CN106848200A - A kind of preparation method of lithium-ion battery lithium iron phosphate positive electrode - Google Patents
A kind of preparation method of lithium-ion battery lithium iron phosphate positive electrode Download PDFInfo
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- CN106848200A CN106848200A CN201710058933.XA CN201710058933A CN106848200A CN 106848200 A CN106848200 A CN 106848200A CN 201710058933 A CN201710058933 A CN 201710058933A CN 106848200 A CN106848200 A CN 106848200A
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1397—Processes of manufacture of electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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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- 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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Abstract
The invention provides a kind of preparation method of lithium-ion battery lithium iron phosphate positive electrode, including step:(1) source of iron, lithium source, carbon source stoichiometrically 1:(0.9‑1.1):(0.05 0.15) it is well mixed;Deionized water is medium, grinds 2~8 hours;(2) mixture after grinding obtains reaction powder by 100~120 DEG C of drying;(3) plasma-arc is imposed under reducing atmosphere to reaction powder, melts reaction powder;(4) frit reaction powder reducing gas is spurted into cooling device, by reducing, being cooled into ball-type fine particle.The method for preparing lithium iron phosphate material that the present invention is provided, it is simple to operate, obtained lithium iron phosphate positive material, pattern rule is highly spherical, stable electrochemical property, purity is high, composition is uniform, it is high using stability test obtained in the lithium iron phosphate positive material, specific capacity is high, excellent electrochemical performance.
Description
Technical field
The present invention relates to battery material field, more particularly to a kind of preparation of lithium-ion battery lithium iron phosphate positive electrode
Method.
Background technology
Lithium ion battery is new generation of green high-energy battery, with voltage is high, energy density big, good cycle, is put certainly
The many merits such as electric small, memory-less effect, operating temperature range be wide, are widely used in phone, notebook computer, electric tool
Deng also being had a good application prospect in electric automobile, by it is believed that being 21 century significant high energy technology
Product.Recently, lithium iron phosphate lithium ion battery anode material is due to its discharge capacity high, excellent security performance, Yi Jiliang
The advantages of cycle performance got well, becomes the focus of current research.
The positive electrode of lithium ion battery is the bottleneck for restricting lithium ion battery development, which determine the property of lithium ion battery
Energy, price and its development.Therefore, researching and developing high performance positive electrode has turned into the crucial institute of lithium ion battery development
.The tradition research emphasis of anode material for lithium-ion batteries is concentrated mainly on transition metal lithium intercalation compound LiMO2(M represent Co,
The metallic elements such as Ni, Mn, Fe) and LiA2O4(A represents the metallic elements such as Mn, Co).Presently commercially available lithium ion battery is used mostly
LiCoO2Used as positive electrode, but tellurian Co resource reserves are limited, while Co is not only expensive but also has certain
Toxicity;LiNiO2Synthesis is difficult, the less stable under full-charge state;LiMn2O4Decay makes it to capacity rapidly at high temperature
There is a certain distance from the commercialization practical stage.With good property when being found to be used as anode material for lithium-ion batteries
Just can more and more be paid close attention to by researcher with relatively low cost, LiFePO4.
The synthetic method of current lithium ion battery anode material lithium iron phosphate mainly has high temperature solid phase synthesis, co-precipitation
Method, sol-gel process, Pechini methods etc..The wherein soft chemical method technique such as coprecipitation, sol-gel method, Pechini methods
Complexity, is difficult to realize industrialization.Therefore conventional synthesis process mainly uses high temperature solid phase synthesis.High temperature solid phase synthesis be by
Lithium salts, ferrous salt and phosphorus compound are well mixed according to a certain percentage, when calcining one section at high temperature using inert gas shielding
Between be obtained LiFePO4.Conventional lithium salts has lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate etc., and source of iron is then ferrous oxalate,
In 600 DEG C~950 DEG C temperature of even more high, calcination time is 10~60h or so to calcining heat.High temperature solid phase synthesis are operated
And Process Route Planning is simple, technological parameter is easily controllable, the strong mechanical property of preparation, it is easy to accomplish industrialization is extensive raw
Produce.But, it is necessary to substantial amounts of inert protective gas when the high temperature solid phase synthesis of routine prepare LiFePO4, inert gas cost compared with
It is high;And in reaction vessel fill inert gas before, it is necessary to first air in reaction vessel be discharged, this will often pass through
Long-time operation could be completed so that building-up process operation increases, time lengthening.In general, conventional high temperature process heat
Method is totally relatively costly.
The content of the invention
In view of the shortcomings of the prior art, it is to provide a kind of convenient and swift to prepare iron phosphate lithium positive pole that the purpose of the present invention is
The method of material.
In order to realize above-mentioned technical purpose, the invention provides a kind of lithium-ion battery lithium iron phosphate positive electrode preparation side
Method, comprises the following steps:
(1) source of iron, lithium source and carbon source press iron:Lithium:Carbon geochemistry metering compares 1:(0.9-1.1):(0.05-0.15) mixing is equal
It is even;It is abrasive media with deionized water, mixture is ground;
(2) mixture after grinding obtains reaction powder by drying and processing;
(3) plasma-arc is imposed under reducing atmosphere to reaction powder, melts reaction powder;
(4) frit reaction powder reducibility gas are spurted into cooling device, forms the fine particle of ball-type.
Preferably, in step (1), source of iron, lithium source and carbon source press iron:Lithium:Carbon geochemistry metering compares 1:1.02:0.10 mixing is equal
It is even.
The source of iron is ferric phosphate or iron oxide or ferroso-ferric oxide;The lithium source is lithium hydroxide or lithium carbonate;Carbon source
It is glucose or sucrose.
In preparation method of the invention, the part by weight of deionized water and mixture is 1-10 in step (1):1;To mixing
Thing be ground to particle diameter be 0.1-5 micron when stop grind.
In the above method, step (2) described drying and processing refers to 100-120 DEG C, is dried under 0.009-0.012MPa vacuums
It is dry.
Plasma high-temperature fusion technology, is a kind of new technique developed in recent years, and principle is:By vacuum system
(generally inert gas, inert gas is helium to introduce plasma working gas after preset vacuum, in melt chamber and cooling chamber
One or more in gas, neon and argon gas, the inert gas in melt chamber and cooling chamber can be same, or mixed
Close gas), voltage is added between the two poles of the earth, the inert gas plasma moment in melt chamber heats up, and temperature can reach several
Thousand degree, the powder in addition feed appliance can be made to be rapidly reached molten condition, plasma high-speed motion can occur between particle
Sharp impacts, the material under molten condition required for in-time generatin, melt chamber is taken out of by the gas for being injected out, is entered
Required lithium iron phosphate positive material is obtained in cooling chamber, after cooling.Due to extreme temperatures, this method can make LiFePO4
Material is formed in moment, and can form continuous prodution.
Plasma electric arc voltage 1-5 ten thousand V, plasma electric arc current 400-800A in step (3).
Wherein, the reducibility gas in step (4) are the mixture of nitrogen and hydrogen, and wherein hydrogen is in mixed gas
Percent by volume 0.01~5%.
It is used for the nozzle diameter 0.5-10mm for spraying in step (4).
In one embodiment of the invention, the length of cooling device is 5~10 meters in step (4), and cooling device is to fill
The closed cavity of full air.
The amount that mixture spurts into cooling device in step (4) is 1-100g/sec.
After a kind of lithium-ion battery lithium iron phosphate method for preparing anode material of the invention also includes step (5) to cooling
Particle is crushed and screened, and the granular size that screening is obtained is 1-20 microns.
Further, lithium-ion electric is being prepared the invention provides lithium iron phosphate positive material obtained in above-mentioned preparation method
Application in pond.
The method for preparing lithium iron phosphate positive material of the invention is simple to operation, low cost, takes short, the phosphoric acid for obtaining
Iron lithium material pattern rule is not reunited uniformly for highly spherical, composition, stable electrochemical property.
Brief description of the drawings
Fig. 1 is the SEM photograph of ball shape ferric phosphate lithium material of the present invention.
Fig. 2 is the electric discharge figure of ball shape ferric phosphate lithium material of the present invention.
Fig. 3 is the circulation experiment figure of LiFePO 4 material of the present invention.
Specific embodiment
Unless otherwise defined, the implication that all technical terms used hereinafter are generally understood that with those skilled in the art
It is identical.Technical term used herein is intended merely to describe the purpose of specific embodiment, is not intended to the limitation present invention
Protection domain.
Except there is a special instruction, the various reagents used in the present invention, raw material be can be commercially commodity or
Person can be by product obtained in known method.
Technical solution of the present invention can be completed using existing plasma spraying equipment, such as ZB-80 types or DH-1080 types.
The preparation method (1) of the LiFePO4 of embodiment 1
(1) ferric carbonate, lithium carbonate and glucose press iron:Lithium:Carbon geochemistry metering compares 1:1.1:0.1 is well mixed;With go from
Sub- water is abrasive media, by step 1) gained mixture 2 hours of grinding.Now the particle mean size of material is 3.2 microns.
(2) mixture after step (1) grinding by 120 DEG C, dry 6 hours by drying and processing under 0.009MPa vacuums,
Obtain reaction powder;
(3) apply that (hydrogen and nitrogen volume ratio are 0.01 in reducing atmosphere to reaction powder:99) with the V's of voltage 10,000 under
Plasma-arc (electric current 400A), melts reaction powder;
(4) frit reaction powder reducibility gas are spurted into the cooling device (length of cooling device with 1g/sec speed
It is 5 meters to spend, and cooling device is the closed cavity full of air), the temperature in cooling chamber is normal temperature, by the cooling of 2 seconds,
Grain meeting freely falling body enters cooling device lower section, forms the fine particle of ball-type.Nozzle diameter is 0.5mm.
(5) particle after cooling is crushed and screened, the granular size that screening is obtained is 20.2 microns, lithium as of the invention
Ion battery lithium iron phosphate positive material.The SEM figures of material show spherical referring to Fig. 1, and composition is not reunited uniformly.
The preparation method (2) of the LiFePO4 of embodiment 2
(1) ferrous oxalate, lithium hydroxide and sucrose press iron:Lithium:Carbon geochemistry metering compares 1:0.9:0.05 is well mixed;To go
Ionized water is abrasive media, by step 1) gained mixture 8 hours of grinding.Now the particle mean size of material is 0.87 micron.
(2) mixture after step (1) grinding is by 100 DEG C, and drying and processing under 0.012MPa vacuums, drying 12 is small
When, obtain reaction powder;
(3) apply that (hydrogen and nitrogen volume ratio are 5 in reducing atmosphere to reaction powder:95) under with the grade of the V of voltage 50,000 from
Sub- electric arc (electric current 800A), melts reaction powder;
(4) by frit reaction powder reducibility gas with 100g/sec speed spurt into cooling device (cooling device
Length is 10 meters, and cooling device is the closed cavity full of air), temperature in cooling chamber is normal temperature, cold by 10 seconds
But, particle meeting freely falling body enters cooling device lower section, forms the fine particle of ball-type.Nozzle diameter is 10mm.
(5) particle after cooling is crushed and screened, the mean particle size that screening is obtained is 30 microns, as of the invention
Lithium-ion battery lithium iron phosphate positive electrode, its SEM figure shows that the lithium-ion battery lithium iron phosphate positive electrode for obtaining is height
Spherical, composition is not reunited uniformly.
The preparation method (3) of the LiFePO4 of embodiment 3
(1) ferric phosphate (being source of iron, phosphorus source), lithium carbonate and polyvinyl alcohol press iron:Lithium:Carbon geochemistry metering compares 1:1.0:0.12
It is well mixed;With deionized water as abrasive media, by step 1) gained mixture 6 hours of grinding.The now average grain of material
Spend is 1.5 microns.
(2) mixture after step (1) grinding by 110 DEG C, dry 8 hours by drying and processing under 0.01MPa vacuums,
Obtain reaction powder;
(3) apply that (hydrogen and nitrogen volume ratio are 2 in reducing atmosphere to reaction powder:98) under with the grade of the V of voltage 30,000 from
Sub- electric arc (electric current 500A), melts reaction powder;
(4) frit reaction powder reducibility gas are spurted into the cooling device (length of cooling device with 50g/sec speed
It is 8 meters to spend, and cooling device is the closed cavity full of air), the temperature in cooling chamber is normal temperature, by the cooling of 4 seconds,
Grain meeting freely falling body enters cooling device lower section, forms the fine particle of ball-type.Nozzle diameter is 2mm.
(5) particle after cooling is crushed and screened, the granular size that obtains of screening is 20 microns, lithium as of the invention from
Sub- battery lithium iron phosphate positive material, its SEM figure shows the lithium-ion battery lithium iron phosphate positive electrode that obtains for highly spherical,
Composition is not reunited uniformly, same to Fig. 1.
Embodiment 4
By the material described in embodiment 1.Lithium ion battery is assembled into, chemical property experiment is carried out.Experiment discovery, material
0.2C discharge capacity reaches 158mAh/g first, mean voltage reaches 3.41V, and (3.37-3.38 far beyond market product is
It is high).Discharge test figure is as shown in Figure 2.This material carries out 500 loop test figures as shown in Figure 3, it is seen that with good
Cyclical stability.The material that embodiment 2 and 3 is obtained is assembled into lithium ion battery, the lithium that its effect is assembled with the material of embodiment 1 from
Sub- battery.
Embodiment above is only that the preferred embodiment of the present invention is described, and not the scope of the present invention is entered
Row is limited, and on the premise of design spirit of the present invention is not departed from, this area ordinary skill technical staff is to technical side of the invention
The all variations and modifications that case is made, all should fall into the protection domain of claims of the present invention determination.
Claims (10)
1. a kind of preparation method of lithium-ion battery lithium iron phosphate positive electrode, comprises the following steps:
(1) source of iron, lithium source and carbon source press iron:Lithium:Carbon geochemistry metering compares 1:(0.9-1.1):(0.05-0.15) is well mixed;With
Deionized water is abrasive media, and mixture is ground;
(2) mixture after grinding obtains reaction powder by drying and processing;
(3) plasma-arc is imposed under reducing atmosphere to reaction powder, melts reaction powder;
(4) frit reaction powder reducibility gas are spurted into cooling device, forms the fine particle of ball-type.
2. preparation method according to claim 1, it is characterised in that the source of iron is ferric phosphate or iron oxide or four oxidations
Three-iron;The lithium source is lithium hydroxide or lithium carbonate;Carbon source is glucose or sucrose.
3. preparation method according to claim 1, it is characterised in that the weight of deionized water and mixture in step (1)
Ratio is 1-10:1;Mixture is ground to particle diameter be 0.1-5 micron when stop grind.
4. preparation method according to claim 1, it is characterised in that step (2) described drying and processing refers to 100-120
DEG C, dried under 0.009-0.012MPa vacuums.
5. preparation method according to claim 1, it is characterised in that the V of plasma electric arc voltage 1-5 ten thousand in step (3),
Plasma electric arc current 400-800A.
6. preparation method according to claim 1, it is characterised in that the reducibility gas in step (4) are nitrogen and hydrogen
The percent by volume 0.01~5% of the mixture of gas, wherein hydrogen in mixed gas.
7. preparation method according to claim 1, it is characterised in that be used for the nozzle diameter 0.5- for spraying in step (4)
10mm。
8. according to any described preparation methods of claim 1-7, it is characterised in that the length of cooling device in the step (4)
It is 5~10 meters to spend, and cooling device is the closed cavity full of air.
9. preparation method according to claim 1, it is characterised in that also crushed to the particle after cooling including step (5)
Screening, the granular size that screening is obtained is 1-20 microns.
10. the lithium iron phosphate positive material according to obtained in claim 1-8 any described preparation methods is preparing lithium-ion electric
Application in pond.
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Cited By (1)
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CN108288704A (en) * | 2018-02-05 | 2018-07-17 | 邳州易萨新型材料有限公司 | A kind of preparation method of anode material of lithium battery |
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