CN107887579A - Lithium ion battery polyanion positive electrode that a kind of surface is modified and preparation method thereof - Google Patents
Lithium ion battery polyanion positive electrode that a kind of surface is modified and preparation method thereof Download PDFInfo
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- CN107887579A CN107887579A CN201710874083.0A CN201710874083A CN107887579A CN 107887579 A CN107887579 A CN 107887579A CN 201710874083 A CN201710874083 A CN 201710874083A CN 107887579 A CN107887579 A CN 107887579A
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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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- 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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- 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
Lithium ion battery polyanion positive electrode being modified the invention discloses a kind of surface and preparation method thereof.The present invention is by the way that the material modified of the nanosizing lithium ion battery polyanion positive electrode powder modified with needs is uniformly mixed by a certain percentage, then the double sintering in inertia or reducing atmosphere, the free lithium reaction in the material modified and polyanion positive electrode surface of nanosizing consumes surface residual alkali, positive electrode pH is reduced, while clad is formed on positive electrode surface.Using the preparation method of the present invention, the residual alkali on positive electrode surface can be effectively reduced, material pH is reduced, improves its processing characteristics.
Description
Technical field
The invention belongs to technical field of lithium batteries, is related to the preparation of anode material for lithium-ion batteries, and in particular to Yi Zhongbiao
Lithium ion battery polyanion positive electrode that face is modified and preparation method thereof.
Background technology
With the popularization of portable electric appts and developing rapidly for electric vehicle engineering, lithium ion battery obtains widely
Concern and research.Wherein positive electrode is the core of lithium ion battery, can be used for the positive electrode of lithium ion battery at present
Including following several：LiFePO4, lithium ferric manganese phosphate, cobalt acid lithium, LiMn2O4, nickel-cobalt-manganese ternary material, nickel cobalt aluminium ternary material,
High-voltage lithium nickel manganate material, rich lithium material etc..Different positive electrodes are in charging/discharging voltage, specific capacity, energy density, physical
Larger difference in matter be present so that its application field difference.
Although different positive electrode structures, property are different, due to lithium salts, and pyroreaction will be used in building-up process
During have Li residuals, cause material surface to have residual alkali LiOH, Li2CO3Or LiHCO3In the presence of, therefore positive electrode generally shows
Alkalescence.There is alkaline matter on positive electrode surface, is easily absorbed water when causing it to expose in atmosphere, is prepared into more difficult baking during electrode slice
It is dry.When prepared by lithium ion battery, during the sizing mixing of positive pole, the residual alkali of material surface can attack PVDF, cause anode sizing agent
Viscosity increase even gel.In the lithium ion battery course of work, the residual alkali of positive electrode surface may be dissolved into electrolyte, right
Battery performance impacts.In very widely used today positive electrode, the alkalescence of LiFePO4 is weaker, and pH is about in 9.0-10.5
Between；And ternary material alkalescence is stronger, particularly nickelic ternary and nickel cobalt aluminium ternary material, pH even can reach 11-12, right
The post-production performance and electrical property of material cause larger puzzlement.
The method that ternary cathode material of lithium ion battery reduces pH at present is mainly WATER-WASHING METHOD：Use a large amount of aqueous cleanings
Positive electrode, the residual alkali of material surface is dissolved into water, reaching reduces material surface residual alkali, and then reduces pH effect.And
Polyanion positive electrode is because pH value is relatively low (comparing ternary material), temporarily also without targetedly drop pH methods.But due to
Polyanion positive electrode is mostly nano material, and specific surface area is larger, even if pH relatively low (9-10), surface residual alkali is also easily and PVDF
Reaction, cause size mixing viscosity increase or pulp gel.
The content of the invention
For above-mentioned technical problem, the present invention proposes a kind of surface for preparing and is being modified the lithium ion battery polyanion of energy just
The method of pole material, its core are the residual alkali for reducing polyanion positive electrode surface, lift its processing characteristics.
To achieve these goals, the present invention uses following technical scheme：
A kind of preparation method for the lithium ion battery polyanion positive electrode that surface is modified, its step include：
1) by the material modified of nanosizing with needing modified lithium ion battery polyanion positive electrode powder to mix
It is even, wherein, material modified formula is MAO4, one or more of the M in Fe, Mn, Co, V, A in P, S, Si one
Kind is several；The formula for needing modified lithium ion battery polyanion positive electrode is LiXBO4, X is in Fe, Mn, Co, V
One or more, one or more of the B in P, S, Si, nanosizing it is material modified with needing modified lithium ion battery
The weight ratio of polyanion positive electrode powder is 0.001-0.2；
2) by the mixture that step 1) obtains in inert atmosphere or reducing atmosphere, 200-800 DEG C of sintering 2-30 hour,
Obtain the lithium ion battery polyanion positive electrode LiXBO of surface modification4@LiMAO4。
Preferably, the material modified granularity of nanosizing described in step 1) is in 10-1000nm.Can be by by ferric phosphate etc.
Obtained by mechanical lapping nanosizing, or directly use nano material.
Preferably, the granularity of modified lithium ion battery polyanion positive electrode powder is needed to exist described in step 1)
In 10-5000nm.
Preferably, the mode of mixing can be solid phase mixing in step 1).
Preferably, the mode of mixing can also first disperse the material modified of nanosizing in a solvent, so in step 1)
Afterwards with needing modified lithium ion battery polyanion positive electrode powder to be well mixed in a solvent, it is equal that re-dry obtains mixing
Even powder.
Preferably, above-mentioned solvent includes water, organic solvent or the mixed solution of the two.
Preferably, above-mentioned organic solvent includes：Alcohols：Such as methanol, ethanol, ethylene glycol；Arene：Benzene, toluene, two
Toluene etc.；Fat hydrocarbon：Pentane, hexane, octane etc.；Alicyclic hydrocarbon type：Hexamethylene etc.；Ethers：Ether, expoxy propane etc.；Lipid：
Methyl acetate, ethyl acetate etc.；Ketone：Acetone, espeleton etc.；It is other：One or more in acetonitrile, pyridine, phenol etc..
Preferably, the inert atmosphere in step 2) includes：The one or more of the inert gases such as nitrogen, argon gas, helium are mixed
Close.
Preferably, the reducing atmosphere in step 2) includes：The reducibility gas such as hydrogen, carbon monoxide one or more
Mixing, and the mixed gas of reducibility gas and inert gas.
Present invention also offers the lithium ion battery polyanion of the surface being prepared by above-mentioned preparation method modification just
Pole material.
The pH for the lithium ion battery polyanion positive electrode that above-mentioned surface is modified is less than 9.
The processing characteristics for the polyanion positive electrode that the surface that this method is prepared is modified is improved, and material is not easy
The moisture absorption, slurry viscosity is smaller when sizing mixing, and is not easy gel, keeps solid content to be sized mixing for 50%, modified polyanion is just
Pole material paste viscosity is reduced more than 50%.Compared with existing LiFePO4 coats tertiary cathode material technology, advantage of the present invention
It is：
1st, lithium source need not additionally be added；
2nd, the material modified MAO of nanosizing4(ferric phosphate etc.) is with needing modified lithium ion battery polyanion positive pole material
Expect LiXBO4Powder be well mixed by a certain percentage, double sintering, nanosizing are then carried out in inertia or reducing atmosphere
Material modified MAO4With needing modified polyanion positive electrode LiXBO4Dissociate lithium reaction generation LiMAO on surface4(phosphoric acid
Iron lithium etc.), lithium ion battery polyanion positive electrode surface residual alkali can be consumed, polyanion positive electrode pH is reduced and arrives
Less than 9, improve its processing characteristics；
3rd, the material modified MAO of nanosizing4(ferric phosphate etc.) is with needing modified lithium ion battery polyanion positive pole material
Expect the residual lithium reaction in-situ generation LiMAO in surface4, and it is coated on LiXBO4Surface, obtained LiMAO4Clad and polyanion are just
Pole material combines even closer.
Brief description of the drawings
Fig. 1 is the stereoscan photograph of the modified phosphate iron lithium prepared according to embodiment in the present invention 1.
Fig. 2 is the charging and discharging curve of the modified phosphate iron lithium prepared according to embodiment in the present invention 1.
Fig. 3 is the stereoscan photograph of the modified phosphate ferrimanganic lithium prepared according to embodiment in the present invention 6.
Embodiment
Embodiment 1：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection, 500
DEG C calcining 5h, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.7, the residual lithium 0.04wt% in surface.Electrode system
When progress positive pole LiFePO4 is sized mixing during work, it is 50% to keep solid content, and the LiFePO4 slurry viscosity before being modified is
13273mpa.s, the LiFePO4 slurry viscosity after being modified are reduced to 5320mpa.s.Its stereoscan photograph as shown in figure 1,
Significant change does not occur for the pattern of initial LiFePO4, and surface little particle is nano ferric phosphate and the initial residual lithium in LiFePO4 surface
React the new LiFePO4 of generation.Modified LiFePO 4 material is fabricated to half-cell, discharge and recharge is carried out under 0.1C, it fills
Discharge curve is as shown in Fig. 2 the lithium iron phosphate positive material being modified by the method shows good electrical property, 0.1C decentralizations
Capacitance reaches 162mAh/g.
Embodiment 2：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection, 200
DEG C calcining 5h, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.6, the residual lithium 0.04wt% in surface.Electrode system
When progress positive pole LiFePO4 is sized mixing during work, it is 50% to keep solid content, and the LiFePO4 slurry viscosity before being modified is
13273mpa.s, the LiFePO4 slurry viscosity after being modified are reduced to 5815mpa.s.
Embodiment 3：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection, 800
DEG C calcining 5h, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.6, the residual lithium 0.04wt% in surface.Electrode system
When progress positive pole LiFePO4 is sized mixing during work, it is 50% to keep solid content, and the LiFePO4 slurry viscosity before being modified is
13273mpa.s, the LiFePO4 slurry viscosity after being modified are reduced to 5023mpa.s.
Embodiment 4：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection,
500 DEG C of calcining 2h, are cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.4, the residual lithium 0.03wt% in surface.
Embodiment 5：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection,
500 DEG C of calcining 30h, are cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.4, the residual lithium 0.03wt% in surface.
Embodiment 6：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 15 minutes to ferric phosphate
Nano particle size be 100nm, then add pH=9.8 (the residual lithium 0.17wt% in surface) lithium ferric manganese phosphate powder 100g, stirring
Uniformly, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection,
5h is calcined at 500 DEG C, room temperature is cooled to and obtains modified lithium ferric manganese phosphate material, material pH=8.4, the residual lithium in surface
0.05wt%.Its stereoscan photograph is as shown in figure 3, surface little particle is that nano ferric phosphate and lithium ferric manganese phosphate surface residual alkali are anti-
The LiFePO4 that should be generated.
Embodiment 7：
Take 1.0g ferrosilites to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 350nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection,
500 DEG C of calcining 5h, are cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.8, the residual lithium 0.07wt% in surface.
Embodiment 8：
Take 1.0g manganous silicates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 400nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection,
500 DEG C of calcining 5h, are cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.8, the residual lithium 0.09wt% in surface.
Embodiment 9：
Take the ferric phosphate and 100g iron phosphate powders (pH=9.6, the residual lithium in surface that 1.0g nano particle sizes are 500nm
0.13wt%), ground 30 minutes in mortar, make the two well mixed.Obtained powder is placed in the reacting furnace of nitrogen protection
In, 10h is calcined at 500 DEG C, room temperature is cooled to and obtains modified LiFePO 4 material, material pH=8.9, the residual lithium in surface
0.08wt%.
Embodiment 10：
Take 1.0g ferric phosphates to be scattered in the 500ml aqueous solution, grind 2000 revs/min using nanometer and grind 5 minutes to phosphoric acid
The nano particle size of iron is 200nm, then adds pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring
Uniformly, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection,
5h is calcined at 500 DEG C, room temperature is cooled to and obtains modified LiFePO 4 material, material pH=8.7, the residual lithium 0.07wt% in surface.
Embodiment 11：
1.0g ferric phosphates are taken to be scattered in the mixed solution of 500ml water and methanol (mass percent of water is 30wt%),
It is 200nm to grind 2000 revs/min of grindings, 5 minutes nano particle sizes to ferric phosphate using nanometer, then adds pH=9.6 (surfaces
Residual lithium 0.13wt%) iron phosphate powder 100g, stir, be subsequently placed in rotation thermal evaporation instrument in, 60 DEG C of heating are evaporated.
Obtained powder is placed in the reacting furnace of nitrogen protection, calcines 5h at 500 DEG C, be cooled to room temperature and obtain modified LiFePO4
Material, material pH=8.7, the residual lithium 0.06wt% in surface.
Embodiment 12：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in and is connected with argon hydrogen gaseous mixture (H25%)
Tube furnace in, calcine 5h at 500 DEG C, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.5, surface is residual
Lithium 0.05wt%.
Embodiment 13：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.The mixed gas that obtained powder is placed in nitrogen and argon gas is protected
In the reacting furnace of shield, 5h is calcined at 500 DEG C, room temperature is cooled to and obtains modified LiFePO 4 material, material pH=8.7, surface
Residual lithium 0.05wt%.
Embodiment 14：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the tube furnace for being connected with hydrogen,
500 DEG C of calcining 5h, are cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.5, the residual lithium 0.04wt% in surface.
Embodiment 15：
Take 5.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in and is connected with argon hydrogen gaseous mixture (H25%)
Tube furnace in, calcine 5h at 500 DEG C, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.0, surface is residual
Lithium 0.02wt%.
Embodiment 16：
Take 20.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in and is connected with argon hydrogen gaseous mixture (H25%)
Tube furnace in, calcine 5h at 500 DEG C, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=7.5, surface is residual
Lithium 0.02wt%.
Embodiment 17：
Take 0.1g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in and is connected with argon hydrogen gaseous mixture (H25%)
Tube furnace in, calcine 5h at 500 DEG C, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.9, surface is residual
Lithium 0.10wt%.
Embodiment 18：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 30 minutes to ferric phosphate
Nano particle size be 20nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in and is connected with argon hydrogen gaseous mixture (H25%)
Tube furnace in, calcine 5h at 500 DEG C, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.0, surface is residual
Lithium 0.03wt%.
Embodiment 19：
Take 1.0g ferric phosphates to be scattered in 500ml methanol, grind 2000 revs/min using nanometer and grind 60 minutes to ferric phosphate
Nano particle size be 10nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in and is connected with argon hydrogen gaseous mixture (H25%)
Tube furnace in, calcine 5h at 500 DEG C, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.0, surface is residual
Lithium 0.03wt%.
Embodiment 20：
The ferric phosphate (alfa) for taking 1.0g nano particle sizes to be 1000nm is scattered in 500ml methanol, then adds pH=9.6
The iron phosphate powder 100g of (the residual lithium 0.13wt% in surface), stirs, and is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating
It is evaporated.Obtained powder is placed in and is connected with argon hydrogen gaseous mixture (H25%) in tube furnace, 5h is calcined at 500 DEG C, is cooled to room temperature
Obtain modified LiFePO 4 material, material pH=8.9, the residual lithium 0.10wt% in surface.
Embodiment 21：
Take 1.0g ferric phosphates to be scattered in 500ml pentanes, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection, 500
DEG C calcining 5h, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.7, the residual lithium 0.04wt% in surface.
Embodiment 22：
Take 1.0g ferric phosphates to be scattered in 500ml ether, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection, 500
DEG C calcining 5h, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.8, the residual lithium 0.05wt% in surface.
Embodiment 23：
Take 1.0g ferric phosphates to be scattered in 500ml acetone, grind 2000 revs/min using nanometer and grind 5 minutes to ferric phosphate
Nano particle size be 200nm, then add pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirring is equal
It is even, it is subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection, 500
DEG C calcining 5h, be cooled to room temperature and obtain modified LiFePO 4 material, material pH=8.5, the residual lithium 0.05wt% in surface.
Embodiment 24：
Take 1.0g ferric phosphates to be scattered in 500ml methyl formates, grind 2000 revs/min using nanometer and grind 5 minutes to phosphorus
The nano particle size of sour iron is 200nm, then adds pH=9.6 (the residual lithium 0.13wt% in surface) iron phosphate powder 100g, stirs
Mix uniformly, be subsequently placed in rotation thermal evaporation instrument, 60 DEG C of heating are evaporated.Obtained powder is placed in the reacting furnace of nitrogen protection
In, 500 DEG C of calcining 5h, it is cooled to room temperature and obtains modified LiFePO 4 material, material pH=8.8, the residual lithium 0.07wt% in surface.
Claims (10)
1. a kind of preparation method for the lithium ion battery polyanion positive electrode that surface is modified, its step include：
1) by the material modified of nanosizing with needing modified lithium ion battery polyanion positive electrode powder to be well mixed, its
In, material modified formula is MAO4, one or more of the M in Fe, Mn, Co, V, the one kind or several of A in P, S, Si
Kind；The formula for needing modified lithium ion battery polyanion positive electrode is LiXBO4, the one kind of X in Fe, Mn, Co, V
Or several, one or more of the B in P, S, Si, nanosizing it is material modified with need modified lithium ion battery it is poly- it is cloudy from
The weight ratio of sub- positive electrode powder is 0.001-0.2；
2) by the mixture that step 1) obtains in inert atmosphere or reducing atmosphere, 200-800 DEG C of sintering 2-30 hour, obtain
The lithium ion battery polyanion positive electrode LiXBO that surface is modified4@LiMAO4。
2. preparation method as claimed in claim 1, it is characterised in that the material modified granularity of nanosizing described in step 1)
In 10-1000nm.
3. preparation method as claimed in claim 1, it is characterised in that the mode of mixing is solid phase mixing in step 1).
4. preparation method as claimed in claim 1, it is characterised in that the mode of mixing is first changing nanosizing in step 1)
Property material it is scattered in a solvent, then with needing modified lithium ion battery polyanion positive electrode powder to mix in a solvent
Uniformly, re-dry obtains well mixed powder.
5. preparation method as claimed in claim 4, it is characterised in that the solvent include water, organic solvent or the two
Mixed solution.
6. preparation method as claimed in claim 5, it is characterised in that the organic solvent includes：Alcohol, aromatic hydrocarbon, aliphatic hydrocarbon,
One or more in alicyclic, ether, lipid, ketone, acetonitrile, pyridine, phenol.
7. preparation method as claimed in claim 1, it is characterised in that the inert atmosphere in step 2) includes：Nitrogen, argon gas,
One or more mixing in helium.
8. preparation method as claimed in claim 1, it is characterised in that the reducing atmosphere in step 2) includes：Reproducibility gas
Body, or the mixed gas of reducibility gas and inert gas, the reducibility gas include hydrogen and carbon monoxide.
9. the lithium ion battery polyanion positive pole that the surface that any described preparation methods of claim 1-8 are prepared is modified
Material.
10. the lithium ion battery polyanion positive electrode that surface as claimed in claim 9 is modified, it is characterised in that described
The pH for the lithium ion battery polyanion positive electrode that surface is modified is less than 9.
Priority Applications (1)
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