CN104835960A - Preparation method for lithium ion battery cathode material VPO4F - Google Patents

Preparation method for lithium ion battery cathode material VPO4F Download PDF

Info

Publication number
CN104835960A
CN104835960A CN201510234376.3A CN201510234376A CN104835960A CN 104835960 A CN104835960 A CN 104835960A CN 201510234376 A CN201510234376 A CN 201510234376A CN 104835960 A CN104835960 A CN 104835960A
Authority
CN
China
Prior art keywords
vanadium
ion battery
preparation
negative material
lithium ion
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
CN201510234376.3A
Other languages
Chinese (zh)
Other versions
CN104835960B (en
Inventor
郑俊超
韩亚东
张宝
朱玉时
周其杰
孙楠
童汇
董鹏远
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.)
Central South University
Original Assignee
Central South University
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 Central South University filed Critical Central South University
Priority to CN201510234376.3A priority Critical patent/CN104835960B/en
Publication of CN104835960A publication Critical patent/CN104835960A/en
Application granted granted Critical
Publication of CN104835960B publication Critical patent/CN104835960B/en
Active 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
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Secondary Cells (AREA)

Abstract

The invention relates to a preparation method for a lithium ion battery cathode material VPO4F. The preparation method comprises a first step of dissolving a vanadium source, a phosphorus source and a reducing agent in deionized water according to the molar ratio of vanadium, phosphorus and reducing agent of 1:1:(1-4); a second step of putting the obtained solution in 60-90DEG C water bath kettle, stirring for 4-8 hours to form a solution; a third step of adjusting pH of the obtained solution to 6-9; a fourth step of spray drying the obtained solution for prilling so as to obtain spherical VPO4F precursor; and a fifth step of putting the obtained VPO4F precursor in a tubular sintering furnace, and sintering for 6-15 hours at 400-800DEG C in non-reducing atmosphere. The VPO4F prepared for the first time has a stable three-dimensional frame structure, a fast particle transmission channel and a unique micro spherical appearance, and shows an excellent electrochemical property.

Description

A kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium
Technical field
The present invention relates to a kind of preparation method of lithium ion battery negative material, especially relate to a kind of spray drying technology that adopts and prepare ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium (VPO 4f) method, belongs to technical field of lithium ion.
Background technology
Negative material is as one of lithium ion battery critical material, and its research is the focus in this field always.At present, commercialization graphite cathode material is due to low (the about 372mAh g of its theoretical capacity -1), metal oxide volumetric expansion in removal lithium embedded process is serious, and invertibity is poor, and these negative materials are all difficult to the instructions for use meeting electrokinetic cell, therefore, explores other alternative Novel anode materials and just seems particularly necessary.
Summary of the invention
The technical problem to be solved in the present invention is, overcome the deficiency of existing negative material, provide a kind of specific capacity high, good rate capability, the preparation method of Stability Analysis of Structures and the good lithium ion battery negative material fluorophosphoric acid vanadium of security performance, the electrochemical performance of gained fluorophosphoric acid vanadium.
The technical scheme that the present invention solves the employing of its technical problem is that a kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium, comprises the following steps:
(1) ratio being 1:1:1:1-4 by vanadium source, phosphorus source, fluorine source, reducing agent according to the mol ratio of v element, P elements, fluorine element and reducing agent is dissolved in deionized water, and the concentration controlling vanadium metal ion is 0.05-1molL -1(preferred 0.08-0.8 molL -1, more preferably 0.1-0.5 molL -1, preferred 0.2-0.4 molL further -1);
(2) step (1) gained mixed liquor is placed in 60-90 DEG C of water-bath and stirs 4-8h, form solution;
(3) step (2) gained solution is regulated pH to 6-9;
(4) step (3) gained solution is carried out drying-granulating by spray-dired method, obtain fluorophosphoric acid vanadium (VPO 4f) presoma;
(5) by step (4) gained fluorophosphoric acid vanadium (VPO 4f) presoma is placed in pipe type sintering furnace, the 400-800 DEG C of preferred 8-15h of sintering 6-20h(under non-reducing atmosphere), cool to room temperature, obtains ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium (VPO 4f).
Further, in step (1), described vanadium source is the one in vanadic oxide, ammonium metavanadate, ammonium vanadate, vanadyl acetylacetonate, vanadyl oxalate.
Further, in step (1), described phosphorus source is the one in phosphoric acid, phosphorus pentoxide, pyrophosphoric acid, ammonium phosphate.
Further, in step (1), described fluorine source is the one in lithium fluoride, ammonium fluoride, sodium fluoride.
Further, in step (1), described reducing agent is the one in tartaric acid, citric acid, oxalic acid, ethanedioic acid, adipic acid, malonic acid, ascorbic acid.
Further, in step (4), described spraying dry intake air temperature is at 180-260 DEG C, and spraying dry peristaltic pump rotating speed is at 1000-1800rpm/min, and spraying dry rotation speed of fan is at 60-100HZ.
Further, in step (5), described non-reducing atmosphere is argon gas, nitrogen or helium, or the mist of non-reducing gas and inert gas.
VPO 4the space structure of F is by PO 4tetrahedron and VO 4f 2the space three-dimensional frame structure of octahedra composition.In this three-dimensional structure, VO 4f 2octahedron forms zig-zag chain and chain is extended at one-dimensional square to by sharing F ion, by shared PO 4 3-tetrahedral angle makes chain intersect, thus forms stable space three-dimensional structure.At VPO 4in F, because F is to PO 4 3-stronger inductive effect, makes its structure more stable; Therefore VPO 4f can provide stable three-dimensional frame structure and particle conveying channels fast for electrode material as during negative material, in charge and discharge process, crystal volume change is little, the security performance of reinforcing material, particle conveying channels can increase the high rate performance of material fast.And there is active chemical property (V to V due to vanadium 5+), VPO 4f chemical valence in charge and discharge process can change from+4 to 0.Therefore, VPO 4f has higher theoretical specific capacity (650mAh/g); And China's vanadium resource enriches, raw material sources is extensive, with low cost.Therefore, VPO 4f is a lithium ion battery negative material with very large potential value.
The present invention obtains spherical precursor through spraying dry first, and synthesis obtains negative material fluorophosphoric acid vanadium; In follow-up non-reducing atmosphere, sintering obtains spherical fluorophosphoric acid vanadium negative material, because fluorophosphoric acid vanadium has stable three-dimensional frame structure, unobstructed passage can be stablized for the deintercalation of lithium ion provides, active active metallic element V can provide higher specific discharge capacity, as showing excellent chemical property during lithium ion battery negative material.
Accompanying drawing explanation
Fig. 1 is the SEM diffraction pattern of the embodiment of the present invention 2 gained ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium;
Fig. 2 uses the first charge-discharge curve chart of the embodiment of the present invention 2 gained ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium institute's assembled battery under 0.1C, 0.5C, 1C multiplying power.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.The embodiment of the present invention is used to provide a further understanding of the present invention, for explaining the present invention, but is not construed as limiting the invention.
Embodiment 1
The present embodiment comprises the following steps:
(1) take vanadic oxide 0.025mol, phosphoric acid 0.05mol, ammonium fluoride 0.05mol, ascorbic acid 0.2mol, mixed, be dissolved in the deionized water of 1000mL;
(2) step (1) gained solution is placed in 80 DEG C of water-bath mechanical agitation 5h, forms uniform solution;
(3) step (2) gained solution is regulated pH to 8;
(4) step (3) gained solution is carried out drying-granulating by spray-dired method, described spraying dry: intake air temperature is 250 DEG C, peristaltic pump rotating speed is 1400rpm/min, and rotation speed of fan is 100HZ, obtains VPO 4f presoma;
(5) by step (4) gained fluorophosphoric acid vanadium (VPO 4f) presoma is placed in pipe type sintering furnace, and under an argon atmosphere in 700 DEG C of sintering 10h, then Temperature fall is to room temperature, obtains ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
The assembling of battery: take boric acid vanadium negative material obtained by 0.24g the present embodiment, add 0.03g Super-P and above-mentioned material is assembled into CR2025 button cell, battery is surveyed its charge/discharge capacity and high rate performance in 0.01V ~ 1.5V voltage range, and test result first discharge specific capacity under 0.1C, 0.5C, 1C multiplying power is followed successively by 651.3mAh/g, 436 mAh/g, 389.5mAh/g.
Embodiment 2
The present embodiment comprises the following steps:
(1) take vanadic oxide 0.0125mol, phosphoric acid 0.025mol, sodium fluoride 0.025mol, oxalic acid 0.05mol, mixed, be dissolved in the deionized water of 250mL;
(2) step (1) gained solution is placed in 60 DEG C of thermostat water bath mechanical agitation 8h, forms solution;
(3) pH is regulated to be 7 step (2) gained solution;
(4) step (3) gained solution is carried out drying-granulating by spray-dired method, described spraying dry, intake air temperature is 260 DEG C, and peristaltic pump rotating speed is 1000rpm/min, and rotation speed of fan is 60HZ, obtains VPO 4f presoma;
(5) by step (4) gained fluorophosphoric acid vanadium (VPO 4f) presoma is placed in pipe type sintering furnace, and under an argon atmosphere in 700 DEG C of sintering 8h, then Temperature fall is to room temperature, obtains ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
Boric acid vanadium negative material obtained by the present embodiment is assembled into CR2025 button cell, battery is surveyed its charge/discharge capacity and high rate performance in 0.01V ~ 1.5V voltage range, and test result first discharge specific capacity under 0.1C, 0.5C, 1C multiplying power is followed successively by 609.5mAh/g, 382.2mAh/g, 289.9mAh/g.
The SEM diffraction pattern of the present embodiment gained ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium as shown in Figure 1; 0.1C, 0.5C, 1C first charge-discharge curve of the battery that the ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium using the present embodiment to prepare is assembled as shown in Figure 2.
Embodiment 3
The present embodiment comprises the following steps:
(1) take vanadic oxide 0.04mol, ammonium phosphate 0.08mol, ammonium fluoride 0.08mol, ethanedioic acid 0.12mol, mixed, be dissolved in the deionized water of 100mL;
(2) step (1) gained solution is placed in 80 DEG C of water-bath mechanical agitation 6h, forms uniform solution;
(3) step (2) gained solution is regulated pH to 9;
(4) step (3) gained solution is carried out drying-granulating by spray-dired method, described spraying dry: intake air temperature is 200 DEG C, peristaltic pump rotating speed is 1500rpm/min, and rotation speed of fan is 100HZ, obtains VPO 4f presoma;
(5) by step (4) gained fluorophosphoric acid vanadium (VPO 4f) presoma is placed in pipe type sintering furnace, and in a nitrogen atmosphere in 500 DEG C of sintering 20h, then Temperature fall is to room temperature, obtains ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
The present embodiment gained lithium ion battery negative material fluorophosphoric acid vanadium is assembled into CR2025 button cell, battery is surveyed its charge/discharge capacity and high rate performance in 0.01V ~ 1.5V voltage range, and test result first discharge specific capacity under 0.1C, 0.5C, 1C multiplying power is followed successively by 451.3mAh/g, 277.6mAh/g, 239.8mAh/g.
Embodiment 4
The present embodiment comprises the following steps:
(1) take ammonium metavanadate 0.01mol, phosphorus pentoxide 0.005mol, sodium fluoride 0.01mol, citric acid 0.04mol, mixed, be dissolved in the deionized water of 200mL;
(2) step (1) gained solution is placed in 90 DEG C of thermostat water bath mechanical agitation 4h, forms uniform solution;
(3) step (2) gained solution is regulated pH to 6;
(4) step (3) gained solution is carried out drying-granulating by spray-dired method, described spraying dry: intake air temperature is 180 DEG C, peristaltic pump rotating speed is 1800rpm/min, and rotation speed of fan is carry out spraying dry under 80HZ, obtains VPO 4f presoma;
(5) by step (4) gained fluorophosphoric acid vanadium (VPO 4f) presoma is placed in pipe type sintering furnace, and under an argon atmosphere in 800 DEG C of sintering 8h, then Temperature fall is to room temperature, obtains ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
Above-mentioned material is assembled into CR2025 button cell, battery is surveyed its charge/discharge capacity and high rate performance in 0.01V ~ 1.5V voltage range, and test result first discharge specific capacity under 0.1C, 0.5C, 1C multiplying power is followed successively by 589.1mAh/g, 305.2mAh/g, 289.5mAh/g.
Embodiment 5
The present embodiment comprises the following steps:
(1) take vanadyl acetylacetonate 0.1mol, phosphoric acid 0.1mol, lithium fluoride 0.1mol, oxalic acid 0.3mol, mixed, be dissolved in the deionized water of 100mL;
(2) step (1) gained solution is placed in 70 DEG C of water-bath mechanical agitation 6h, forms uniform solution;
(3) step (2) gained solution is regulated pH to 7;
(4) step (3) gained solution is carried out drying-granulating by spray-dired method, described spraying dry: intake air temperature is 240 DEG C, peristaltic pump rotating speed is 1100rpm/min, and rotation speed of fan is 80HZ, obtains VPO 4f presoma;
(5) by step (4) gained fluorophosphoric acid vanadium (VPO 4f) presoma is placed in pipe type sintering furnace, and under an argon atmosphere in 650 DEG C of sintering 10h, then Temperature fall is to room temperature, obtains ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
Above-mentioned material is assembled into CR2025 button cell, battery is surveyed its charge/discharge capacity and high rate performance in 0.01V ~ 1.5V voltage range, and test result first discharge specific capacity under 0.1C, 0.5C, 1C multiplying power is followed successively by 591.5mAh/g, 482.2mAh/g, 399.4mAh/g.
By finding out above, the fluorophosphoric acid (VPO prepared by the present invention 4f) negative material, for assembled battery, the charging and discharging capacity of gained battery is higher, and high rate performance is good.Compared with the battery that the negative material graphite adopted with CN 102110813 B is assembled into, its highest first discharge specific capacity under 0.1C multiplying power is only 360.9mAh/g, is far smaller than the fluorophosphoric acid vanadium negative material prepared by the present invention.Therefore, the lithium ion battery negative material fluorophosphoric acid vanadium (VPO prepared by the present invention can be found out 4f) be a kind of Novel cathode material for lithium ion battery of excellent performance.

Claims (9)

1. a preparation method for lithium ion battery negative material fluorophosphoric acid vanadium, is characterized in that, comprises the following steps:
(1) ratio being 1:1:1:1-4 by vanadium source, phosphorus source, fluorine source, reducing agent according to the mol ratio of v element, P elements, fluorine element and reducing agent is dissolved in deionized water, and the concentration controlling vanadium metal ion is 0.05-1molL -1;
(2) step (1) gained mixed liquor is placed in 60-90 DEG C of water-bath and stirs 4-8h, form solution;
(3) step (2) gained solution is regulated pH to 6-9;
(4) step (3) gained solution is carried out drying-granulating by spray-dired method, obtain fluorophosphoric acid vanadium presoma;
(5) step (4) gained fluorophosphoric acid vanadium presoma is placed in pipe type sintering furnace, 400-800 DEG C of sintering 6-20h under non-reducing atmosphere, cool to room temperature, obtains ball-shaped lithium-ion battery negative material fluorophosphoric acid vanadium.
2. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1, is characterized in that, in step (1), the concentration controlling vanadium metal ion is 0.08-0.8 molL -1.
3. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 2, is characterized in that, the concentration controlling vanadium metal ion is 0.1-0.5 molL -1.
4. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 3, is characterized in that, the concentration controlling vanadium metal ion is 0.2-0.4 molL -1.
5. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1 and 2, is characterized in that, in step (1), described vanadium source is the one in vanadic oxide, ammonium metavanadate, ammonium vanadate, vanadyl acetylacetonate, vanadyl oxalate; Described phosphorus source is the one in phosphoric acid, phosphorus pentoxide, pyrophosphoric acid, ammonium phosphate; Described fluorine source is the one in lithium fluoride, ammonium fluoride, sodium fluoride.
6. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1 and 2, it is characterized in that, in step (1), described reducing agent is the one in tartaric acid, citric acid, oxalic acid, ethanedioic acid, adipic acid, malonic acid, ascorbic acid.
7. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1 and 2, it is characterized in that, in step (4), described spraying dry intake air temperature is at 180-260 DEG C, spraying dry peristaltic pump rotating speed is at 1000-1800rpm/min, and spraying dry rotation speed of fan is at 60-100HZ.
8. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1 and 2, is characterized in that, in step (5), described non-reducing atmosphere is argon gas, nitrogen or helium, or the mist of non-reducing gas and inert gas.
9. the preparation method of lithium ion battery negative material fluorophosphoric acid vanadium according to claim 1 and 2, is characterized in that, in step (6), described sintering time is 8-15h.
CN201510234376.3A 2015-05-08 2015-05-08 A kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium Active CN104835960B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510234376.3A CN104835960B (en) 2015-05-08 2015-05-08 A kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510234376.3A CN104835960B (en) 2015-05-08 2015-05-08 A kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium

Publications (2)

Publication Number Publication Date
CN104835960A true CN104835960A (en) 2015-08-12
CN104835960B CN104835960B (en) 2017-08-25

Family

ID=53813691

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510234376.3A Active CN104835960B (en) 2015-05-08 2015-05-08 A kind of preparation method of lithium ion battery negative material fluorophosphoric acid vanadium

Country Status (1)

Country Link
CN (1) CN104835960B (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106495124A (en) * 2015-09-08 2017-03-15 中国科学院过程工程研究所 A kind of fluorophosphoric acid vanadium sodium salt, low temperature environment-friendly preparation method thereof and application thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102079517A (en) * 2009-11-29 2011-06-01 宁波大学 Method for preparing fluorizated lithium vanadium phosphate as lithium-ion battery anode material by using spray pyrolysis method
CN102386407A (en) * 2011-11-02 2012-03-21 中南大学 Method for preparing anode material lithium vanadium phosphate by adopting quenching
CN103864045A (en) * 2014-03-28 2014-06-18 张宝 Preparation method of porous channel-shaped lithium ion battery negative electrode material VPO4
CN103872324A (en) * 2014-03-28 2014-06-18 郑俊超 Preparation method of petaloid lithium ion battery negative electrode material VPO4

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102079517A (en) * 2009-11-29 2011-06-01 宁波大学 Method for preparing fluorizated lithium vanadium phosphate as lithium-ion battery anode material by using spray pyrolysis method
CN102386407A (en) * 2011-11-02 2012-03-21 中南大学 Method for preparing anode material lithium vanadium phosphate by adopting quenching
CN103864045A (en) * 2014-03-28 2014-06-18 张宝 Preparation method of porous channel-shaped lithium ion battery negative electrode material VPO4
CN103872324A (en) * 2014-03-28 2014-06-18 郑俊超 Preparation method of petaloid lithium ion battery negative electrode material VPO4

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106495124A (en) * 2015-09-08 2017-03-15 中国科学院过程工程研究所 A kind of fluorophosphoric acid vanadium sodium salt, low temperature environment-friendly preparation method thereof and application thereof

Also Published As

Publication number Publication date
CN104835960B (en) 2017-08-25

Similar Documents

Publication Publication Date Title
CN108046231B (en) Sodium ion battery positive electrode material and preparation method thereof
CN107978739B (en) Manganese titanium sodium fluophosphate/carbon composite material, preparation method thereof and application of composite material as sodium ion anode material
CN109755514B (en) Carbon-coated lithium vanadium fluorophosphate lithium-ion battery positive electrode material and preparation method thereof
CN111377462A (en) Prussian blue positive electrode material, sodium ion battery and preparation method and application of prussian blue positive electrode material and sodium ion battery
CN103840157B (en) A kind of preparation method of nano-sheet lithium ion battery anode material vanadium lithium phosphate
CN103035906B (en) Lithium manganese phosphate clad lithium-rich layered oxide cathode material as well as preparation and application thereof
CN103367746A (en) Multi-ion-doped carbon-coated lithium iron phosphate battery material and preparation method thereof
CN103682275B (en) Lithium ion battery composite cathode material vanadyl phosphate lithium-phosphoric acid vanadium lithium preparation method
CN105261744A (en) Preparation method of porous vanadium manganese oxide anode material
CN112919442B (en) Preparation method of sodium ion battery positive electrode material sodium vanadium fluorophosphate
CN103515582A (en) Preparation method of lithium ion battery silicon-carbon composite cathode material
CN104103832A (en) Preparation method for LiFePO4-LiVPO4F for cathode material for lithium ion battery
CN103972476A (en) Preparation method of positive electrode material, phosphoric acid oxygen vanadium lithium, of lithium ion battery
CN104037413A (en) Preparation method of positive electrode material (carbon-coated iron-manganese-lithium phosphate) of lithium ion battery
CN110350198A (en) A kind of preparation method of sodium phosphate surface modification sodium-ion battery positive material
CN103972506B (en) A kind of preparation method of nano-sheet lithium ion battery negative material vanadyl phosphate
CN108821256A (en) A kind of nanometer fibrous anode material for lithium-ion batteries LiVPO4The preparation method of F
CN104821392B (en) Preparation method of spherical lithium ion battery anode material vanadium borate
CN104124455A (en) Preparation method of three-dimensional interlayer lithium vanadium phosphate as anode material for lithium ion battery
CN103872289A (en) Preparation method of spherical lithium ion battery positive electrode material LiVPO4F
CN103693632B (en) A kind of preparation method of lithium vanadyl phosphate positive material for lithium ion battery
CN102403500B (en) Method for preparation of lithium iron phosphate material in static mixing tube type reactor
CN103928683A (en) Preparation method of lithium ion battery cathode material (lithium vanadyl phosphate) with core-shell structure
CN102079517A (en) Method for preparing fluorizated lithium vanadium phosphate as lithium-ion battery anode material by using spray pyrolysis method
CN106058221B (en) Preparation method of phosphate polyanion composite manganese salt coated lithium-rich manganese-based positive electrode material

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
EXSB Decision made by sipo to initiate substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant