CN106505197A - A kind of method for preparing vanadium phosphate cathode material - Google Patents

A kind of method for preparing vanadium phosphate cathode material Download PDF

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Publication number
CN106505197A
CN106505197A CN201510567876.9A CN201510567876A CN106505197A CN 106505197 A CN106505197 A CN 106505197A CN 201510567876 A CN201510567876 A CN 201510567876A CN 106505197 A CN106505197 A CN 106505197A
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lithium
source
vanadium
cathode material
phosphate cathode
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CN106505197B (en
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冯凯
程意
张华民
李先锋
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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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
    • 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
    • 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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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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  • Manufacturing & Machinery (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
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Abstract

The present invention relates to a kind of method for preparing vanadium phosphate cathode material, prepares vanadium phosphate cathode material using fusion method, by the ground and mixed melting in proportion of raw material vanadium source, phosphorus source, lithium source；Product is taken out after naturally cooling to room temperature and adds carbon source grinding uniform；3-5h will be calcined under the conditions of 300-400 DEG C of product, calcining 6-10h obtains vanadium phosphate cathode material under the conditions of 700-850 DEG C after obtaining material previously treated.The present invention directly adopts vanadic anhydride or vanadic acid amine as raw material, it is to avoid trivalent vanadium is oxidized；Synthetic method is simple, and the time is short, low cost, with industrial applications prospect.

Description

A kind of method for preparing vanadium phosphate cathode material
Technical field
The present invention relates to a kind of method for preparing lithium vanadium phosphate lithium ion positive electrode.
Background technology
Lithium ion battery has that specific energy is high, self discharge coefficient is little, has extended cycle life, lightweight and advantages of environment protection, becomes the contenders of electric automobile and hybrid vehicle power supply.Common lithium ion power positive electrode has spinel lithium manganate, cobalt acid lithium and polyanion class positive electrode (LiMPO4, M=Mn, Fe, V etc.).Wherein cobalt acid lithium structure in lithium abjection and telescopiny is very unstable, and its expensive.Spinels LiMn2O4 causes its cyclical stability and high rate performance poor due to jahn teller effect.Compared with this two classes material, polyanionic positive electrode has preferable heat stability and structural stability.Wherein, LiFePO4 (LiFePO4) have extended cycle life, safe, cheap, but there is the defects such as electronic and ionic poorly conductive, lithium ion diffusion coefficient be low and heavy-current discharge characteristic is poor.It is all the phosphoric acid vanadium lithium (Li of polyanionic structure3V2(PO4)3) theoretical energy density up to 500mWh/g, compares LiFePO4 with higher ion-electron electric conductivity, theoretical charge/discharge capacity and charging/discharging voltage platform, therefore become the positive electrode in lithium ion battery with very big application prospect.
But phosphoric acid vanadium lithium has the disadvantages that and hinders its practical application：(1) lithium ion is in Li3V2(PO4)3Middle diffusion difficulty causes the utilization rate of active material low；(2) high voltage (4.8V) cyclical stability and high rate performance are poor；(3) synthetic method takes.Existing research improves Li by following approach3V2(PO4)3Performance：(1) synthesize the Li of small particle3V2(PO4)3Come the Li for improving+Diffusivity；(2) coated with carbon improves electronic conductivity；(3) cation doping improves the stability of electrical conductivity and structure；(4) synthetic method, Simplified flowsheet are improved.
Content of the invention
Present invention aim at there is provided a kind of new simpler method synthesis phosphoric acid vanadium lithium.Technical problem to be solved is the synthetic method for simplifying phosphoric acid vanadium lithium, simplifies synthesis technique, shortens generated time, and improves its chemical property.
For realizing object above, technical scheme is as follows：
A kind of method for preparing vanadium phosphate cathode material, prepares vanadium phosphate cathode material using fusion method, comprises the following steps that：
1) raw material vanadium source, phosphorus source, lithium source are pressed vanadium：Phosphorus：Lithium is with (1-2):3:(1.5-1.65) or (1-2):3:(3-3.3) molar ratio ground and mixed uniformly melts 0.5-2h at a temperature of 700-900 DEG C；
2) product is taken out after naturally cooling to room temperature and adds carbon source grinding uniform；Carbon source is (0.2-0.4) with the mass ratio of synthetic product:1；
3) 3-5h will be calcined under the conditions of 300-400 DEG C of step (2) product, obtains material previously treated
4) material previously treated is calcined 6-10h under the conditions of 700-850 DEG C and obtains vanadium phosphate cathode material；
Described vanadium source is one or two in vanadic anhydride or vanadic acid amine.
Wherein step (3) and (4) are carried out in an inert atmosphere, and described inert atmosphere is that nitrogen or argon or volume ratio are 1:1 argon and the mixed gas of hydrogen.
Phosphorus source described in step (1) is diammonium phosphate, the one kind in ammonium dihydrogen phosphate or two kinds；The carbon source is sucrose, glucose, one or two or more kinds in SP；The lithium source is lithium carbonate, Lithium hydrate, lithium acetate, lithium nitrate, lithium fluoride, one or two or more kinds in lithium oxalate.
Beneficial effect
The present invention directly adopts vanadic anhydride or vanadic acid amine as raw material, it is to avoid trivalent vanadium is oxidized；Synthetic method is simple, and the time is short, low cost, with industrial applications prospect；Compared with traditional sol-gal process, there is the phosphoric acid vanadium lithium of synthesis higher initial discharge specific capacity, more preferable cyclical stability and high rate performance, reason mainly to react under the high temperature conditions, and the degree of crystallinity of phosphoric acid vanadium lithium is greatly improved, crystal formation is more perfect, and structure is more stable.
Description of the drawings
Sample and the phosphoric acid vanadium lithium that using sol-gal process synthesized first charging and discharging curves under the running voltage of 3-4.3V of the Fig. 1 for embodiment 1；
Fig. 2 is the cyclical stability comparison diagram under the running voltage of the 3-4.3V of the sample and the phosphoric acid vanadium lithium synthesized using sol-gal process of embodiment 1.
Specific embodiment
Embodiment 1
0.9094g vanadic anhydrides are taken, 1.7253g ammonium dihydrogen phosphates, 0.6294g Lithium hydrates mix, be placed in crucible after grinding is uniform, in the Muffle furnace that then crucible is placed in 850 DEG C, taken out after 20 minutes.Taking out product therein after natural cooling adds 20% sucrose to be ground to powder.The powder is placed in tube furnace, under argon atmosphere, 350 DEG C is warmed up to the programming rate of 3 °/min and is incubated 4h, take out grinding after cooling, continue to be raised to 750 DEG C with the programming rate of 3 °/min and be incubated 10h.By resulting materials according to active substance, conductive black, binding agent three mass ratio be 8:1:1 is dissolved in mix homogeneously in appropriate N-Methyl pyrrolidone, is coated into the electrode film that thickness is 0.15mm with wet film maker, is cut into the electrode slice of a diameter of 12mm after vacuum drying with microtome, weighs and calculate the quality of active substance.Simultaneously using lithium piece as positive pole, using Clogard 2500 as barrier film, the LiPF of 1mol/L6EC+DMC (volume ratio is 1:1) solution is electrolyte, dresses up button cell, the battery of assembling is carried out electro-chemical test then in the glove box full of argon.
From Fig. 1, Fig. 2 it is apparent that：Relative to conventional sol-gal process, using the initial discharge specific capacity of the phosphoric acid vanadium lithium of this new method-Melting Synthesis, cycle performance and high rate performance are greatly improved, and reason is to improve the degree of crystallinity of phosphoric acid vanadium lithium in the reaction condition of high temperature, make that its crystal formation is more perfect, structure is more stable.
Embodiment 2
0.9094g vanadic anhydrides are taken, 1.9807g diammonium phosphate, 1.1083g lithium carbonate mix, be placed in crucible after grinding is uniform, in the Muffle furnace that then crucible is placed in 850 DEG C, taken out after 20 minutes.Taking out product therein after natural cooling adds 20% sucrose to be ground to powder.The powder is placed in tube furnace, under argon atmosphere, 350 DEG C is warmed up to the programming rate of 3 °/min and is incubated 4h, take out grinding after cooling, continue to be raised to 750 DEG C with the programming rate of 3 °/min and be incubated 10h.By resulting materials, it is 8 according to the mass ratio of active substance, conductive black, binding agent three:1:1 is dissolved in mix homogeneously in appropriate N-Methyl pyrrolidone, is coated into the electrode film that thickness is 0.15mm with wet film maker, is cut into the electrode slice of a diameter of 12mm after vacuum drying with microtome, weighs and calculate the quality of active substance.Simultaneously using lithium piece as positive pole, using Clogard 2500 as barrier film, the LiPF of 1mol/L6EC+DMC (volume ratio is 1:1) solution is electrolyte, in the glove box full of argon dresses up button cell.Then the battery of assembling is carried out electro-chemical test.

Claims (3)

1. a kind of method for preparing vanadium phosphate cathode material, prepares vanadium phosphate cathode material using fusion method, its It is characterised by：
(1) raw material vanadium source, phosphorus source, lithium source are pressed vanadium：Phosphorus：Lithium is with (1-2):3:(1.5-1.65) or (1-2): 3:(3-3.3) molar ratio ground and mixed uniformly melts 0.5-2h at a temperature of 700-900 DEG C；
(2) product is taken out after naturally cooling to room temperature and adds carbon source grinding uniform；Carbon source and synthetic product Mass ratio be (0.2-0.4):1；
(3) 3-5h will be calcined under the conditions of 300-400 DEG C of step (2) product, obtains material previously treated；
(4) material previously treated is calcined 6-10h under the conditions of 700-850 DEG C and obtains vanadium phosphate cathode material；
Described vanadium source is one or two in vanadic anhydride or vanadic acid amine.
2. method according to claim 1, it is characterised in that：Wherein step (3) and (4) are in indifferent gas Carry out in atmosphere, described inert atmosphere is that nitrogen or argon or volume ratio are 1:1 argon is mixed with hydrogen Close gas.
3. method according to claim 1, it is characterised in that：Phosphorus source described in step (1) is phosphoric acid hydrogen two One kind in ammonium, ammonium dihydrogen phosphate or two kinds；The carbon source is sucrose, glucose, the one kind or two in SP More than kind；The lithium source be lithium carbonate, Lithium hydrate, lithium acetate, lithium nitrate, lithium fluoride, in lithium oxalate One or two or more kinds.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107611431A (en) * 2017-08-22 2018-01-19 天津泰和九思科技有限公司 A kind of lithium vanadium phosphate material and preparation method thereof and lithium ion battery prepared therefrom
CN109775681A (en) * 2018-12-27 2019-05-21 大连博融新材料有限公司 A method of recycling vpo catalyst directly prepares phosphoric acid vanadium lithium
CN116119640A (en) * 2022-12-08 2023-05-16 攀钢集团攀枝花钢铁研究院有限公司 Method for improving tap density of lithium vanadium phosphate material of lithium battery anode material

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1872671A (en) * 2006-06-09 2006-12-06 广州鸿森材料有限公司 Method for preparing lithium vanadium phosphoric acid of anode material of lithium ion battery under high pressure
CN101304084A (en) * 2007-05-11 2008-11-12 深圳市比克电池有限公司 Method for preparing Li3V2(PO4)3/C composite anode material and anode material made by the same
US20090148377A1 (en) * 2007-12-11 2009-06-11 Moshage Ralph E Process For Producing Electrode Active Material For Lithium Ion Cell

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1872671A (en) * 2006-06-09 2006-12-06 广州鸿森材料有限公司 Method for preparing lithium vanadium phosphoric acid of anode material of lithium ion battery under high pressure
CN101304084A (en) * 2007-05-11 2008-11-12 深圳市比克电池有限公司 Method for preparing Li3V2(PO4)3/C composite anode material and anode material made by the same
US20090148377A1 (en) * 2007-12-11 2009-06-11 Moshage Ralph E Process For Producing Electrode Active Material For Lithium Ion Cell

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107611431A (en) * 2017-08-22 2018-01-19 天津泰和九思科技有限公司 A kind of lithium vanadium phosphate material and preparation method thereof and lithium ion battery prepared therefrom
CN109775681A (en) * 2018-12-27 2019-05-21 大连博融新材料有限公司 A method of recycling vpo catalyst directly prepares phosphoric acid vanadium lithium
CN116119640A (en) * 2022-12-08 2023-05-16 攀钢集团攀枝花钢铁研究院有限公司 Method for improving tap density of lithium vanadium phosphate material of lithium battery anode material
CN116119640B (en) * 2022-12-08 2024-09-06 攀钢集团攀枝花钢铁研究院有限公司 Method for improving tap density of lithium vanadium phosphate material of lithium battery anode material

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