CN105336929B - A kind of method that atomization prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode - Google Patents
A kind of method that atomization prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode Download PDFInfo
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- CN105336929B CN105336929B CN201510662300.0A CN201510662300A CN105336929B CN 105336929 B CN105336929 B CN 105336929B CN 201510662300 A CN201510662300 A CN 201510662300A CN 105336929 B CN105336929 B CN 105336929B
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- lithium
- atomization
- positive electrode
- 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
- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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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
- 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
Abstract
The present invention relates to a kind of method that atomization prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode.The scheme that the present invention uses is：1st, lithium salts, molysite and phosphate are dissolved in be well mixed after the water containing carbon matrix precursor and obtain settled solution.2nd, the pH value of above-mentioned solution is adjusted.3）Solution is positioned over and continues to stir in water-bath and flows back to obtain the precursor liquid for atomization.4）Small droplet is atomized into by precursor liquid and by quartz tube furnace or corundum tube furnace, with the spherical lithium iron phosphate precursor of powder catcher collection after drying.5）Ferric lithium phosphate precursor is placed in atmosphere furnace and is sintered and calcines, obtains spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode.Chemical composition, phase constituent and the particle diameter of the invention for effectively controlling spherical LiFePO 4, improve the high rate during charging-discharging and cycle performance of LiFePO4.Synthesis technique, production cost is reduced, product quality is improved, is easy to industrially practice.
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 electric
Pond technical field of material.
Technical background
Lithium ion battery is the green high-capacity battery of a new generation, have that operating voltage is high, specific capacity is big, self-discharge rate is low and
The advantages that service life is long, it is widely used in the fields such as portable digital equipment, electric tool and military industry equipment, in electric car
Also have a good application prospect, it is considered to be the 21 century new and high technology significant to national economy and people's lives
Product.
Positive electrode is the important component of lithium ion battery.It is compared to other positive electrodes such as LiCoO2、LiNiO2、
LiNi1/3Co1/3Mn1/3O2、LiMn2O4And LiFeSiO4Deng, the LiFePO4 with olivine structural due to cost it is low,
The advantages that specific capacity is higher, stable operating voltage and security performance are high, it is expected to turning into the main flow of power lithium-ion battery from now on
Positive electrode.From Goodenough（“Phospho-olivines as Positive-Electrode Materials for
Rechargeable Lithium Batteries” Journal of The Electrochemical Society, 144
(1997) 1188-1194）Research group's synthesizing iron lithium phosphate at first（LiFePO4）Since, lithium iron phosphate positive material obtains
Greatly pay attention to, widely studied and rapid development, have been enter into the practical stage at present.
(it is at room temperature 10 because LiFePO4 electrical conductivity itself is low-9~10-10S/cm) and lithium ion diffusion rate it is low (
10-14~10-16 m2/ s) the reason for, cause capacity during LiFePO4 large current charge all to play and influence it and extensively should
With.The electronic conductivity of LiFePO4, Chinese invention patent specification are mainly improved by the method for carbon coating at present（" carbon
The LiFePO 4 by microwaves preparation method of cladding and the LiFePO 4 material of carbon coating " application number 200910110427.6）, use
The cladding mode of microwave heating technique and a variety of carbon synergy, it is prepared for the LiFePO 4 material of high performance carbon coating.
Chinese invention patent specification（A kind of " preparation method using carbon black as the carbon-coated LiFePO 4 for lithium ion batteries material of carbon source " patent No.
201310144810）, the LiFePO 4 material with excellent cycle performance is prepared for using high temperature solid-state method.But carbon coating
Pattern that technique easily causes LiFePO 4 material is irregular, the uneven drawback such as low with tap density of size distribution, Jin Erying
Application in high-energy-density market is rung to LiFePO 4 material.Numerous studies show that the spheroidization of material can greatly improve
The tap density and volume energy density of material.Chinese invention patent specification（" one kind prepares ball using spray-wall interaction technology
The method of shape LiFePO 4 of anode material " application number 201010110985.5）, using high pure nitrogen as current-carrying gas, lithium will be contained
Source, the slurry atomization of phosphorus source and carbon source pass through and ball shape ferric phosphate lithium material are obtained after being calcined in nitrogen into droplet.However,
Droplet under the effect of current-carrying gas can not avoid the collision between droplet in transmitting procedure, cause LiFePO 4 material
Agglomeration and size distribution it is uneven, finally deteriorate the chemical property of LiFePO4.
The content of the invention
, should it is an object of the invention to provide a kind of method that atomization prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode
Method technical process is simple, equipment requirement is low, it is low to prepare cost.
To realize the purpose of the present invention, the technical scheme of use is：
1st, it is 0.95~1.1 by mol ratio:1:1 lithium salts, molysite and phosphate mixes after being dissolved in the water containing carbon matrix precursor
Close uniformly, lasting stirring obtains settled solution.
Described lithium salts refers to lithium acetate or lithium nitrate.
Described carbon containing predecessor 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.
2nd, the pH value of above-mentioned solution, pH value range 4~7 are adjusted with ammoniacal liquor or ethylenediamine.
3rd, solution is positioned in the water-bath that temperature is 60~80 DEG C and continues to stir and flow back, speed of agitator is per minute
50~120 turns, stirring obtains the precursor liquid for atomization after 8~20 hours.
4th, small droplet is atomized into by precursor liquid, allows small droplet to pass through quartz tube furnace or alundum tube using pumped vacuum systems
Formula stove, the speed that droplet passes through tube furnace are 0.5~5cm/s, and small droplet, which is dried, becomes precursor powder, is received with powder catcher
The precursor liquid powder of collection after drying, that is, obtain spherical lithium iron phosphate precursor.
The frequency of oscillation that described atomizer uses is 1.7MHz or 2.4MHz.
Described atomizer atomization quantity is 2ml/min~20ml/min.
Described tubular type furnace temperature is some temperature in 400~700 DEG C of sections；The speed that droplet passes through tube furnace is
0.5~5cm/s.
5th, the ferric lithium phosphate precursor being collected into is placed in atmosphere furnace, be sintered step by step under protective gas atmosphere with
Calcining：
1. sinter：Sintering temperature is 350~400 DEG C, and the heating rate that sintering temperature is raised to from room temperature is 1~5 DEG C/minute
Clock, calcination time are 3~6 hours；
2. calcine：Calcining heat is 600~800 DEG C, and the heating rate that calcining heat is raised to from sintering temperature is 2~10
DEG C/min, calcination time is 6~24 hours.
Described protective gas refers to nitrogen, argon gas or argon gas/hydrogen mixed gas.
Room temperature is cooled to stove in protective gas atmosphere after above-mentioned calcining, obtains spherical carbon coating of the present invention
Lithium iron phosphate positive material.
After measured, spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode is black powder, general molecular formula Li1+xFe P O4/ C,
Wherein -0.05< x <0.10, carbonaceous amount is 3%~9%.
The preparation system of ferric lithium phosphate precursor of the present invention, including three parts：Ultrasound atomization system, droplet are solid
Change area and precursor powder collection system.
1）Ultrasonic spray system
Supersonic frequency 1.7MHz or 2.4MHz, maximum condensation rate 20mL/min, atomising head 2~12, it is using vacuumizing
Droplet is brought into droplet curing area by system（High temperature process furnances）；
2）Droplet curing area
The cavity being made up of quartz ampoule or alundum tube, 3~6cm of cavity diameter, heat warm area 50~100cm of length, heating
400~700 DEG C of temperature；
The inventive method effectively controls chemical composition, phase constituent and the particle diameter of spherical LiFePO 4, improves ferric phosphate
The high rate during charging-discharging and cycle performance of lithium.Synthesis technique is simplified simultaneously, production cost is reduced, improves product
Quality, it is easy to industrially practice.
Brief description of the drawings
Fig. 1 is sample A prepared by the embodiment of the present invention 1 XRD spectrum.
Fig. 2 is sample A prepared by the embodiment of the present invention 1 electron scanning micrograph.
Fig. 3 is sample A prepared by the embodiment of the present invention 1 1C charging and discharging curves.
Fig. 4 is sample B prepared by the embodiment of the present invention 2 electron scanning micrograph.
Fig. 5 is sample B prepared by the embodiment of the present invention 2 0.2C charging and discharging curves.
Embodiment
Below in conjunction with the accompanying drawings and embodiment, the present invention will be further described
Embodiment 1
8.40 grams of citric acids are dissolved in 400 ml deionized waters, at room temperature after 1 hour of magnetic agitation, weighed
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 are added in mixed liquor, by
It is added dropwise to concentrated ammonia liquor regulation solution pH value constantly to stir, final solution pH value is 6.5 or so.Mixing after regulation pH value is molten
Liquid is placed in 80 DEG C of water-baths persistently stir 3 hours after be fitted into ultrasonic atomizing device, set atomization quantity as per minute 0.4 milli
Rise, open the atomising device that piezoelectric ceramic piece frequency is 1.7MHz, caused atomized drop is loaded into temperature by vacuum air pump
For in 550 °C of tube furnaces (the quartzy bore of tube furnace is 20 mm, and external diameter is 25 mm), atomized drop is in quartz ampoule
Pace is 2cm/s, atomized drop caused precursor powder after 550 °C of tube furnace, passes through powder collection device
Collect.The precursor powder that will be collected into, at 700 DEG C（Programming rate is 3 DEG C/min）, the lower calcining of argon gas protection 8 hours, calcining
Room temperature is naturally cooling to stove after end, powder, grinding and sieving is taken out and obtains carbon-coated LiFePO 4 for lithium ion batteries（LiFePO4/C, contain
7wt% carbon）.
The sample being prepared by above-mentioned steps is labeled as A.Fig. 1 is the X-ray diffraction that the present embodiment prepares sample A
Collection of illustrative plates, it will be seen from figure 1 that diffraction maximum is sharp, illustrate the present embodiment sample for the very high olivine-type LiFePO4 of crystallinity
Phase.Fig. 2 is the stereoscan photograph that the present embodiment prepares sample A, it is shown that obtained iron phosphate powder has good ball
Shape pattern.
Weigh LiFePO made from 0.16g4/ C powder, 0.02g conductive blacks and 0.02g binding agents PVDF（Polyvinylidene fluoride
Alkene）, it is scattered in 1-METHYLPYRROLIDONE solution, is applied to after well mixed on aluminium foil, is dried in vacuo 20 hours in 100 DEG C, system
Obtain iron phosphate lithium positive pole.1.0 mol/L LiPF6/EC/DEC/DMC is used as electrolyte, wherein LiPF6For conducting salt, EC
(ethylene carbonate)/DEC (diethyl carbonate)/DMC (dimethyl carbonate) is double solvents, the volume ratio of three（EC:DEC:
DMC）For 1：1：1.It is barrier film by negative pole, the polypropylene screens of Cellgard 2300 of metal lithium sheet, button is assembled into above-mentioned positive pole
Formula battery, with 1C（1C = 170 mA/g）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
Electricity circulation figure, as seen from the figure, capacity can be maintained at 140mAh/g after being circulated 50 times under 25 DEG C, 1C multiplying powers, illustrate our legal system
The LiFePO 4 material obtained has good chemical property.
Embodiment 2
8.20 grams of citric acids are dissolved in 300 ml deionized waters, magnetic agitation weighs 4.15 after 30 minutes at room temperature
Gram lithium dihydrogen phosphate, 10.81 grams of ferric chloride hexahydrates, 1.20 grams of glucose are added in mixed liquor, and ethylenediamine tune is added dropwise
Section solution pH value constantly stirs, and final solution pH value is 7 or so.Mixed solution after regulation pH value is placed in 70 DEG C of water-baths
It is fitted into after persistently stirring 1 hour in ultrasonic atomizing device, sets atomization quantity as 0.6 milliliter per minute, opens piezoelectric ceramic piece
Frequency is 2.4MHz atomising device, and caused atomized drop is loaded into the tube furnace (pipe that temperature is 500 °C by vacuum air pump
The quartzy bore of formula stove is 50 mm, and external diameter is 60 mm) in, pace of the atomized drop in quartz ampoule is 3cm/s, mist
Change drop caused precursor powder after 500 °C of tube furnace, collected by powder collection device.The forerunner that will be collected into
Body powder, at 750 DEG C（Programming rate is 2 DEG C/min）, the lower calcining of nitrogen protection 6 hours, calcining terminate after with stove Temperature fall
To room temperature, take out powder, grinding and sieving and obtain carbon-coated LiFePO 4 for lithium ion batteries（LiFePO4/C, carbon containing 8wt%）.
The sample being worth by above-mentioned steps is labeled as B.Fig. 4 is sample B stereoscan photograph, it is shown that obtained phosphorus
Sour iron lithium powder has good spherical morphology.
Weigh LiFePO4/C powder made from 0.16g, 0.02g conductive blacks and 0.02g binding agents PVDF（Polyvinylidene fluoride
Alkene）, it is scattered in 1-METHYLPYRROLIDONE solution, is applied to after well mixed on aluminium foil, is dried in vacuo 24 hours in 110 DEG C, system
Obtain iron phosphate lithium positive pole.1.0 mol/L LiPF6/EC/DEC/DMC is used as electrolyte, wherein LiPF6For conducting salt, EC
(ethylene carbonate)/DEC (diethyl carbonate)/DMC (dimethyl carbonate) is double solvents, the volume ratio of three（EC:DEC:
DMC）For 1：1：1.It is barrier film by negative pole, the polypropylene screens of Cellgard 2300 of metal lithium sheet, button is assembled into above-mentioned positive pole
Formula battery, with 1C（1C = 170 mA/g）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
Electricity circulation figure, as seen from the figure, the specific discharge capacity of LiFePO 4 material can reach 150mAh/g under 25 DEG C, 0.2C multiplying powers,
Illustrate that LiFePO 4 material made from this method has good chemical property.
Claims (7)
1. a kind of method that atomization prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, technical scheme are：
1）It is 0.95~1.1 by mol ratio:1:1 lithium salts, molysite and phosphate mixes after being dissolved in the water containing carbon matrix precursor
Even, lasting stirring obtains settled solution；
2）The pH value of above-mentioned solution, pH value range 4~7 are adjusted with ammoniacal liquor or ethylenediamine；
3）It is to continue to stir and flow back in 60~80 DEG C of water-bath that solution is positioned over into temperature, speed of agitator is per minute 50~
120 turns, stirring obtains the precursor liquid for atomization after 8~20 hours；
4）Precursor liquid is atomized into small droplet, small droplet is allowed by quartz tube furnace or corundum tube furnace using pumped vacuum systems,
The speed that droplet passes through tube furnace is 0.5~5cm/s, and small droplet, which is dried, becomes precursor powder, is collected and passed through with powder catcher
Dried precursor liquid powder, that is, obtain spherical lithium iron phosphate precursor；
5）The ferric lithium phosphate precursor being collected into is placed in atmosphere furnace, is sintered and forges step by step under protective gas atmosphere
Burn：
1. sinter：Sintering temperature is 350~400 DEG C, and the heating rate that sintering temperature is raised to from room temperature is 1~5 DEG C/min, is forged
It is 3~6 hours to burn the time；
2. calcine：Calcining heat is 600~800 DEG C, and the heating rate that calcining heat is raised to from sintering temperature is 2~10 DEG C/minute
Clock, calcination time are 6~24 hours.
2. the method that a kind of atomization according to claim 1 prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is special
Sign is that described lithium salts refers to lithium acetate or lithium nitrate.
3. the method that a kind of atomization according to claim 1 prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is special
Sign is that described carbon matrix precursor refers to sucrose or glucose.
4. the method that a kind of atomization according to claim 1 prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is special
Sign is that described phosphate refers to ammonium dihydrogen phosphate or diammonium hydrogen phosphate.
5. the method that a kind of atomization according to claim 1 prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is special
Sign is that described molysite refers to ferric nitrate, ferrous sulfate or iron chloride.
6. the method that a kind of atomization according to claim 1 prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is special
Sign is described atomization, and the frequency of oscillation used is 1.7MHz or 2.4MHz.
7. the method that a kind of atomization according to claim 1 prepares spherical carbon-coated LiFePO 4 for lithium ion batteries positive electrode, it is special
Sign is described atomization, and atomization quantity is 2ml/min~20ml/min.
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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 |
| CN114031062B (en) * | 2021-11-18 | 2023-04-14 | 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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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 |
| 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 |
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