CN106374104B - A kind of method that air atmosphere prepares fluorophosphoric acid vanadium sodium material - Google Patents
A kind of method that air atmosphere prepares fluorophosphoric acid vanadium sodium material Download PDFInfo
- Publication number
- CN106374104B CN106374104B CN201610881047.2A CN201610881047A CN106374104B CN 106374104 B CN106374104 B CN 106374104B CN 201610881047 A CN201610881047 A CN 201610881047A CN 106374104 B CN106374104 B CN 106374104B
- Authority
- CN
- China
- Prior art keywords
- sodium
- vanadium
- source
- air atmosphere
- fluorophosphoric acid
- 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.)
- Active
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
-
- 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)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses the preparation methods that a kind of air atmosphere prepares fluorophosphoric acid vanadium sodium material, steps are as follows: by vanadium source, phosphoric acid root and carbon source mixing or vanadium source and the mixing of phosphoric acid root, grinding, under an argon atmosphere, through calcinations and sintering, it is cooled to room temperature, grinding, obtain vanadium phosphate, by vanadium phosphate, Fluorine source and sodium source are added separately in deionized water, magnetic agitation, transfer them to autoclave hydro-thermal reaction, reaction kettle is then naturally cooled into room temperature, it takes out, drying with water bath, take out grinding, tabletting, in air atmosphere, through calcinations and sintering, furnace cooling is to room temperature, grinding, obtain product fluorophosphoric acid vanadium sodium.Material particle size prepared by the present invention is evenly distributed, and purity is high has good high rate performance and cycle performance.
Description
Technical field
The invention belongs to compound polyanionic material preparation technical field, it is related to a kind of air atmosphere and prepares fluorophosphoric acid vanadium sodium
The method of material.
Background technique
Fluorophosphoric acid vanadium sodium is earliest by Barker et al. proposition, crystal structure and fluorophosphoric acid aluminium sodium (α-Na3Al2(PO4)2F3)
Similar (Masquelier C.;Croguennec L. Polyanionic (Phosphates, Silicates,
Sulfates) Frameworks as Electrode Materials for Rechargeable Li (or Na)
Batteries. Chem. Rev. 2013,113:6552-6591), there is cubic symmetrical structure, space group isI4/ mmm.It is by [MO4F2] octahedra and [PO4] the coplanar three-dimensional net structure of tetrahedron, this three-D space structure be sodium from
Son provides the channel of insertion and deintercalation；There is good reversible specific volume with the sodium-ion battery that fluorophosphoric acid vanadium sodium makees positive electrode
Amount has insertion stability well between 23 DEG C to 60 DEG C.
Fluorophosphoric acid vanadium sodium can be synthesized by sol-gal process, and fluorophosphoric acid vanadium sodium does positive electrode, and lithium piece does cathode
Material illustrates the voltage platform and fabulous capacity retention ratio (Zhao J. Q. of 3.6 V in small circulation;He
J. P.; Ding X. C.; Zhou J. H.; Ma Y. Wu S. C. Huang R. M.; A novel sol-gel
synthesis route to NaVPO4F as cathode material for hybrid lithium ion
Batteries. J. Power Sources 2010,195:6854-6859).Fluorophosphoric acid vanadium sodium can also be solid by two steps
The synthesis of phase method, and the capacity of fluorophosphoric acid vanadium sodium positive electrode can be improved by different amounts of carbon coating, it is 5 in carbon coating amount
When wt.%, discharge capacity reaches 97.8 mAh g for the first time-1(Lu Y.;Zhang S.;Li Y.;Xue L. G.;Xu G.
J.; Zhang X. W. Preparation and characterization of carbon-coated NaVPO4F as
cathode material for rechargeable sodium-ion batteries. J. Power Sources
2014,247:770-777).
But the defect of fluorophosphoric acid vanadium sodium hinders it that could not also be used widely so far, is embodied in: (1) material times
Rate performance is poor, poor circulation；(2) traditional fluorophosphoric acid vanadium sodium preparation method needs high temperature to carry out under protection of argon gas.
In order to enable fluorophosphoric acid vanadium sodium to put into industrialized production, it is necessary to be improved by improving preparation method or modification
Its chemical property, the capacity retention ratio under capacity retention ratio and big multiplying power discharging after improving its multiple charge and discharge cycles.
Currently, fluorophosphoric acid vanadium sodium raw material prepared in having been reported, after multiple charge and discharge cycles, capacity is kept
Rate is low, poorly conductive, and capacity retention ratio is low under big multiplying power, and under traditional argon atmosphere prepared by high temperature, and preparation process needs one
Straight-through inert gas shielding, thus be not suitable for industrialization demand.The present invention successfully uses water-heat process to be prepared for presoma, and
It realizes and prepares NaVPO under air atmosphere4F.Excellent chemical property is shown using material prepared by this method, 2.0 ~
Recycling 100 times in the potential range of 4.5V still has 80 mAhg-1Above specific discharge capacity, and still have 64 mAhg at 8C-1
Specific discharge capacity.It has no both at home and abroad at present and prepares NaVPO under any air atmosphere4The relevant report of F.
Summary of the invention
The object of the present invention is to provide the preparation methods that a kind of air atmosphere prepares fluorophosphoric acid vanadium sodium material.The present invention changes
The method that fluorophosphoric acid vanadium sodium is prepared under traditional high temperature argon atmosphere protection, the forerunner of fluorophosphoric acid vanadium sodium is prepared using hydro-thermal method
Body, and fluorophosphoric acid vanadium sodium is prepared in air atmosphere, the obtained fluorophosphoric acid vanadium sodium material of preparation method of the invention, granularity point
Cloth is uniform, and purity is high has preferable high rate performance and cycle performance.
Embodiment of the present invention is as follows:
A kind of air atmosphere prepares the preparation method of fluorophosphoric acid vanadium sodium material, the specific steps are as follows:
1) vanadium source, phosphoric acid root and carbon source being mixed, grinding under an argon atmosphere, through calcinations and sintering, is cooled to room temperature,
Grinding, obtains vanadium phosphate, vanadium phosphate, Fluorine source and sodium source is added separately in deionized water, mixed after being uniformly mixed
Close solution；
2) the resulting mixed solution of step 1) is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, it is anti-through hydro-thermal
Should after be cooled to room temperature, after water removal is dry presoma；
3) the resulting presoma of step 2 is taken out into grinding, tabletting through calcinations and sintering, is cooled to room in air atmosphere
Temperature, up to target product fluorophosphoric acid vanadium sodium after grinding.
It is further preferred that vanadium source described in step (1) is vanadic anhydride, ammonium metavanadate, one in vanadium trioxide
Kind, the phosphoric acid root is one of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, and the carbon source is glucose, Vitamin C
One of acid, sucrose, the Fluorine source are one of sodium fluoride, ammonium fluoride, and the sodium source is sodium acetate, sodium carbonate, fluorination
At least one of sodium, sodium hydroxide.
It is further preferred that the molar ratio in vanadium source, phosphoric acid root and carbon source described in step (1) is 1:1:1 or vanadium source
Molar ratio with phosphoric acid root is 1:1.
It is further preferred that calcination temperature described in step (1) is 600 ~ 800 DEG C, 4 ~ 10h of calcination time.
It is further preferred that the molar ratio of intermediate product vanadium phosphate, Fluorine source and sodium source described in step (1) is 1:1:1.
It is further preferred that the temperature of hydro-thermal reaction described in step (2) is 180 ~ 250 DEG C, the time of hydro-thermal reaction is
24~56h。
It is further preferred that the water removal drying mode of gained mixture adds after hydro-thermal reaction described in step (2) for water-bath
One of thermal evaporation, drying box drying, vacuum drying, dry temperature for removing water is 50 ~ 120 DEG C.
It is further preferred that the pressure of precursor powder tabletting base described in step (3) is 1 ~ 10MPa.
It is further preferred that calcination temperature described in step (3) is 200 ~ 600 DEG C, calcination time is 2 ~ 10h.
It is further preferred that the type of cooling described in step (3) is process control slow cooling, natural cooling, by sample
One of put into water or quenched in liquid nitrogen.
The present invention has the advantages that compared with the prior art
(1) present invention changes the step of fluorophosphoric acid vanadium sodium is prepared under traditional argon atmosphere, passes through hydro-thermal method, air atmosphere
Lower heat treatment is prepared for fluorophosphoric acid vanadium sodium；
(2) present invention obtained material show excellent chemical property, in the potential range of 2.0 ~ 4.5V
Recycling 100 times still has not less than 80 mAhg-1Specific discharge capacity, and still have 64 mAhg at 8C-1Specific discharge capacity.
Detailed description of the invention
In order to illustrate more clearly of technical solution of the present invention, below to required use in the present invention and embodiment description
Attached drawing do simple introduction.It should be evident that drawings in the following description are only some embodiments of the invention, for this
For the those of ordinary skill in field, without creative efforts, it can also be obtained according to these attached drawings other
Attached drawing.
Fig. 1 is present invention preparation NaVPO4The x-ray diffraction pattern of F material sample.
Fig. 2 is present invention preparation NaVPO4The scanning electron microscope (SEM) photograph of F material sample.
Fig. 3 is present invention preparation NaVPO4The x-ray photoelectron spectroscopy figure of F material sample vanadium.
Fig. 4 is present invention preparation NaVPO4The charge and discharge cycles high rate performance figure of F material sample.
Specific embodiment
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Whole description.
Embodiment 1:
0.01mol ammonium dihydrogen phosphate, 0.005mol vanadic anhydride, 0.00167mol glucose are mixed, grinding is uniform,
In tube furnace under argon atmosphere protection, 750 DEG C of calcining 8h, then cool to room temperature with the furnace, it takes out grinding uniformly, obtains
0.01mol intermediate product vanadium phosphate, then by 0.01mol intermediate product vanadium phosphate, 0.01mol sodium fluoride, 0.01mol sodium acetate
It is added in the deionized water of 40ml, magnetic agitation 3h, the mixed solution then formed is transferred in autoclave, In
48h is reacted at 200 DEG C, autoclave is then naturally cooled into room temperature, 60 DEG C of drying with water baths of product is taken out, after drying
Product takes out, grinding, in the case where pressure is 6MPa by pressed powder base, then in air atmosphere, 300 DEG C of calcining 5h, in tubular type
Room temperature is naturally cooled in furnace, is ground, is obtained product fluorophosphoric acid vanadium sodium；The X-ray powder diffraction figure of sample is produced referring to Fig. 1, gained
The purity of object is higher, and crystallinity is high；Referring to fig. 2, products therefrom particle is cube and the octahedral bodily form to the scanning electron microscope (SEM) photograph of sample
Shape, and even particle size is consistent；Referring to Fig. 3, products therefrom vanadium is learnt by x-ray photoelectron spectroscopy and analysis titration
Main valence state be trivalent；Using resulting product as positive electrode, composition experiment is button-shaped in the glove box full of argon gas
Sodium-ion battery, with 0.1C(14.3mA/g) multiplying power charge and discharge cycles are carried out between 2.0-4.5V, discharge capacity is for the first time
88.30mAh/g, the discharge capacity at 8C, 16C respectively reach 53.00,33.20mAh/g, have good cycle performance and
High rate performance returns under low current after heavy-current discharge and remains to restore its initial reversible capacity, refer to Fig. 4.
Embodiment 2:
0.01mol diammonium hydrogen phosphate, 0.005mol vanadium trioxide are mixed, grinding is uniform, the argon gas gas in tube furnace
Under atmosphere protection, 600 DEG C of calcining 10h, then cool to room temperature with the furnace, it takes out grinding uniformly, obtains 0.01mol intermediate product phosphoric acid
0.01mol intermediate product vanadium phosphate, 0.01mol ammonium fluoride, 0.01mol sodium carbonate are then added to the deionization of 40ml by vanadium
In water, magnetic agitation 1h, the mixed solution then formed is transferred in autoclave, reacts 51h at 180 DEG C, with
Autoclave is naturally cooled into room temperature afterwards, takes out 50 DEG C of drying with water baths of product, the product after drying is taken out, grinding, In
Pressure is under 1MPa by pressed powder base, then in air atmosphere, 200 DEG C of calcining 10h, process control is slowly decreased to room temperature,
Grinding, obtains product fluorophosphoric acid vanadium sodium.
Embodiment 3:
0.01mol ammonium phosphate, 0.01mol ammonium metavanadate, 0.00167mol glucose are mixed, grinding is uniform, in tubular type
In furnace under argon atmosphere protection, 800 DEG C of calcining 4h, then cool to room temperature with the furnace, it takes out grinding uniformly, obtains among 0.01mol
0.01mol intermediate product vanadium phosphate, 0.01mol sodium fluoride, 0.01mol sodium fluoride are then added to 40ml by product vanadium phosphate
Deionized water in, magnetic agitation 2h, the mixed solution then formed is transferred in autoclave, anti-at 250 DEG C
Autoclave then should be naturally cooled into room temperature for 24 hours, take out 60 DEG C of drying with water baths of product, the product after drying is taken out,
Grinding, in the case where pressure is 8MPa by pressed powder base, then in air atmosphere, 600 DEG C of calcining 2h are plunged the sample into water and are quenched
Fire cooling, grinding obtain product fluorophosphoric acid vanadium sodium.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to invention protection scope
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
It is still within the scope of the present invention to make the creative labor the various modifications or changes that can be made.
Claims (6)
1. a kind of air atmosphere prepares fluorophosphoric acid vanadium sodium NaVPO4The method of F material, which is characterized in that specific step is as follows:
It 1) is that 1:1:1 is mixed according to the ratio between amount of substance by vanadium source, phosphoric acid root and carbon source, grinding, in argon atmosphere, 600 ~
4 ~ 10h is calcined at 800 DEG C, is then cooled to room temperature, grinds, obtains intermediate product vanadium phosphate, and the carbon source is glucose, anti-bad
One of hematic acid, sucrose；
2) the resulting intermediate product vanadium phosphate of step 1) and Fluorine source and sodium source are added separately in deionized water, are stirred
Mixed solution is obtained after even；
3) the resulting mixed solution of step 2 is transferred in the stainless steel cauldron of polytetrafluoroethyllining lining, after hydro-thermal reaction
It is cooled to room temperature, obtains presoma after water removal is dry；
4) the resulting presoma of step 3) is taken out and is ground, tabletting, in air atmosphere, through 200 ~ 600 DEG C of temperature lower calcinations 2 ~
10h is cooled to room temperature, up to target product fluorophosphoric acid vanadium sodium NaVPO after grinding4F。
2. air atmosphere according to claim 1 prepares fluorophosphoric acid vanadium sodium NaVPO4The method of F material, which is characterized in that step
It is rapid 1) described in vanadium source be one of vanadic anhydride, ammonium metavanadate, vanadium trioxide, the phosphoric acid root be biphosphate
One of ammonium, diammonium hydrogen phosphate, ammonium phosphate, the Fluorine source are one of sodium fluoride, ammonium fluoride, and the sodium source is acetic acid
At least one of sodium, sodium carbonate, sodium fluoride, sodium hydroxide.
3. air atmosphere according to claim 1 prepares fluorophosphoric acid vanadium sodium NaVPO4The method of F material, which is characterized in that step
It is rapid 2) described in the ratio between intermediate product vanadium phosphate, Fluorine source and the amount of substance of sodium source be 1:1:1.
4. air atmosphere according to claim 1 prepares fluorophosphoric acid vanadium sodium NaVPO4The method of F material, which is characterized in that step
It is rapid 3) described in the temperature of hydro-thermal reaction be 180 ~ 250 DEG C, time of hydro-thermal reaction is 24 ~ 56h；Gained mixing after hydro-thermal reaction
The water removal drying mode of object be heating water bath evaporation, drying box drying, vacuum drying one of, water removal drying temperature be 50 ~
120℃。
5. air atmosphere according to claim 1 prepares fluorophosphoric acid vanadium sodium NaVPO4The method of F material, which is characterized in that step
It is rapid 4) described in precursor powder tabletting base pressure be 1 ~ 10MPa.
6. air atmosphere according to claim 1 prepares fluorophosphoric acid vanadium sodium NaVPO4F MATERIALS METHODS, which is characterized in that step
4) type of cooling described in be process control slow cooling, natural cooling, plunge the sample into water or in liquid nitrogen quenching in one
Kind.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610881047.2A CN106374104B (en) | 2016-10-10 | 2016-10-10 | A kind of method that air atmosphere prepares fluorophosphoric acid vanadium sodium material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610881047.2A CN106374104B (en) | 2016-10-10 | 2016-10-10 | A kind of method that air atmosphere prepares fluorophosphoric acid vanadium sodium material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106374104A CN106374104A (en) | 2017-02-01 |
| CN106374104B true CN106374104B (en) | 2019-12-03 |
Family
ID=57895591
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610881047.2A Active CN106374104B (en) | 2016-10-10 | 2016-10-10 | A kind of method that air atmosphere prepares fluorophosphoric acid vanadium sodium material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106374104B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109037630B (en) * | 2018-07-25 | 2019-04-30 | 三峡大学 | A kind of phosphorus doping carbon coating Na3V2(PO4)2O2F positive electrode and preparation method thereof |
| CN112018339B (en) * | 2019-05-31 | 2023-03-24 | 中南大学 | Method for preparing sodium ion battery vanadium fluorophosphate/carbon composite positive electrode material from vanadium-containing mineral aggregate and prepared positive electrode material |
| CN112850684B (en) * | 2019-11-27 | 2022-07-08 | 中国科学院大连化学物理研究所 | Preparation method and application of lithium vanadium fluorophosphate |
| CN112864358B (en) * | 2019-11-27 | 2023-11-07 | 中国科学院大连化学物理研究所 | Vanadium-based polyanion compound prepared by one-step method and application thereof |
| CN112490448A (en) * | 2020-11-27 | 2021-03-12 | 中南大学 | Preparation and purification method of (fluoro) vanadium sodium phosphate compound cathode material |
| CN112701285A (en) * | 2020-12-29 | 2021-04-23 | 东北师范大学 | Positive electrode material and preparation method and application thereof |
| CN114094066A (en) * | 2021-10-29 | 2022-02-25 | 江苏大学 | Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101627493A (en) * | 2007-03-06 | 2010-01-13 | 威伦斯技术公司 | Method of making active materials for use in secondary electrochemical cells |
| CN104112858A (en) * | 2014-06-26 | 2014-10-22 | 西南大学 | Preparation method and application of network structure nano NaVPO4F/C composite material and application thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100814540B1 (en) * | 2001-04-06 | 2008-03-17 | 발렌스 테크놀로지, 인코포레이티드 | Sodium Ion Batteries |
| US20110052986A1 (en) * | 2002-04-04 | 2011-03-03 | Jeremy Barker | Sodium Ion Batteries |
-
2016
- 2016-10-10 CN CN201610881047.2A patent/CN106374104B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101627493A (en) * | 2007-03-06 | 2010-01-13 | 威伦斯技术公司 | Method of making active materials for use in secondary electrochemical cells |
| CN104112858A (en) * | 2014-06-26 | 2014-10-22 | 西南大学 | Preparation method and application of network structure nano NaVPO4F/C composite material and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106374104A (en) | 2017-02-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106374104B (en) | A kind of method that air atmosphere prepares fluorophosphoric acid vanadium sodium material | |
| CN108046231B (en) | Sodium ion battery positive electrode material and preparation method thereof | |
| CN109755514B (en) | Carbon-coated lithium vanadium fluorophosphate lithium-ion battery positive electrode material and preparation method thereof | |
| CN110226252B (en) | Polyanion type sodium ion battery positive electrode material and preparation method thereof | |
| GB2495279A (en) | A condensed polyanion electrode material | |
| CN105810902B (en) | A kind of method of solvent hot preparation nano-carbon coated fluorophosphoric acid Naferon | |
| CN103956493B (en) | The preparation method of carbon cladding hierarchical organization LiFePO4 | |
| CN104401957B (en) | A kind of hydrothermal preparing process of positive electrode material of lithium secondary cell fluorophosphoric acid cobalt lithium | |
| CN108417796A (en) | A kind of nickel cobalt lithium aluminate cathode material of low surface alkalinty and preparation method thereof | |
| CN103872289A (en) | Preparation method of spherical lithium ion battery positive electrode material LiVPO4F | |
| CN103887497B (en) | A kind of preparation method of the more caryogram core shell structure phosphatic composite cathode materials of lithium ion battery | |
| CN104733709A (en) | Preparation method of lithium manganese iron phosphate or lithium manganese iron phosphate composite material in controllable crystal form | |
| CN108117098B (en) | Coralliform α -Cu2V2O7Method for preparing powder | |
| CN104752723B (en) | The method of microwave solvothermal fabricated in situ carbon-coated LiFePO 4 for lithium ion batteries | |
| CN106505197B (en) | A method of preparing vanadium phosphate cathode material | |
| CN103035882A (en) | Method for synthesizing Li3V2(PO4)3/C by using glycine-nitrate combustion method | |
| CN108448105A (en) | A kind of preparation method of lithium ion battery anode material lithium iron phosphate/redox graphene | |
| CN107768621A (en) | A kind of preparation method of LiFePO4/graphene/carbon composite positive pole | |
| CN107799754A (en) | A kind of preparation method of fluorophosphoric acid vanadium lithium/fluorinated graphene composite positive pole | |
| CN111777050B (en) | Preparation method of lithium vanadium phosphate anode material, product and application thereof | |
| CN104934600B (en) | Multi-element composite phosphate nanometer anode material and preparation method thereof | |
| CN111082018A (en) | LiVOPO4Preparation method of/C composite positive electrode material | |
| CN105428617B (en) | A method of preparing the modified LiFePO4 of inside and outside conductive carbon | |
| CN114572958B (en) | Preparation method of fluorine-containing polyanion-type positive electrode material and fluorine-containing polyanion-type positive electrode material | |
| CN105006571B (en) | The method of microwave method synthesizing iron lithium phosphate porous microsphere |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |