CN109935809A - A kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material - Google Patents
A kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material Download PDFInfo
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- CN109935809A CN109935809A CN201910151749.9A CN201910151749A CN109935809A CN 109935809 A CN109935809 A CN 109935809A CN 201910151749 A CN201910151749 A CN 201910151749A CN 109935809 A CN109935809 A CN 109935809A
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- cathode material
- vanadium phosphate
- aluminum fluoride
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- phosphate cathode
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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 invention discloses a kind of preparation methods of aluminum fluoride cladding vanadium phosphate cathode material, belong to battery and its preparation technical field.It is aluminium fluoride synthesized by ammonium fluoride and aluminum nitrate, it is then coated on vanadium phosphate cathode material surface, aluminum fluoride cladding can be effectively prevented positive electrode not by the corrosion of hydrofluoric acid, to stabilize electrode and electrolyte interface, improve the structural stability of material.
Description
Technical field
The present invention relates to a kind of preparation methods of cell positive material, and in particular to a kind of aluminum fluoride cladding phosphoric acid vanadium lithium is just
The preparation method of pole material.
Background technique
The increasingly serious exploitation for making new energy materials of energy environment issues is more urgent, and lithium ion battery is as green
The key that reproducible energy storage device receives significant attention, and improves lithium ion battery energy density is to prepare high capacity
Positive electrode.NASICON type phosphoric acid vanadium lithium (Li3V2(PO4)3) as anode material for lithium-ion batteries be that recent domestic is ground
The person's of studying carefully focus of attention.Monoclinic system Li3V2(PO4)3It was reported for the first time by people in 2002, thermal stability is good, charge and discharge are electric
It is 3.0-4.8V, theoretical specific capacity 197mAh/g between pressure area, it is more much higher than other phosphoric acid salt positive electrode specific capacities, it is expected to
As lithium ion power battery cathode material of new generation.
Monoclinic system Li3V2(PO4)3Material is due to enabling lithium ion to pass in space isotropism with 3D network structure
It is defeated, but VO in material cell configuration6Octahedron is by PO4Tetrahedron separation causes material to have lower electronic conductivity, about
10-7S/cm, and lithium ion diffusion coefficient is lower, limits Li3V2(PO4)3The development and application of material.
Summary of the invention
A kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material is provided to solve the problem above-mentioned the present invention.This
The technical solution of invention includes the following steps；
A kind of preparation method of vanadium phosphate cathode material: starch and acetylene black is soluble in water, V is added2O5, LiOH
H2O, NH4H2PO4Form homogeneous latex emulsion.Wherein LiOHH2O:V2O5:NH4H2PO4Molar ratio be 3-3.05:2-2.05:3, so
Mixed solution is spray-dried afterwards, drying temperature is 180-200 DEG C；Then ball milling, time 1.5-2.5h are carried out；Finally
It calcines in air again, temperature is 700-900 DEG C, and the time is that 8-10h obtains the Li of hollow microsphere3V2(PO4)3Powder.
A kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material: in Al (NO3)3Li is added in aqueous solution3V2
(PO4)3Powder, wherein Al (NO3)3With Li3V2(PO4)3The molar ratio of powder is 1:0.8-1.2；NH is slowly added dropwise4F solution, so
After stir 5-10h.Wherein the molar ratio of Al element and F element is 1:3；In 80-100 DEG C of vacuum drying 10-12h, by gained powder
5-10h is calcined at 350-450 DEG C under argon atmosphere in end, obtains AlF3Coat Li3V2(PO4)3Material.
Further, starch quality accounts for gross mass 0.1-0.5%, and acetylene black quality accounts for the 0.1-0.5% of gross mass.
The invention has the benefit that during the reaction, starch being added and acetylene black provides carbon source, phosphoric acid can be improved
The electric conductivity of vanadium lithium.
Positive electrode can be effectively prevented not by the by-product for aoxidizing generation under high pressure by electrolyte in aluminum fluoride cladding simultaneously
Object hydrofluoric acid is corroded, to stabilize the interface between electrode and electrolyte, prevents the formation thickness on positive electrode surface
Anode-electrolyte interface (CEI) film, to improve the structural stability of material.
Detailed description of the invention
Fig. 1 is under 5C current density, and vanadium phosphate cathode material and aluminum fluoride cladding vanadium phosphate cathode material circulation are steady
Qualitative test.
Specific embodiment
Embodiment 1:
0.05g starch and 0.05g acetylene black are dissolved in 20ml deionization by a kind of preparation method of vanadium phosphate cathode material
In water, 3.64gV is then added2O5, 0.72gLiOHH2O, 3.45gNH4H2PO4, stir evenly, form homogeneous latex emulsion.Wherein,
Mixed solution is spray-dried at room temperature, intake air temperature is 180 DEG C, and powder is obtained after dry, ball milling 1.5h is carried out, then
700 DEG C of holding 8h are calcined in air obtains the Li of hollow microsphere3V2(PO4)3Powder.
A kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material, by 3.75gAl (NO3)3It is dissolved in aqueous solution,
Then 2g Li is added3V2(PO4)3Powder, by the NH of 1.92g4F is dissolved in deionized water, at 70 DEG C, by NH4F solution is slow
It is added drop-wise to Al (NO3)3In solution, continue to stir 5h.The dry 10h under 80 DEG C of vacuum, by gained powder 350 in argon atmosphere
5h is calcined at DEG C, obtains aluminum fluoride cladding vanadium phosphate cathode material.
Embodiment 2:
0.02g starch and 0.02g acetylene black are dissolved in 20ml deionization by a kind of preparation method of vanadium phosphate cathode material
In water, 3.73gV is added2O5, 0.72gLiOHH2O, 3.45gNH4H2PO4Form homogeneous latex emulsion.At room temperature by mixed solution
It is spray-dried, intake air temperature is 190 DEG C.Powder ball milling 2.0h is obtained, then calcines 800 DEG C of holding 10h in air and obtains
The Li of hollow microsphere3V2(PO4)3Powder.
A kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material, by the NH of 1.92g4The Al of F and 4.8g
(NO3)3·9H2O is dissolved in respectively in 20mL deionized water.In Al (NO3)32g Li is added in aqueous solution3V2(PO4)3Powder, so
NH is slowly added dropwise under 80 DEG C of stirrings afterwards4F solution continues to stir 8h.In 100 DEG C of vacuum drying 12h, by gained powder in argon gas
8h is calcined at 400 DEG C in atmosphere, obtains aluminum fluoride cladding vanadium phosphate cathode material.
Embodiment 3:
0.10g starch and 0.10g acetylene black are dissolved in 20ml deionization by a kind of preparation method of vanadium phosphate cathode material
In water, 3.73gV is added2O5, 0.73gLiOHH2O, 3gNH4H2PO4Form homogeneous latex emulsion.Mixed solution is carried out at room temperature
Spray drying, intake air temperature are 190 DEG C.Obtain powder ball milling 2.0h, then in air calcine 800 DEG C of holding 10h obtain it is hollow
The Li of microballoon3V2(PO4)3Powder.
A kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material, by the NH of 1.92g4The Al of F and 4.5g
(NO3)3·9H2O is dissolved in respectively in 20mL deionized water.In Al (NO3)32g Li is added in aqueous solution3V2(PO4)3Powder, so
NH is slowly added dropwise under 80 DEG C of stirrings afterwards4F solution continues to stir 8h.In 100 DEG C of vacuum drying 12h, by gained powder in argon gas
8h is calcined at 400 DEG C in atmosphere, obtains AlF3Coat Li3V2(PO4)3Material.
The electrochemical property test of vanadium phosphate cathode material and aluminum fluoride cladding vanadium phosphate cathode material: by vanadium phosphate
Lithium anode material and aluminum fluoride coat vanadium phosphate cathode material as positive electrode and full battery are made using graphite as cathode,
AlF is tested under 5C current density3And AlF3@Li3V2(PO4)3The cyclical stability of material.
Analysis test result shows that the initial discharge specific capacity of aluminum fluoride cladding vanadium phosphate cathode material is 123mAh/
G, specific capacity only has lost 3.2% after 100 circle cycle charge-discharges, however AlF3The cycle charge discharge under identical current density
Specific capacity and capacitance loss are to distinguish 92mAh/g after 100 circle of electricity, 12.0%.Thus, monophosphate monophosphate vanadium lithium anode material is through fluorine
There is initial discharge specific capacity with circulation discharge performance after change aluminium cladding is obviously improved.
Claims (9)
1. a kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material, includes the following steps:
(1) starch and acetylene black is soluble in water, V is added2O5, LiOHH2O, NH4H2PO4Lotion is formed, is then sprayed
Dry, ball milling, calcining obtains Li3V2(PO4)3Powder；
(2) in Al (NO3)3Li is added in solution3V2(PO4)3Then NH is added dropwise in powder4F solution；Then dry, calcining, final
Vanadium phosphate cathode material is coated to aluminum fluoride.
2. a kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material according to claim 1, it is characterised in that:
The LiOHH2O:V2O5: NH4H2PO4Molar ratio be 3-3.05:2-2.05:3.
3. a kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material according to claim 1, it is characterised in that:
The quality of the starch is the 0.1-0.5% of solution quality, and the quality of the acetylene black is the 0.1- of solution gross mass
0.5%.
4. a kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material according to claim 1, it is characterised in that:
In the step (1), drying temperature is 180-200 DEG C.
5. a kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material according to claim 1, feature exist
In: in the step (1), calcination temperature is 700-900 DEG C, calcination time 8-10h.
6. a kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material according to claim 1, it is characterised in that:
Al (the NO3)3With NH4F molar ratio is 1:3-3.2.
7. a kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material according to claim 1, it is characterised in that:
The Li3V2(PO4)3With Al (NO3)3Molar ratio be 1:0.8-1.2.
8. a kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material according to claim 1, it is characterised in that:
In the step (2), reaction temperature is 70-90 DEG C, reaction time 5-10h.
9. a kind of preparation method of aluminum fluoride cladding vanadium phosphate cathode material according to claim 1, it is characterised in that:
In the step (2), calcination temperature is 350-450 DEG C, calcination time 5-10h.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734637A (en) * | 2008-11-20 | 2010-06-16 | 中国科学院理化技术研究所 | Preparation method of anode material vanadium-lithium phosphate powder for lithium ion battery |
| CN102544505A (en) * | 2011-12-15 | 2012-07-04 | 湖北万润新能源科技发展有限公司 | Surface modification method of lithium iron phosphate cathode material |
| CN104577120A (en) * | 2015-01-04 | 2015-04-29 | 合肥国轩高科动力能源股份公司 | Preparation method of lithium vanadium phosphate and fluorination lithium vanadium phosphate composite positive pole material |
| CN105958017A (en) * | 2016-05-10 | 2016-09-21 | 山东玉皇新能源科技有限公司 | Preparation method for aluminum-fluoride-coated lithium nickel cobalt manganate positive electrode material |
| CN108832104A (en) * | 2018-06-20 | 2018-11-16 | 合肥乘电科技有限责任公司 | A kind of preparation method of aluminum fluoride cladding nickel cobalt aluminic acid lithium material |
-
2019
- 2019-02-28 CN CN201910151749.9A patent/CN109935809A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101734637A (en) * | 2008-11-20 | 2010-06-16 | 中国科学院理化技术研究所 | Preparation method of anode material vanadium-lithium phosphate powder for lithium ion battery |
| CN102544505A (en) * | 2011-12-15 | 2012-07-04 | 湖北万润新能源科技发展有限公司 | Surface modification method of lithium iron phosphate cathode material |
| CN104577120A (en) * | 2015-01-04 | 2015-04-29 | 合肥国轩高科动力能源股份公司 | Preparation method of lithium vanadium phosphate and fluorination lithium vanadium phosphate composite positive pole material |
| CN105958017A (en) * | 2016-05-10 | 2016-09-21 | 山东玉皇新能源科技有限公司 | Preparation method for aluminum-fluoride-coated lithium nickel cobalt manganate positive electrode material |
| CN108832104A (en) * | 2018-06-20 | 2018-11-16 | 合肥乘电科技有限责任公司 | A kind of preparation method of aluminum fluoride cladding nickel cobalt aluminic acid lithium material |
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