CN105185990A - Preparation method of spherical lithium-ion secondary battery cathode material vanadium phosphate monohydrate - Google Patents

Preparation method of spherical lithium-ion secondary battery cathode material vanadium phosphate monohydrate Download PDF

Info

Publication number
CN105185990A
CN105185990A CN201510503366.5A CN201510503366A CN105185990A CN 105185990 A CN105185990 A CN 105185990A CN 201510503366 A CN201510503366 A CN 201510503366A CN 105185990 A CN105185990 A CN 105185990A
Authority
CN
China
Prior art keywords
secondary battery
ion secondary
preparation
lithium ion
spherical lithium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510503366.5A
Other languages
Chinese (zh)
Other versions
CN105185990B (en
Inventor
陈泽华
麻鹏程
孙广
曹建亮
王晓冬
孟哈日巴拉
张传祥
张战营
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Henan University of Technology
Original Assignee
Henan University of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Henan University of Technology filed Critical Henan University of Technology
Priority to CN201510503366.5A priority Critical patent/CN105185990B/en
Publication of CN105185990A publication Critical patent/CN105185990A/en
Application granted granted Critical
Publication of CN105185990B publication Critical patent/CN105185990B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • 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

Abstract

The invention relates to a preparation method of a spherical lithium-ion secondary battery cathode material vanadium phosphate monohydrate. The spherical lithium-ion secondary battery cathode material VPO4.H2O is prepared by a hydrothermal method. The preparation method has the advantages of being mild in reaction condition, high in product purity, good in crystallinity, uniform in particle size distribution and free of an agglomeration phenomenon; the average particle sizes of the particles are 1.5-3 microns; the prepared cathode material is regular spherical particles, and has relatively high specific surface area in structure; sufficient moistening of electrolyte is facilitated; lithium ion transportation in the cathode material is facilitated in the charging and discharging processes; and the spherical lithium-ion secondary battery cathode material VPO4.H2O synthesized by the method shows good electrochemical properties.

Description

A kind of preparation method of spherical lithium ion secondary battery positive electrode one water vanadium phosphate
Technical field
The present invention relates to electrochemical field, is a kind of preparation method of spherical lithium ion secondary battery positive electrode one water vanadium phosphate specifically.
Background technology
Lithium rechargeable battery is a kind of novel Green Chemistry power supply, has the advantages such as voltage is high, the life-span is long and energy density is large, volume is little, self-discharge rate is low compared with traditional nickel-cadmium cell, Ni-MH battery.Since nineteen ninety comes into the market for the first time, the scope of application is more and more wider, has been widely used in various portable electric appts.Along with the rise of new-energy automobile, lithium ion battery, with the characteristic of its excellence, is considered to one of desirable energy storage device of new-energy automobile.
Due in the composition of lithium rechargeable battery, positive electrode is the key factor determining its chemical property, security performance, price and future thrust.At present, positive electrode mostly is lithium-transition metal composite oxides, and people have studied the cobalt lithia of layer structure, the lithium manganese oxygen of spinel structure, also have lithium ni-mh to overcharge dangerous, and cobalt resource is in short supply at present; Lithium manganese oxygen capacity is low and have JohnTail effect, and have impact on its chemical property, high temperature cyclic performance is poor.Cobalt nickel lithium manganate ternary material becomes high due to the resource shortage of cobalt with nickel, cobalt and the reason such as price fluctuation is large, be difficult to the main flow becoming power-type lithium ion battery used for electric vehicle, so need development of new lithium ion secondary positive electrode to meet the development need of society.
China's navajoite aboundresources, reserves account for 38.5% of the whole world, the explored vanadium iron magnetic ore reserves about 10,000,000,000 tons in Panzhihua Region, and vanadium reserves account for 62% of China.But navajoite exploitation is subject to the restriction of correlation technique, if combined with energy technology, turns to target with industry, not only can development and utilization new forms of energy, but also the application of vanadium resource can be expanded, promote the comprehensive utilization value of vanadium resource energetically.Therefore VPO 4h 2o is a lithium ion secondary battery anode material with very large potential value, and domestic at present do not have about VPO 4h 2o reports as the preparation of lithium ion secondary battery anode material.
Summary of the invention
The object of this invention is to provide a kind of preparation method of spherical lithium ion secondary battery positive electrode one water vanadium phosphate.
For solving the problems of the technologies described above, the technical solution used in the present invention is:
A preparation method for spherical lithium ion secondary battery positive electrode one water vanadium phosphate, comprises the following steps:
1) by H 3pO 4and VCl 3be that 3:1 ~ 5:1 joins in polytetrafluoroethylene reactor according to mol ratio, add water and be uniformly mixed, while stirring adjust ph to 1.5 ~ 3.5, then polytetrafluoroethylene reactor is sealed, stir 45 ~ 50h;
2) reactor is put into Muffle furnace and carry out intensification heating with 5 DEG C/min speed, when being warming up to 150 ~ 200 DEG C, insulation 70 ~ 75h;
3) reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, by gained washing of precipitate, drying, obtain target product VPO 4h 2o;
For regulating the conditioning agent of pH to be methyl triethyl ammonium chloride in described step 1);
Mixing time in described step 1) is 48h;
Described step 2) in temperature retention time be 72h;
Solvent for washing in described step 3) is absolute ethyl alcohol;
Baking temperature in described step 3) is 90 DEG C.
Beneficial effect of the present invention:
The preparation method of spherical lithium ion secondary battery positive electrode one water vanadium phosphate provided by the invention, utilizes hydro thermal method to prepare spherical lithium ion secondary battery positive electrode VPO 4h 2o, reaction condition is gentle, and product purity is high, better crystallinity degree, and mean particle size is 1.5 ~ 3 μm, even particle size distribution, soilless sticking phenomenon; The positive electrode of preparation is regular spheric granules, and its structure has higher specific area, is conducive to the fully moistening of electrolyte, is conducive to lithium ion transmission therein in charge and discharge process; The spherical lithium ion secondary battery positive electrode VPO of the present invention's synthesis 4h 2o shows good chemical property.
Accompanying drawing explanation
Fig. 1 is spherical lithium ion secondary battery positive electrode VPO prepared by embodiment 1 4h 2the SEM figure mono-of O;
Fig. 2 is spherical lithium ion secondary battery positive electrode VPO prepared by embodiment 1 4h 2the SEM figure bis-of O;
Fig. 3 is spherical lithium ion secondary battery positive electrode VPO prepared by embodiment 1 4h 2the XRD figure of O;
Fig. 4 is spherical lithium ion secondary battery positive electrode VPO prepared by embodiment 1 4h 2o is 0.09mA/cm in current density 2under first charge-discharge curve.
Embodiment
Below in conjunction with embodiment, the present invention is further elaborated.
A preparation method for spherical lithium ion secondary battery positive electrode one water vanadium phosphate, comprises the following steps:
1) by H 3pO 4and VCl 3be that 3:1 ~ 5:1 joins in polytetrafluoroethylene reactor according to mol ratio, add water and be uniformly mixed, while stirring adjust ph to 1.5 ~ 3.5, then polytetrafluoroethylene reactor is sealed, stir 45 ~ 50h;
2) reactor is put into Muffle furnace and carry out intensification heating with 5 DEG C/min speed, when being warming up to 150 ~ 200 DEG C, insulation 70 ~ 75h;
3) reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, by gained washing of precipitate, drying, obtain target product VPO 4h 2o.
Embodiment 1
A preparation method for spherical lithium ion secondary battery positive electrode one water vanadium phosphate, comprises the following steps:
1) by H 3pO 4and VCl 3be that 4:1 joins in polytetrafluoroethylene reactor according to mol ratio, add water and be uniformly mixed, use methyl triethyl ammonium chloride adjust ph to 2.5 while stirring, then polytetrafluoroethylene reactor is sealed, stir 48h;
2) reactor is put into Muffle furnace and carry out intensification heating with 5 DEG C/min speed, when being warming up to 200 DEG C, insulation 72h;
3) reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, by gained precipitation absolute ethanol washing, then dry under 90 DEG C of conditions, obtain target product VPO 4h 2o;
As shown in Figure 1 and Figure 2, as shown in Figure 3, product is comparatively pure for X-ray analysis, and Fig. 4 is products therefrom is 0.09mA/cm in current density for the SEM figure of products therefrom 2under first charge-discharge curve, first discharge specific capacity can reach 62mAh/g.
Embodiment 2
A preparation method for spherical lithium ion secondary battery positive electrode one water vanadium phosphate, comprises the following steps:
1) by H 3pO 4and VCl 3be that 3:1 joins in polytetrafluoroethylene reactor according to mol ratio, add water and be uniformly mixed, use methyl triethyl ammonium chloride adjust ph to 3.5 while stirring, then polytetrafluoroethylene reactor is sealed, stir 45h;
2) reactor is put into Muffle furnace and carry out intensification heating with 5 DEG C/min speed, when being warming up to 150 DEG C, insulation 75h;
3) reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, by gained precipitation absolute ethanol washing, then dry under 90 DEG C of conditions, obtain target product VPO 4h 2o.
Embodiment 3
A preparation method for spherical lithium ion secondary battery positive electrode one water vanadium phosphate, comprises the following steps:
1) by H 3pO 4and VCl 3be that 5:1 joins in polytetrafluoroethylene reactor according to mol ratio, add water and be uniformly mixed, use methyl triethyl ammonium chloride adjust ph to 1.5 while stirring, then polytetrafluoroethylene reactor is sealed, stir 50h;
2) reactor is put into Muffle furnace and carry out intensification heating with 5 DEG C/min speed, when being warming up to 180 DEG C, insulation 70h;
3) reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, by gained precipitation absolute ethanol washing, then dry under 90 DEG C of conditions, obtain target product VPO 4h 2o.

Claims (6)

1. a preparation method for spherical lithium ion secondary battery positive electrode one water vanadium phosphate, is characterized in that, comprise the following steps:
1) by H 3pO 4and VCl 3be that 3:1 ~ 5:1 joins in polytetrafluoroethylene reactor according to mol ratio, add water and be uniformly mixed, while stirring adjust ph to 1.5 ~ 3.5, then polytetrafluoroethylene reactor is sealed, stir 45 ~ 50h;
2) reactor is put into Muffle furnace and carry out intensification heating with 5 DEG C/min speed, when being warming up to 150 ~ 200 DEG C, insulation 70 ~ 75h;
3) reactor is down to room temperature with 5 DEG C/min speed, obtains greenish precipitate, by gained washing of precipitate, drying, obtain target product VPO 4h 2o.
2. the preparation method of spherical lithium ion secondary battery positive electrode one water vanadium phosphate as claimed in claim 1, is characterized in that: for regulating the conditioning agent of pH to be methyl triethyl ammonium chloride in described step 1).
3. the preparation method of spherical lithium ion secondary battery positive electrode one water vanadium phosphate as claimed in claim 1, is characterized in that: the mixing time in described step 1) is 48h.
4. the preparation method of spherical lithium ion secondary battery positive electrode one water vanadium phosphate as claimed in claim 1, is characterized in that: described step 2) in temperature retention time be 72h.
5. the preparation method of spherical lithium ion secondary battery positive electrode one water vanadium phosphate as claimed in claim 1, is characterized in that: the solvent for washing in described step 3) is absolute ethyl alcohol.
6. the preparation method of spherical lithium ion secondary battery positive electrode one water vanadium phosphate as claimed in claim 1, is characterized in that: the baking temperature in described step 3) is 90 DEG C.
CN201510503366.5A 2015-08-17 2015-08-17 A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one Expired - Fee Related CN105185990B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510503366.5A CN105185990B (en) 2015-08-17 2015-08-17 A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510503366.5A CN105185990B (en) 2015-08-17 2015-08-17 A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one

Publications (2)

Publication Number Publication Date
CN105185990A true CN105185990A (en) 2015-12-23
CN105185990B CN105185990B (en) 2018-01-02

Family

ID=54907941

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510503366.5A Expired - Fee Related CN105185990B (en) 2015-08-17 2015-08-17 A kind of preparation method of the water vanadium phosphate of spherical lithium ion secondary battery positive electrode one

Country Status (1)

Country Link
CN (1) CN105185990B (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016127024A (en) * 2014-12-26 2016-07-11 三星電子株式会社Samsung Electronics Co., Ltd. Composite positive electrode active material, method for manufacturing the same, positive electrode including the same, and lithium battery including the same
CN107230771A (en) * 2017-07-14 2017-10-03 中南大学 A kind of method of vanadium phosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002338217A (en) * 2001-05-19 2002-11-27 Korea Electronics Telecommun Method for ultrasonic-chemically preparing vopo4.2h2o, and application of the product for lithium secondary battery positive electrode material
CN103872324A (en) * 2014-03-28 2014-06-18 郑俊超 Preparation method of petaloid lithium ion battery negative electrode material VPO4

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002338217A (en) * 2001-05-19 2002-11-27 Korea Electronics Telecommun Method for ultrasonic-chemically preparing vopo4.2h2o, and application of the product for lithium secondary battery positive electrode material
CN103872324A (en) * 2014-03-28 2014-06-18 郑俊超 Preparation method of petaloid lithium ion battery negative electrode material VPO4

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
A.CASTETS ET AL.: ""NMR study of the LiMnPO4•OH and MPO4•H2O(M=Mn,V) homeotypic phases and DFT caculations"", 《SOLID STATE NUCLEAR MAGNETIC RESONANCE》 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2016127024A (en) * 2014-12-26 2016-07-11 三星電子株式会社Samsung Electronics Co., Ltd. Composite positive electrode active material, method for manufacturing the same, positive electrode including the same, and lithium battery including the same
CN107230771A (en) * 2017-07-14 2017-10-03 中南大学 A kind of method of vanadium phosphate coated lithium ion battery anode material nickel cobalt manganic acid lithium
CN107230771B (en) * 2017-07-14 2020-08-14 中南大学 Method for coating lithium ion battery cathode material nickel cobalt lithium manganate with vanadium phosphate

Also Published As

Publication number Publication date
CN105185990B (en) 2018-01-02

Similar Documents

Publication Publication Date Title
CN104218234B (en) A kind of lithium ion battery composite cathode material of high circulation performance and preparation method thereof
CN103311532B (en) Preparation method of lithium-enriched anode material with nano-grade lamellar-spinel composite structure
CN103280574A (en) Lithium-enriched ternary anode material of power lithium-ion battery and preparation method of lithium-enriched ternary anode material
CN103943844A (en) Cobalt-free lithium-rich manganese-based cathode material as well as preparation method and application thereof
CN106299282B (en) Nitrogen-doped carbon nanotube sulfur composite material and preparation method thereof
CN105390693B (en) A kind of nanocrystalline positive electrode LiNi of high power capacity0.8Co0.1Mn0.1O2And its high pressure synthesis method
CN103474625A (en) Coating method for core-shell novel positive electrode material for lithium ion battery
CN102315450A (en) Hydrothermal synthesis preparation method of ion doping high-performance lithium iron phosphate
CN103390748B (en) A kind of preparation method of alumina-coated lithium cobaltate cathode material
CN106058238A (en) Modified spherical nickel cobalt lithium manganate NCM622 anode material and preparation method thereof
WO2020098275A1 (en) Sio2-covered ternary positive electrode material and preparation method therefor
CN105789615A (en) Modified lithium nickel cobalt manganese cathode material and preparation method thereof
CN102275890A (en) Microwave-assisted synthesis method of nanometer lithium iron phosphate
CN105355892A (en) Preparation method of lithium ion battery cathode
CN108400320B (en) Method for vulcanizing surface of spinel lithium nickel manganese oxide positive electrode material
CN105702956A (en) Negative material for sodium-ion battery and preparation method of negative material
CN102185154A (en) Nano ferric phosphate hollow sphere lithium ion battery and preparation method thereof
CN102832381A (en) Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life
CN106340621A (en) Ferric negative electrode material for lithium battery and preparation method thereof
CN105958039A (en) Preparation method of modified lithium nickel manganese oxide cathode material, and high-voltage lithium ion battery
CN105789621B (en) A method of molten state lithium source surface tension is reduced so as to improve anode material for lithium-ion batteries high temperature solid-phase sintering process
CN111268727A (en) Calcium vanadate composite material and preparation method and application thereof
CN105006563B (en) Lithium ion battery anode active material Li2ZnTi3O8Preparation method
CN104201342A (en) Method for improving physical property of lithium and manganese enriched lithium ion battery pole pieces
CN103413935A (en) Mo-doped lithium-rich positive electrode material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20180102

Termination date: 20190817