CN105514428A - Composite electrode material and preparation technology thereof - Google Patents
Composite electrode material and preparation technology thereof Download PDFInfo
- Publication number
- CN105514428A CN105514428A CN201510972754.8A CN201510972754A CN105514428A CN 105514428 A CN105514428 A CN 105514428A CN 201510972754 A CN201510972754 A CN 201510972754A CN 105514428 A CN105514428 A CN 105514428A
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- CN
- China
- Prior art keywords
- electrode material
- preparation technology
- combination electrode
- ball milling
- ball
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Classifications
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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)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (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 composite electrode material and a preparation technology thereof. The composite electrode material is prepared from raw materials including FeC2O4*2H2O, Li2CO3, NH4H2PO4 and metal Mn. The preparation technology of the composite electrode material comprises the following steps: the raw materials including FeC2O4*2H2O, Li2CO3, NH4H2PO4 and Mn are mixed in certain proportion and poured into a ball milling tank together with proper amount of sucrose, the materials are subjected to ball milling through a planetary ball mill under protection of an acetone solution, ground metal mixed micro-powder is taken out and air-dried after ball milling is performed for a period of time, the air-dried micro-powder is calcined at a high temperature under protection of argon, then the micro-powder is cooled, and the composite electrode material is obtained. The preparation technology is simple and easy to operate.
Description
Technical field
The present invention relates to a kind of electrode material, particularly a kind of ferric phosphate aluminium combination electrode material of doped with Mn and preparation technology thereof, belong 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.
In order to overcome the problems referred to above, the present invention is at LiFePO
4in the preparation process of electrode material, add metal M n, make LiFePO
4adulterate in lattice a small amount of metal M n ion, and the electrode material of preparation substantially increases the conduction rate of ion, compensate for the shortcoming that ion diffusion rates is low, has a good application prospect in electrode material.
Summary of the invention
The object of this invention is to provide a kind of ferric phosphate aluminium combination electrode material and preparation technology thereof of doped with Mn.This preparation technology comprises the steps:
(1) get appropriate FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and Mn, by it according to Li:P:Fe:Mn=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 a kind of ferric phosphate aluminium combination electrode material of doped with Mn.
Preferentially, step (1) in, FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4be chemical pure with the purity of Mn.
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 Mn, its ratio according to Li:P:Fe:Mn=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, calcine at 600 DEG C, take out after 15h and cool to obtain a kind of ferric phosphate aluminium combination electrode material of doped with Mn.
Embodiment two:
Get appropriate FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and Mn, its ratio according to Li:P:Fe:Mn=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, calcine at 650 DEG C, take out after 13h and cool to obtain a kind of ferric phosphate aluminium combination electrode material of doped with Mn.
Embodiment three:
Get appropriate FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and Mn, its ratio according to Li:P:Fe:Mn=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, calcine at 700 DEG C, take out after 10h and cool to obtain a kind of ferric phosphate aluminium combination electrode material of doped with Mn.
Claims (5)
1. a preparation technology for combination electrode material, is characterized in that, this preparation technology comprises the following steps:
(1) get appropriate FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4and Mn, by it according to Li:P:Fe:Mn=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 a kind of ferric phosphate aluminium combination electrode material of doped with Mn.
2. the preparation technology of a kind of combination electrode material according to claim 1, it is characterized in that step (1) in, FeC
2o
42H
2o, Li
2cO
3, NH
4h
2pO
4be chemical pure with the purity of Mn.
3. the preparation technology of a kind of 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.
4. the preparation technology of a kind of 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.
5. the preparation technology of a kind of 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.
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Family
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Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108615858A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of combination electrode material and its technique of doping Pr, Sm |
CN108615883A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of Li of doping Yb, Gd1-(x+y)FeYbxGdyPO4Combination electrode material |
CN108615882A (en) * | 2016-12-11 | 2018-10-02 | 张彩缘 | A kind of Li1-(x+y)FeCexNdyPO4Combination electrode material |
CN108609597A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of li-ion electrode materials of rare earth doped terbium, dysprosium |
CN108615881A (en) * | 2016-12-11 | 2018-10-02 | 张彩缘 | A kind of Li1-(x+y)FeHOxLayPO4Combination electrode material and its technique |
Citations (6)
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---|---|---|---|---|
CN1792780A (en) * | 2005-10-27 | 2006-06-28 | 复旦大学 | Zinc ion mixed olivine structure LiFePo4 and its preparation process and application |
CN101013751A (en) * | 2007-02-12 | 2007-08-08 | 王海波 | Ball-shaped lithium-ion battery anode material doped with rare earth and method for making same |
CN101369657A (en) * | 2007-08-13 | 2009-02-18 | 深圳市比克电池有限公司 | Multicomponent doping spherical lithium iron phosphate anode material and method of manufacturing the same |
CN102104148A (en) * | 2010-12-31 | 2011-06-22 | 北京中科浩运科技有限公司 | Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof |
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 |
CN103078113A (en) * | 2013-01-15 | 2013-05-01 | 浙江南都电源动力股份有限公司 | Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof |
-
2015
- 2015-12-23 CN CN201510972754.8A patent/CN105514428A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN1792780A (en) * | 2005-10-27 | 2006-06-28 | 复旦大学 | Zinc ion mixed olivine structure LiFePo4 and its preparation process and application |
CN101013751A (en) * | 2007-02-12 | 2007-08-08 | 王海波 | Ball-shaped lithium-ion battery anode material doped with rare earth and method for making same |
CN101369657A (en) * | 2007-08-13 | 2009-02-18 | 深圳市比克电池有限公司 | Multicomponent doping spherical lithium iron phosphate anode material and method of manufacturing the same |
CN102104148A (en) * | 2010-12-31 | 2011-06-22 | 北京中科浩运科技有限公司 | Mixed rare earth compound-doped and modified lithium iron phosphate cathode material and preparation method thereof |
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 |
CN103078113A (en) * | 2013-01-15 | 2013-05-01 | 浙江南都电源动力股份有限公司 | Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN108615882A (en) * | 2016-12-11 | 2018-10-02 | 张彩缘 | A kind of Li1-(x+y)FeCexNdyPO4Combination electrode material |
CN108615881A (en) * | 2016-12-11 | 2018-10-02 | 张彩缘 | A kind of Li1-(x+y)FeHOxLayPO4Combination electrode material and its technique |
CN108615858A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of combination electrode material and its technique of doping Pr, Sm |
CN108615883A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of Li of doping Yb, Gd1-(x+y)FeYbxGdyPO4Combination electrode material |
CN108609597A (en) * | 2016-12-12 | 2018-10-02 | 张彩缘 | A kind of li-ion electrode materials of rare earth doped terbium, dysprosium |
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