CN105336929A - Method for preparing spherical carbon-coated lithium iron phosphate positive electrode material through atomization method - Google Patents
Method for preparing spherical carbon-coated lithium iron phosphate positive electrode material through atomization method Download PDFInfo
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- CN105336929A CN105336929A CN201510662300.0A CN201510662300A CN105336929A CN 105336929 A CN105336929 A CN 105336929A CN 201510662300 A CN201510662300 A CN 201510662300A CN 105336929 A CN105336929 A CN 105336929A
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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
- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention relates to a method for preparing a spherical carbon-coated lithium iron phosphate positive electrode material through an atomization method. The technical scheme of the present invention comprises: 1, dissolving a lithium salt, an iron salt and a phosphate in water containing a carbon precursor, and uniformly mixing to obtain a clarified solution; 2, adjusting the pH value of the solution; 3, placing the solution in a water bath pot, continuously stirring, and carrying out reflux to obtain a precursor liquid for atomization; 4, atomizing the precursor liquid into small mist droplets, passing through a quartz tube furnace or corundum tube furnace, and collecting the dried spherical lithium iron phosphate precursor by using a powder collector; and 5, placing the spherical lithium iron phosphate precursor into an atmosphere furnace, and carrying out sintering and calcination to obtain the spherical carbon-coated lithium iron phosphate positive electrode material. According to the present invention, the chemical component, the phase component and the particle size of the spherical lithium iron phosphate are effectively controlled, the large current charge-discharge performance and the cycle performance of the lithium iron phosphate are improved, the synthesis process is provided, the production cost is reduced, the product quality is improved, and the method is suitable for industrial implementation application.
Description
technical field:
The present invention relates to a kind of method that atomization prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, belong to lithium ion battery material preparing technical field.
Technical background
Lithium ion battery is the green high-capacity battery of a new generation, have that operating voltage is high, specific capacity is large, self-discharge rate is low and the advantage such as long service life, be widely used in the fields such as portable digital equipment, electric tool and military industry equipment, also have a good application prospect in electric motor car, be considered to 21 century to national economy and the significant new high-tech product of people's lives.
Positive electrode is the important component part of lithium ion battery.Be compared to other positive electrode as LiCoO
2, LiNiO
2, LiNi
1/3co
1/3mn
1/3o
2, LiMn
2o
4, and LiFeSiO
4deng, there is the LiFePO4 of olivine structural cost is low, specific capacity is higher owing to having, stable operating voltage and security performance advantages of higher, be expected to become the main flow positive electrode of power lithium-ion battery from now on.From Goodenough(" Phospho-olivinesasPositive-ElectrodeMaterialsforRecharge ableLithiumBatteries " JournalofTheElectrochemicalSociety, 144 (1997) 1188-1194) research group synthesizing iron lithium phosphate (LiFePO at first
4) since, lithium iron phosphate positive material obtains very big attention, extensively research and develops rapidly, enters the practical stage at present.
(be 10 under room temperature because the conductivity of LiFePO4 own is low
-9~ 10
-10s/cm) and lithium ion diffusion rate low by (10
-14~ 10
-16m
2/ s) reason, when causing LiFePO4 large current charge, capacity can not all play and affect its extensive use.The electronic conductivity of LiFePO4 is improved at present mainly through the method that carbon is coated, Chinese invention patent specification (" the LiFePO 4 by microwaves preparation method that carbon is coated and the coated LiFePO 4 material of carbon " application number 200910110427.6), adopt microwave heating technique and the synergistic coated mode of multiple carbon, prepare the LiFePO 4 material that high performance carbon is coated.Chinese invention patent specification (preparation method of the carbon-coated LiFePO 4 for lithium ion batteries material of carbon source " a kind of be with the carbon black " patent No. 201310144810), adopts high temperature solid-state method to prepare the LiFePO 4 material with excellent cycle performance.But carbon cladding process easily causes that the pattern of LiFePO 4 material is irregular, particle size distribution is uneven and the drawback such as tap density is low, and then has influence on the application of LiFePO 4 material in high-energy-density market.Large quantity research shows, the spheroidization of material can improve tap density and the volume energy density of material greatly.Chinese invention patent specification (" a kind of method adopting spray-wall interaction technology to prepare spherical anode material LiFePO4 " application number 201010110985.5), take high pure nitrogen as current-carrying gas, slurry containing lithium source, phosphorus source and carbon source is atomized into droplet, by obtaining ball shape ferric phosphate lithium material after calcining in nitrogen.But the droplet under the effect of current-carrying gas cannot avoid the collision between droplet in transmitting procedure, cause the agglomeration of LiFePO 4 material and the uneven of particle size distribution, finally deteriorate the chemical property of LiFePO4.
Summary of the invention
The object of the present invention is to provide a kind of atomization to prepare the method for spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, the method technical process is simple, equipment requirement is low, preparation cost is low.
For realizing object of the present invention, the technical scheme of employing is:
1, be the lithium salts of 0.95 ~ 1.1:1:1 by mol ratio, molysite and phosphate mixes after being dissolved in containing carbon matrix precursor water, and Keep agitation obtains settled solution.
Described lithium salts refers to lithium acetate or lithium nitrate.
The predecessor of described carbon containing refers to sucrose or glucose.
Described phosphate refers to ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
Described molysite refers to ferric nitrate, ferrous sulfate or iron chloride.
2, the pH value of above-mentioned solution is regulated with ammoniacal liquor or ethylenediamine, pH value range 4 ~ 7.
3, solution being positioned over temperature is continue in the water-bath of 60 ~ 80 DEG C stir and reflux, and speed of agitator is 50 ~ 120 turns per minute, stirs the precursor liquid obtained after 8 ~ 20 hours for being atomized.
4, little droplet is atomized into by precursor liquid, pumped vacuum systems is utilized to allow little droplet by quartz tube furnace or corundum tube furnace, droplet is 0.5 ~ 5cm/s by the speed of tube furnace, little droplet drying becomes precursor powder, with powder catcher collection precursor liquid powder after drying, namely obtain spherical lithium iron phosphate precursor.
The concussion frequency that described atomizer adopts is 1.7MHz or 2.4MHz.
Described atomizer atomization quantity is 2ml/min ~ 20ml/min.
Described tube furnace temperature is 400 ~ 700 DEG C of interval some temperature; Droplet is 0.5 ~ 5cm/s by the speed of tube furnace.
5, the ferric lithium phosphate precursor collected is placed in atmosphere furnace, under protective gas atmosphere, substep carries out sintering and calcines:
1. sinter: sintering temperature is 350 ~ 400 DEG C, and the heating rate being raised to sintering temperature from room temperature is 1 ~ 5 DEG C/min, and calcination time is 3 ~ 6 hours;
2. calcine: calcining heat is 600 ~ 800 DEG C, and the heating rate being raised to calcining heat from sintering temperature is 2 ~ 10 DEG C/min, and calcination time is 6 ~ 24 hours.
Described protective gas refers to nitrogen, argon gas or argon gas/hydrogen mixed gas.
After above-mentioned calcining, in protective gas atmosphere, be cooled to room temperature with stove, obtain spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode of the present invention.
After measured, spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode is black powder, and general molecular formula is Li
1+xfePO
4/ C, wherein-0.05<x<0.10, carbonaceous amount is 3% ~ 9%.
The preparation system of ferric lithium phosphate precursor of the present invention, comprises three parts: ultrasound atomization system, droplet curing area and precursor powder gathering system.
1) ultrasonic spray system
Supersonic frequency 1.7MHz or 2.4MHz, maximum condensation rate 20mL/min, atomising head 2 ~ 12, utilizes pumped vacuum systems droplet to be brought into droplet curing area (high temperature process furnances);
2) droplet curing area
The cavity be made up of quartz ampoule or alundum tube, cavity diameter 3 ~ 6cm, heating warm area length 50 ~ 100cm, heating-up temperature 400 ~ 700 DEG C;
The inventive method effectively controls the chemical composition of spherical LiFePO 4, phase constituent and particle diameter, improves high rate during charging-discharging and the cycle performance of LiFePO4.Simplify synthesis technique simultaneously, reduce production cost, improve the quality of product, be easy to industrially practice.
Accompanying drawing explanation
Fig. 1 is the XRD collection of illustrative plates of sample A prepared by the embodiment of the present invention 1.
Fig. 2 is the electron scanning micrograph of sample A prepared by the embodiment of the present invention 1.
Fig. 3 is the 1C charging and discharging curve of sample A prepared by the embodiment of the present invention 1.
Fig. 4 is the electron scanning micrograph of sample B prepared by the embodiment of the present invention 2.
Fig. 5 is the 0.2C charging and discharging curve of sample B prepared by the embodiment of the present invention 2.
Embodiment
Below in conjunction with drawings and Examples, the present invention will be further described
embodiment 1
8.40 grams of citric acids are dissolved in 400 ml deionized water, after room temperature lower magnetic force stirs 1 hour, take 16.16 gram of three nitric hydrate iron, 2.84 grams of lithium nitrates, 1.10 grams of sucrose, 4.74 grams of ammonium dihydrogen phosphates join in mixed liquor, dropwise adding concentrated ammonia liquor regulates solution pH value constantly to stir, and final solution pH value is about 6.5.Mixed solution after adjustment pH value is placed in 80 DEG C of water-bath Keep agitation and after 3 hours, loads ultrasonic atomizing device, setting atomization quantity is 0.4 milliliter per minute, opening piezoelectric ceramic piece frequency is the atomising device of 1.7MHz, the atomized drop produced is loaded into by vacuum air pump the tube furnace that temperature is 550 ° of C, and (the quartz ampoule internal diameter of tube furnace is 20mm, external diameter is 25mm) in, the pace of atomized drop in quartz ampoule is 2cm/s, the precursor powder that atomized drop produces after the tube furnace of 550 ° of C, is collected by powder collection device.By the precursor powder collected; calcine 8 hours under 700 DEG C (programming rate is 3 DEG C/min), argon shield; after calcining terminates with stove Temperature fall to room temperature, take out powder, grinding sieve and namely obtain carbon-coated LiFePO 4 for lithium ion batteries (LiFePO4/C, containing 7wt% carbon).
The identified as samples prepared by above-mentioned steps is designated as A.Fig. 1 is the X-ray diffracting spectrum that the present embodiment prepares sample A, and as can be seen from Figure 1, diffraction maximum is sharp-pointed, illustrates that the present embodiment sample is the olivine-type LiFePO4 phase that degree of crystallinity is very high.Fig. 2 is the stereoscan photograph that the present embodiment prepares sample A, shows obtained iron phosphate powder and has good spherical morphology.
Take the LiFePO that 0.16g is obtained
4/ C powder, 0.02g conductive black and 0.02g binding agent PVDF(Kynoar), be scattered in 1-METHYLPYRROLIDONE solution, be applied to after mixing on aluminium foil, in 100 DEG C of vacuumizes 20 hours, obtained iron phosphate lithium positive pole.The LiPF6/EC/DEC/DMC adopting 1.0mol/L is electrolyte, wherein LiPF
6for conducting salt, EC (ethylene carbonate)/DEC (diethyl carbonate)/DMC (dimethyl carbonate) is double solvents, and the volume ratio (EC:DEC:DMC) of three is 1:1:1.Taking metal lithium sheet as negative pole, Cellgard2300 polypropylene screen be barrier film, be assembled into button cell, with 1C(1C=170mA/g with above-mentioned positive pole) multiplying power carries out discharge and recharge, and the voltage range of discharge and recharge is 2.5 ~ 4.3V.Fig. 3 is charge and discharge cycles figure, and as seen from the figure, at 25 DEG C, the capacity after 50 times that circulates under 1C multiplying power can remain on 140mAh/g, illustrates that the LiFePO 4 material that this method obtains has good chemical property.
embodiment 2
8.20 grams of citric acids are dissolved in 300 ml deionized water, after room temperature lower magnetic force stirs 30 minutes, take 4.15 grams of lithium dihydrogen phosphates, 10.81 grams of ferric chloride hexahydrates, 1.20 grams of glucose join in mixed liquor, dropwise adding ethylenediamine regulates solution pH value constantly to stir, and final solution pH value is about 7.Mixed solution after adjustment pH value is placed in 70 DEG C of water-bath Keep agitation and after 1 hour, loads ultrasonic atomizing device, setting atomization quantity is 0.6 milliliter per minute, opening piezoelectric ceramic piece frequency is the atomising device of 2.4MHz, the atomized drop produced is loaded into by vacuum air pump the tube furnace that temperature is 500 ° of C, and (the quartz ampoule internal diameter of tube furnace is 50mm, external diameter is 60mm) in, the pace of atomized drop in quartz ampoule is 3cm/s, the precursor powder that atomized drop produces after the tube furnace of 500 ° of C, is collected by powder collection device.By the precursor powder collected; calcine 6 hours under 750 DEG C (programming rate is 2 DEG C/min), nitrogen protection; after calcining terminates with stove Temperature fall to room temperature, take out powder, grinding sieve and namely obtain carbon-coated LiFePO 4 for lithium ion batteries (LiFePO4/C, containing 8wt% carbon).
The identified as samples be worth by above-mentioned steps is designated as B.Fig. 4 is the stereoscan photograph of sample B, shows obtained iron phosphate powder and has good spherical morphology.
Take LiFePO4/C powder, 0.02g conductive black and 0.02g binding agent PVDF(Kynoar that 0.16g is obtained), be scattered in 1-METHYLPYRROLIDONE solution, be applied to after mixing on aluminium foil, in 110 DEG C of vacuumizes 24 hours, obtained iron phosphate lithium positive pole.The LiPF6/EC/DEC/DMC adopting 1.0mol/L is electrolyte, wherein LiPF
6for conducting salt, EC (ethylene carbonate)/DEC (diethyl carbonate)/DMC (dimethyl carbonate) is double solvents, and the volume ratio (EC:DEC:DMC) of three is 1:1:1.Taking metal lithium sheet as negative pole, Cellgard2300 polypropylene screen be barrier film, be assembled into button cell, with 1C(1C=170mA/g with above-mentioned positive pole) multiplying power carries out discharge and recharge, and the voltage range of discharge and recharge is 2.5 ~ 4.3V.Fig. 5 is charge and discharge cycles figure, and as seen from the figure, at 25 DEG C, under 0.2C multiplying power, the specific discharge capacity of LiFePO 4 material can reach 150mAh/g, illustrates that the LiFePO 4 material that this method obtains has good chemical property.
Claims (8)
1. atomization prepares a method for spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, and technical scheme is:
1) be the lithium salts of 0.95 ~ 1.1:1:1 by mol ratio, molysite and phosphate mixes after being dissolved in containing carbon matrix precursor water, and Keep agitation obtains settled solution;
2) pH value of above-mentioned solution is regulated with ammoniacal liquor or ethylenediamine, pH value range 4 ~ 7;
3) solution being positioned over temperature is continue in the water-bath of 60 ~ 80 DEG C stir and reflux, and speed of agitator is 50 ~ 120 turns per minute, stirs the precursor liquid obtained after 8 ~ 20 hours for being atomized;
4) little droplet is atomized into by precursor liquid, pumped vacuum systems is utilized to allow little droplet by quartz tube furnace or corundum tube furnace, droplet is 0.5 ~ 5cm/s by the speed of tube furnace, little droplet drying becomes precursor powder, with powder catcher collection precursor liquid powder after drying, namely obtain spherical lithium iron phosphate precursor;
5) ferric lithium phosphate precursor collected is placed in atmosphere furnace, under protective gas atmosphere, substep carries out sintering and calcines:
1. sinter: sintering temperature is 350 ~ 400 DEG C, and the heating rate being raised to sintering temperature from room temperature is 1 ~ 5 DEG C/min, and calcination time is 3 ~ 6 hours;
2. calcine: calcining heat is 600 ~ 800 DEG C, and the heating rate being raised to calcining heat from sintering temperature is 2 ~ 10 DEG C/min, and calcination time is 6 ~ 24 hours.
2. a kind of atomization according to claim 1 prepares the method for spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is characterized in that described lithium salts refers to lithium acetate or lithium nitrate.
3. a kind of atomization according to claim 1 prepares the method for spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is characterized in that the predecessor of described carbon containing refers to sucrose or glucose.
4. a kind of atomization according to claim 1 prepares the method for spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is characterized in that described phosphate refers to ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
5. a kind of atomization according to claim 1 prepares the method for spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is characterized in that described molysite refers to ferric nitrate, ferrous sulfate or iron chloride.
6. a kind of atomization according to claim 1 prepares the method for spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is characterized in that the concussion frequency that described atomizer adopts is 1.7MHz or 2.4MHz.
7. a kind of atomization according to claim 1 prepares the method for spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is characterized in that described atomizer atomization quantity is 2ml/min ~ 20ml/min.
8. a kind of atomization according to claim 1 prepares the method for spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is characterized in that described tube furnace temperature is 400 ~ 700 DEG C of interval some temperature; Droplet is 0.5 ~ 5cm/s by the speed of tube furnace.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107634216A (en) * | 2017-08-31 | 2018-01-26 | 福建师范大学 | A kind of ultrasonic atomizatio preparation method of the spherical lithium-rich manganese-based anode material of porous hollow |
| CN114031062A (en) * | 2021-11-18 | 2022-02-11 | 海南大学 | Method for preparing pure lithium iron phosphate by high-temperature spray spiral pipe |
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| CN101478045A (en) * | 2008-01-03 | 2009-07-08 | 深圳市沃特玛电池有限公司 | Preparation for high vibration high density lithium iron phosphate |
| CN102275887A (en) * | 2011-01-17 | 2011-12-14 | 横店集团东磁股份有限公司 | Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof |
| CN103996846A (en) * | 2014-04-14 | 2014-08-20 | 江苏中欧材料研究院有限公司 | Preparation method for lithium iron phosphate positive electrode material with controllable particle size |
| CN104241648A (en) * | 2014-09-28 | 2014-12-24 | 唐贵凤 | Preparation method for water system lithium ion battery material |
| CN104425820A (en) * | 2013-09-09 | 2015-03-18 | 北京国能电池科技有限公司 | Lithium ferric manganese phosphate material and preparation method thereof and lithium ion battery cathode material |
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- 2015-10-15 CN CN201510662300.0A patent/CN105336929B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101478045A (en) * | 2008-01-03 | 2009-07-08 | 深圳市沃特玛电池有限公司 | Preparation for high vibration high density lithium iron phosphate |
| CN102275887A (en) * | 2011-01-17 | 2011-12-14 | 横店集团东磁股份有限公司 | Preparation method of high capacity high compacted density lithium iron phosphate material and product thereof |
| CN104425820A (en) * | 2013-09-09 | 2015-03-18 | 北京国能电池科技有限公司 | Lithium ferric manganese phosphate material and preparation method thereof and lithium ion battery cathode material |
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| CN107634216A (en) * | 2017-08-31 | 2018-01-26 | 福建师范大学 | A kind of ultrasonic atomizatio preparation method of the spherical lithium-rich manganese-based anode material of porous hollow |
| CN114031062A (en) * | 2021-11-18 | 2022-02-11 | 海南大学 | Method for preparing pure lithium iron phosphate by high-temperature spray spiral pipe |
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