CN108134061A - A kind of preparation method of carbon-coated iron phosphate lithium positive pole composite material - Google Patents
A kind of preparation method of carbon-coated iron phosphate lithium positive pole composite material Download PDFInfo
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- CN108134061A CN108134061A CN201711388926.2A CN201711388926A CN108134061A CN 108134061 A CN108134061 A CN 108134061A CN 201711388926 A CN201711388926 A CN 201711388926A CN 108134061 A CN108134061 A CN 108134061A
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
- C01B25/375—Phosphates of heavy metals of iron
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
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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
- 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
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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
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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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
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- 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
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- 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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Abstract
The invention discloses a kind of preparation methods of carbon-coated iron phosphate lithium positive pole composite material, using lithium fluoride, ferrous acetate, ammonium hydrogen phosphate as raw material, absolute ethyl alcohol and DEXTROSE ANHYDROUS are added in, is sprayed after being ultrasonically treated through high frequency sprayer, the cloudy solution rapid draing at high temperature of ejection；It is ground after desciccate is once sintered, then carries out double sintering, obtain carbon-coated LiFePO4 (LiFePO4/ C) anode composite material, after which recycles 20 times under 0.2C, specific capacity conservation rate is more than 94%.
Description
Technical field
The present invention relates to technical field of lithium batteries, and in particular to a kind of carbon-coated LiFePO4 (LiFePO4/ C) anode
The preparation method of composite material.
Background technology
With the development of electric vehicle, the requirement for electrode material is higher and higher, especially positive electrode, positive electrode
As the important component of lithium ion battery, price accounts for about 1/3rd of lithium ion battery cost, be not only lithium from
The carrier of sub- deintercalation, and provide lithium source for entire 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.
LiFePO4Preparation method have high temperature solid-state method at present, hydrothermal synthesis method, coprecipitation, sol-gal process and micro-
Wave method etc..
High temperature solid-state method technique is relatively simple, and synthesis condition is easily controllable, is easy to be factory produced.
Hydrothermal synthesis method refers to that at high temperature under high pressure, raw material compound is reacted in the solution, and the method can be prepared
With specific valence state, special tectonic, the crystal for balancing defect.Hydrothermal synthesis method is uniform with product form, morphology controllable, material
The characteristics of particle is small, and flow is relatively simple.But large-scale high temperature high voltage resistant high equipment cost, it can only small lot production, it is difficult to big
Scale puts into production.
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.
Invention content
The present invention is intended to provide a kind of preparation method of carbon-coated iron phosphate lithium positive pole composite material, with lithium fluoride, vinegar
Sour ferrous, ammonium hydrogen phosphate is raw material, and add in DEXTROSE ANHYDROUS, and after sonicated and sintering, carbon-coated ferric phosphate is made
Lithium (LiFePO4/ C) anode composite material, after being recycled 20 times under 0.2C, specific capacity conservation rate is more than 94%.
The object of the invention to solve the technical problems is realized using following technical scheme.It proposes according to the present invention
A kind of carbon-coated iron phosphate lithium positive pole composite material preparation method, include 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, it after stirring evenly, is ultrasonically treated at 50 DEG C, supersonic frequency 15KHz, ultrasonic time 30min；
(2) mixed solution after gained ultrasound is sprayed by high frequency sprayer, the cloudy solution of ejection is fast at high temperature
Rapid-curing cutback is dry；Desciccate is transferred in electron tubes type resistance furnace, is sintered 3h under nitrogen protection, room is naturally cooled to after sintering
Temperature is fully ground；
(3) product after grinding is re-fed into electron tubes type resistance furnace and is sintered 5h again, obtain carbon-coated ferric phosphate
Lithium (LiFePO4/ C) anode composite material.
The object of the invention to solve the technical problems also can be used following technical measures and further realize.
A kind of preparation method of aforementioned carbon-coated iron phosphate lithium positive pole composite material, wherein, step (1) lithium fluoride,
Ferrous acetate, ammonium hydrogen phosphate molar ratio be 1:1:1.
A kind of preparation method of aforementioned carbon-coated iron phosphate lithium positive pole composite material, wherein, anhydrous Portugal in step (1)
The addition of grape sugar account for lithium fluoride, ferrous acetate, ammonium hydrogen phosphate gross mass 6-10%.
A kind of preparation method of aforementioned carbon-coated iron phosphate lithium positive pole composite material, wherein, it is fast described in step (2)
The dry temperature of rapid-curing cutback is 120 DEG C.
A kind of preparation method of aforementioned carbon-coated iron phosphate lithium positive pole composite material, wherein, the temperature of step (2) sintering
Spend is 400 DEG C.
A kind of preparation method of aforementioned carbon-coated iron phosphate lithium positive pole composite material, wherein, the temperature of step (3) sintering
Spend is 750 DEG C.
The present invention adds in DEXTROSE ANHYDROUS using lithium fluoride, ferrous acetate, ammonium hydrogen phosphate as raw material, it is sonicated simultaneously
After sintering, LiFePO4 (LiFePO is made4) anode composite material, after being recycled 20 times under 0.2C, specific capacity conservation rate is more than
94%, there is excellent chemical property.
Description of the drawings
Nothing
Specific embodiment
Illustrate the present invention referring to specific embodiment.These embodiments are merely to illustrate the present invention, not with appoint
Where formula limits the scope of the invention.
Embodiment 1
(1) it is 1 according to molar ratio:1:1 weighs a certain amount of lithium fluoride, ferrous acetate, ammonium hydrogen phosphate, is put into beaker,
Absolute ethyl alcohol and DEXTROSE ANHYDROUS are added in beaker, and it is total that the addition of DEXTROSE ANHYDROUS accounts for lithium fluoride, ferrous acetate, ammonium hydrogen phosphate
The 6-10% of quality after stirring evenly, is ultrasonically treated, supersonic frequency 15KHz, ultrasonic time 30min at 50 DEG C；
(2) mixed solution after gained ultrasound is sprayed by high frequency sprayer, the cloudy solution of ejection is fast at 120 DEG C
Rapid-curing cutback is dry；Desciccate is transferred in electron tubes type resistance furnace, is sintered 3h in 400 DEG C under nitrogen protection, naturally cold after sintering
But it to room temperature, is fully ground；
(3) product after grinding is re-fed into electron tubes type resistance furnace and is sintered 5h again in 750 DEG C, obtained carbon-coated
LiFePO4 (LiFePO4/ C) anode composite material.
By the carbon-coated LiFePO4 (LiFePO of gained4/ C) anode composite material is fabricated to button cell, pass through blue electricity
Battery test system tests its charge-discharge performance, and discharge capacity is 137.5mAh/g for the first time.
By the carbon-coated LiFePO4 (LiFePO of gained4/ C) anode composite material carries out cycle 20 times under 0.2C, and it is multiple
The discharge capacity of condensation material is 130mAh/g, is the 94.5% of discharge capacity for the first time.Illustrate carbon packet prepared by the method for the present invention
LiFePO4 (the LiFePO covered4/ C) anode composite material 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, however is not limited to the present invention, any technology people for being familiar with this profession
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, technical spirit according to the present invention
Any simple modification, equivalent change and modification made to the above embodiment, in the range of still falling within technical solution of the present invention.
Claims (6)
1. a kind of preparation method of carbon-coated iron phosphate lithium positive pole composite material, it is characterised in that include 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, is ultrasonically treated, supersonic frequency 15KHz, ultrasonic time 30min at 50 DEG C；
(2) mixed solution after gained ultrasound is sprayed by high frequency sprayer, the cloudy solution of ejection fast rapid-curing cutback at high temperature
It is dry；Desciccate is transferred in electron tubes type resistance furnace, is sintered 3h under nitrogen protection, and cooled to room temperature after sintering is filled
Divide grinding；
(3) product after grinding is re-fed into electron tubes type resistance furnace and is sintered 5h again, obtain carbon-coated LiFePO4
LiFePO4/ C anode composite materials.
2. the preparation method of carbon-coated iron phosphate lithium positive pole composite material as described in claim 1, it is characterised in that step
(1) lithium fluoride, ferrous acetate, ammonium hydrogen phosphate molar ratio be 1:1:1.
3. the preparation method of carbon-coated iron phosphate lithium positive pole composite material as described in claim 1, it is characterised in that step
(1) in the addition of DEXTROSE ANHYDROUS account for lithium fluoride, ferrous acetate, ammonium hydrogen phosphate gross mass 6-10%.
4. the preparation method of carbon-coated iron phosphate lithium positive pole composite material as described in claim 1, it is characterised in that step
(2) the quick-drying temperature described in is 120 DEG C.
5. the preparation method of carbon-coated iron phosphate lithium positive pole composite material as described in claim 1, it is characterised in that step
(2) temperature of sintering is 400 DEG C.
6. the preparation method of carbon-coated iron phosphate lithium positive pole composite material as described in claim 1, it is characterised in that step
(3) temperature of sintering is 750 DEG C.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201711388926.2A CN108134061A (en) | 2017-12-21 | 2017-12-21 | A kind of preparation method of carbon-coated iron phosphate lithium positive pole composite material |
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| CN201711388926.2A CN108134061A (en) | 2017-12-21 | 2017-12-21 | A kind of preparation method of carbon-coated iron phosphate lithium positive pole composite material |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081696A (en) * | 2007-05-15 | 2007-12-05 | 深圳市贝特瑞电子材料有限公司 | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof |
| CN101420034A (en) * | 2008-06-02 | 2009-04-29 | 李庆余 | Carbon coated granularity controllable spherical lithium ferric phosphate composite positive pole material and preparation method thereof |
| CN101916853A (en) * | 2010-08-20 | 2010-12-15 | 中国科学院过程工程研究所 | Method for preparing lithium iron phosphate anode active material with low energy consumption |
| CN106887570A (en) * | 2017-03-01 | 2017-06-23 | 沧州锐星化学科技有限公司 | Lithium-ion-power cell LiFePO 4 composite positive pole and preparation method thereof |
-
2017
- 2017-12-21 CN CN201711388926.2A patent/CN108134061A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101081696A (en) * | 2007-05-15 | 2007-12-05 | 深圳市贝特瑞电子材料有限公司 | Ferric phosphate lithium material for lithium ion powder cell and preparation method thereof |
| CN101420034A (en) * | 2008-06-02 | 2009-04-29 | 李庆余 | Carbon coated granularity controllable spherical lithium ferric phosphate composite positive pole material and preparation method thereof |
| CN101916853A (en) * | 2010-08-20 | 2010-12-15 | 中国科学院过程工程研究所 | Method for preparing lithium iron phosphate anode active material with low energy consumption |
| CN106887570A (en) * | 2017-03-01 | 2017-06-23 | 沧州锐星化学科技有限公司 | Lithium-ion-power cell LiFePO 4 composite positive pole and preparation method thereof |
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Application publication date: 20180608 |