 1997, the people such as Padhit proposed olivine-type LiFePO 4positive electrode, it is extensive that it possesses raw material sources, with low cost, pollution-free, security performance is high, the advantages such as resulting materials no hygroscopicity, and it has higher specific capacity, and (theoretical specific capacity is 170mAh/g, specific energy is 550Wh/kg) and higher operating voltage (3.4V), along with the rising of temperature, the specific capacity of battery also can significantly improve, it is more satisfactory a kind of positive electrode, but the defect of the crystal structure due to self, LiFePO4 has extremely low electronic conductivity and ion diffusion rates, hinder its application in commercial cells.By doping Co metal, make LiFePO 4adulterate in lattice a small amount of metal Co ion, can compensate for the shortcoming that ion diffusion rates is low.
Prepare above-mentioned LiFePO4 combination electrode material, mainly contain high temperature solid-state method, coprecipitation, sol-gal process, spray pyrolysis etc., wherein high temperature solid-state method is general first by the lithium salts of metering ratio, transition metal oxide, acetate or hydroxide Homogeneous phase mixing, and then high temperature sintering obtains product.But the method mixing uniformity is limited, and granular size is uneven, affects material property.In order to overcome the problems referred to above, the present invention is before the high-temperature calcination of LiFePO4 combination electrode material, synthesis material is passed through ball-milling technology, by abundant for its metallic particles powdered, make in high temperature solid-state process, metallic reacts completely, and has a good application prospect in the preparation technology of electrode material.
Summary of the invention
The object of this invention is to provide a kind of technique utilizing ball milling-high-temperature calcination to prepare combination electrode material.This preparation technology comprises the steps:
(1) get appropriate FeC 2o 42H 2o, Li 2cO 3, NH 4h 2pO 4and Co, by it according to Li:P:Fe:Co=1:1:1-x:x(0.01≤X≤0.1) ratio mixing;
(2) get a ball grinder again, the raw material of appropriate mixing and sucrose are poured in tank, then drop into the steel ball of certain mass ratio, then fill tank with acetone, after being covered tightly by lid, place ball milling on ball mill;
(3) after ball milling terminates, open ball grinder, pour out supernatant liquid, then take out lower metal powder;
(4) the metal dust poured out fully is dried;
Again by dry powder place in a high-temperature calcination stove;
(6), after high-temperature calcination stove being full of argon gas, calcine;
(7) the powder through calcination processing is taken out, cool to obtain electrode material.
Preferentially, step (2) in, ratio of grinding media to material is 20:1, and planetary ball mill speeds control 300-400r/min runs.
Preferentially, step (3) in, the time of carrying out ball milling with planetary ball mill is 4-6h.
Preferentially, step (6) in, high-temperature calcination temperature is 600-700 DEG C, and time controling is at 10-15h.
The present invention has following advantages and characteristic:
(1) preparation technology is simple, easy to operate;
(2) flow process is short, is easy to realize industrialization.
Embodiment one:
Get appropriate FeC 2o 42H 2o, Li 2cO 3, NH 4h 2pO 4and Co, its ratio according to Li:P:Fe:Co=1:1:0.99:0.1 is mixed, get a ball grinder again, the raw material of the mixing of appropriate 5g and the sucrose of 3g are poured in tank, drop into the steel ball of 200g again, then tank is filled with acetone soln, lid is covered tightly ball milling on rear placement ball mill, mill speed arranges 300r/min, after ball milling 6h, stop ball milling, pour out supernatant liquid, take out lower metal powder again, metal dust is fully dried, again by dry powder place in a high-temperature calcination stove, after high-temperature calcination stove is full of argon gas, calcining 15h is carried out at 600 DEG C, finally cool to obtain electrode material.
Embodiment two:
Get appropriate FeC 2o 42H 2o, Li 2cO 3, NH 4h 2pO 4and Co, its ratio according to Li:P:Fe:Co=1:1:0.95:0.05 is mixed, get a ball grinder again, the raw material of the mixing of appropriate 10g and the sucrose of 5g are poured in tank, drop into the steel ball of 400g again, then tank is filled with acetone soln, lid is covered tightly ball milling on rear placement ball mill, mill speed arranges 400r/min, after ball milling 4h, stop ball milling, pour out supernatant liquid, take out lower metal powder again, metal dust is fully dried, again by dry powder place in a high-temperature calcination stove, after high-temperature calcination stove is full of argon gas, calcining 13h is carried out at 650 DEG C, finally cool to obtain electrode material.
Embodiment three:
Get appropriate FeC 2o 42H 2o, Li 2cO 3, NH 4h 2pO 4and Co, its ratio according to Li:P:Fe:Co=1:1:0.9:0.1 is mixed, get a ball grinder again, the raw material of the mixing of appropriate 10g and the sucrose of 5g are poured in tank, drop into the steel ball of 400g again, then tank is filled with acetone soln, lid is covered tightly ball milling on rear placement ball mill, mill speed arranges 400r/min, after ball milling 5h, stop ball milling, pour out supernatant liquid, take out lower metal powder again, metal dust is fully dried, again by dry powder place in a high-temperature calcination stove, after high-temperature calcination stove is full of argon gas, calcining 10h is carried out at 700 DEG C, finally cool to obtain electrode material.

Claims (4)

1. utilize ball milling-high-temperature calcination to prepare a technique for combination electrode material, it is characterized in that, this technique comprises the following steps:
(1) get appropriate FeC 2o 42H 2o, Li 2cO 3, NH 4h 2pO 4and Co, by it according to Li:P:Fe:Co=1:1:1-x:x(0.01≤X≤0.1) ratio mixing;
(2) get a ball grinder again, the raw material of appropriate mixing and sucrose are poured in tank, then drop into the steel ball of certain mass ratio, then fill tank with acetone, after being covered tightly by lid, place ball milling on ball mill;
(3) after ball milling terminates, open ball grinder, pour out supernatant liquid, then take out lower metal powder;
(4) the metal dust poured out fully is dried;
Again by dry powder place in a high-temperature calcination stove;
(6), after high-temperature calcination stove being full of argon gas, calcine;
(7) the powder through calcination processing is taken out, cool to obtain electrode material.
2. a kind of technique utilizing ball milling-high-temperature calcination to prepare combination electrode material according to claim 1, is characterized in that, step (2) in, ratio of grinding media to material is 20:1, and planetary ball mill speeds control 300-400r/min runs.
3. a kind of technique utilizing ball milling-high-temperature calcination to prepare combination electrode material according to claim 1, is characterized in that, step (3) in, the time of carrying out ball milling with planetary ball mill is 4-6h.
4. a kind of technique utilizing ball milling-high-temperature calcination to prepare combination electrode material according to claim 1, is characterized in that, step (6) in, high-temperature calcination temperature is 600-700 DEG C, and time controling is at 10-15h.
CN201510972828.8A 2015-12-23 2015-12-23 Technology for preparing composite electrode material with ball milling-high temperature calcination method Pending CN105514429A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101789502A (en) * 2010-03-12 2010-07-28 江苏工业学院 Metal ion doping and carbon coating jointly modified lithium ion battery anode material
CN101789504A (en) * 2010-03-17 2010-07-28 中南大学 Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material
CN102324519A (en) * 2011-09-28 2012-01-18 中国东方电气集团有限公司 High-conductivity ferrous phosphate lithium cathode material for lithium ion battery and preparation method thereof
CN104701503A (en) * 2013-12-09 2015-06-10 青岛平度市旧店金矿 Process for preparing iron site doped LiFePO4/C through spray drying method

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101789502A (en) * 2010-03-12 2010-07-28 江苏工业学院 Metal ion doping and carbon coating jointly modified lithium ion battery anode material
CN101789504A (en) * 2010-03-17 2010-07-28 中南大学 Preparation method of nano LiFel-xMxPO4/C lithium phosphate composite positive pole material
CN102324519A (en) * 2011-09-28 2012-01-18 中国东方电气集团有限公司 High-conductivity ferrous phosphate lithium cathode material for lithium ion battery and preparation method thereof
CN104701503A (en) * 2013-12-09 2015-06-10 青岛平度市旧店金矿 Process for preparing iron site doped LiFePO4/C through spray drying method

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Application publication date: 20160420