CN111072004A - Sodium-doped lithium vanadium fluorophosphate material, and preparation method and application thereof - Google Patents
Sodium-doped lithium vanadium fluorophosphate material, and preparation method and application thereof Download PDFInfo
- Publication number
- CN111072004A CN111072004A CN201911325644.7A CN201911325644A CN111072004A CN 111072004 A CN111072004 A CN 111072004A CN 201911325644 A CN201911325644 A CN 201911325644A CN 111072004 A CN111072004 A CN 111072004A
- Authority
- CN
- China
- Prior art keywords
- sodium
- source
- vanadium
- doped lithium
- doped
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/455—Phosphates containing halogen
-
- 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
-
- 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
- H01M4/582—Halogenides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a sodium-doped lithium vanadium fluorophosphate material, a preparation method and application thereof, wherein the general formula of the sodium-doped lithium vanadium fluorophosphate material is as follows: li(1‑x)/NaxVPO4F, wherein x is more than 0 and less than or equal to 0.3. The preparation method of the sodium-doped lithium vanadium fluorophosphate material comprises the following steps: mixing a vanadium source, a phosphorus source and a carbon source at the temperature of 60-100 ℃, and drying; calcining the product in inert atmosphere to obtain carbon-doped vanadium phosphate; mixing vanadium phosphate doped with carbon, LiF and a sodium source, and performing dry ball milling to obtain uniformly mixed powder; calcining the powder to obtain a sodium-doped lithium vanadium fluorophosphate material, wherein the calcining temperature is as follows: and calcining for 1-6h at 650-800 ℃ to prepare the sodium-doped lithium vanadium fluorophosphate material. By doping with Na+The electrochemical performance of the lithium vanadium fluorophosphate is effectively improved, and the method has a simple process routeThe method is easy to operate, low in production cost and capable of realizing large-scale production.
Description
Technical Field
The invention relates to a material technology, in particular to a sodium-doped lithium vanadium fluorophosphate material, a preparation method and application thereof.
Background
Lithium ion batteries have been widely used in various fields of life, production, energy storage, etc. in recent years, and therefore, the development of high-performance energy storage materials is imminent. The traditional lead-acid, cadmium-nickel and nickel-hydrogen batteries have a series of defects of low working voltage and density, environmental pollution and the like, and are gradually eliminated from the market. The advantages of lithium ion batteries such as good safety, no memory effect and no pollution are well known. The anode material is used as a key factor of the lithium ion battery, and has direct influence on the overall performance of the lithium ion battery. With the development of lithium ion battery industrialization, obtaining batteries with high specific capacity, high cycle performance and high charge-discharge rate is the final goal of the development
The vanadium resource is rich in China, and the annual yield of vanadium oxide is high, so that LiVPO4F is a lithium ion battery anode material with great potential application value. However, in the application, due to the limit of the self-structure, the electronic conductivity is relatively low and the diffusion coefficient of lithium ions is small, so that the LiVPO of pure phase is realized4The electrochemical performance of the F material is not sufficiently exerted.
The metal doping can modify the material, and the result shows that the LiVPO with high purity4F is difficult to obtain, high purity is a key factor affecting electrochemical performance, and pure phase LiVPO4The relatively low conductivity is correspondingly limited, and the mobility of Li + ions directly determines the charge-discharge rate of the electrode material, so that Li+The problem of diffusion of ions has also recently received much attention.
Disclosure of Invention
The invention is directed to phase-pure LiVPO4F, the problem of relatively low conductivity, and provides a sodium-doped lithium vanadium fluorophosphate material which is prepared by doping Na+The electrochemical performance of the lithium vanadium fluorophosphate is effectively improved.
In order to achieve the purpose, the invention adopts the technical scheme that: a sodium-doped lithium vanadium fluorophosphate material has the general formula: li(1-x)/NaxVPO4F, wherein 0 < x.ltoreq.0.3, preferably 0.1. ltoreq.x.ltoreq.0.2.
The invention also discloses a preparation method of the sodium-doped lithium vanadium fluorophosphate material, which is characterized in that Na is doped+Effectively improve the electrochemical performance of the lithium vanadium fluorophosphateThe method has simple process route, easy operation and low generation cost, and can realize large-scale production.
In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of a sodium-doped lithium vanadium fluorophosphate material comprises the following steps:
step 1, mixing a vanadium source, a phosphorus source and a carbon source at 60-100 ℃ for 10-30 min, and drying;
step 2, calcining the product dried in the step 1 in inert atmosphere to obtain carbon-doped Vanadium Phosphate (VPO)4/C), the calcining temperature is 700-900 ℃, and the calcining time is 6-10 h;
step 3, mixing the carbon-doped vanadium phosphate, LiF and a sodium source, and performing dry ball milling to obtain uniformly mixed powder;
and 4, calcining the powder obtained in the step 3 (placing the powder in a steel kettle for packaging and calcining), and grinding to obtain a sodium-doped lithium vanadium fluorophosphate material, wherein the calcining temperature is as follows: the calcination time is 1-6h at 650-800 ℃.
Further, the molar ratio of vanadium to phosphorus in the vanadium source and the phosphorus source is 1:0.9 to 1.1 is preferably 1:1, the carbon source is added in an amount of 20 to 80 wt%, preferably 30 to 50 wt%, based on the total weight.
Further, the vanadium source is vanadyl sulfate, Ammonium Polyvanadate (APV), vanadyl oxalate, V2O4、V2O5And one or more of Ammonium Metavanadate (AMV).
Further, the phosphorus source is concentrated phosphoric acid and/or ammonium dihydrogen phosphate.
Further, the carbon source is one or a mixture of glucose, Polyacrylamide (PAM), fructose and sucrose.
Further, in the step 1, the drying temperature is 60-100 ℃, preferably 60-80 ℃, and the drying time is 3-8 h.
Further, the inert atmosphere in step 2 includes, but is not limited to, argon.
Further, the sodium source is NaCl, NaOH and CH3COONa or a mixture of several of COONa.
Further, in the step 3, the molar ratio of vanadium, lithium and sodium elements of the carbon-doped vanadium phosphate, LiF and sodium source is 1: 1-x: x is more than 0 and less than or equal to 0.3.
Further, the ball milling conditions in the step 3 are as follows: 200-400 r/min, running for 6-15 h, separating the ball materials, and grinding into powder.
The preparation principle of the sodium-doped lithium vanadium fluorophosphate material of the invention is as follows: na and Li belong to the same group of elements and have many similar properties, the Na ion radius is larger than the ion radius, Na is used+Ion replacement of Li+Can change the diffusion channel of the material, improve the electronic conductivity of the electrode material by ion doping, and dope a small amount of Na+Is beneficial to Li+The discharge capacity can be improved. The method for preparing the sodium-doped lithium vanadium fluorophosphate is roughly divided into two steps, firstly, an intermediate product vanadium phosphate is prepared by a carbothermic method, and then, the sodium-doped lithium vanadium fluorophosphate is obtained by mixing a fluorine source and a sodium source and calcining.
The invention also discloses the application of the sodium-doped lithium vanadium fluorophosphate material in the field of battery anode materials, in particular the application in the field of lithium ion battery anode materials.
The lithium-sodium-doped vanadium lithium fluorophosphate cathode material with good crystallization performance and uniform components is prepared by adding a proper amount of sodium source by utilizing a liquid phase method which is easy to produce and a simple mixing process of solid phase ball milling, and compared with pure-phase vanadium lithium fluorophosphate, the capacity and the cycle performance of the battery are improved. And is also suitable for industrial production.
Compared with the prior art, the sodium-doped lithium vanadium fluorophosphate material, the preparation method and the application thereof have the following advantages:
1) the preparation method of the sodium-doped lithium vanadium fluorophosphate has the advantages of simple process route, easy operation and low production cost, and can realize large-scale production.
2) The sodium-doped lithium vanadium fluorophosphate material has high purity, uniform granularity and excellent electrochemical performance. Na and Li belong to the same group of elements and have many similar properties, Na+Radius of ion
Greater than Li+Radius of ion
With Na+Ion replacement of Li+Can change the material diffusion channel, Na+Ion-substituted Li+Ions can reduce Li and simultaneously dope and enlarge the distance between layers, so that the ion migration channel expands, and the Li in the material is effectively reduced+Transition potential barrier of ion, enhancing Li+The rate of ion diffusion.
3) The sodium-doped lithium vanadium fluorophosphate material can be used for preparing a battery anode material, the voltage platform of the anode material is 4.2V, and the voltage platform of the anode material is LiVPO4F is the same. The charging and discharging specific capacity of the sodium-doped lithium vanadium fluorophosphate is improved, and the cycle performance is enhanced.
Drawings
FIG. 1 is a charge-discharge curve of a button cell made of pure-phase lithium vanadium fluorophosphate;
FIG. 2 is a charge-discharge curve of a button cell doped with a sodium-doped lithium vanadium fluorophosphate material according to the present invention;
FIG. 3 is an XRD pattern of a sodium-doped lithium vanadium fluorophosphate material;
fig. 4 is an SEM image of the sodium-doped lithium vanadium fluorophosphate material.
Detailed Description
The invention is further illustrated by the following examples:
example 1
The embodiment discloses a sodium-doped lithium vanadium fluorophosphate material, and the general formula of the material is Li0.9/Na0.1VPO4F。
The preparation method of the sodium-doped lithium vanadium fluorophosphate material comprises the following steps:
mixing vanadyl oxalate and ammonium dihydrogen phosphate, adding glucose accounting for 40% of the total mass fraction, mixing and stirring uniformly in a water bath kettle, wherein the water bath temperature is 70 ℃, the stirring time is 20min, the poured liquid is in a uniform viscous state, and drying in a 60 ℃ oven. Calcining the dried sample in a tubular furnace filled with argon to obtain VPO4and/C. The calcination conditions were: 750 ℃ 10h。
VPO (vacuum pressure oxidation) is performed4Dry ball milling of/C and LiF with sodium source, VPO4The mol ratio of vanadium to lithium of/C and LiF is 1:1, and the ball milling conditions are as follows: 200r/min, running for 6h, separating the ball material and grinding into powder. Wherein, the sodium source is NaCl, NaOH and CH3COONa。
The powdery sample was put into a tube furnace and calcined. The calcination temperature is as follows: the mixture is calcined at 650 ℃ for 6h and ground into a uniform powder without large particles at room temperature.
The specific preparation process of the battery comprises the following steps: PVDF is used as a binder, N-methyl pyrrolidone (NMP) is used as a solvent to be completely dissolved, and the prepared sample and the conductive agent Super-P are mixed according to the following active substances: conductive agent: and (3) preparing the slurry according to the proportioning relation of 8:1:1 of PVDF, and then carrying out magnetic stirring until the slurry is uniform.
After drying and preparing the membrane electrode, tabletting the pole pieces of each batch number (8-10MPa for 1min), weighing, and putting into a glove box for assembly.
The obtained product lithium vanadium phosphate is used as the lithium ion battery anode material, and the lithium sheet is used as the counter electrode to assemble the lithium ion button cell, and the XRD spectrogram (shown in figure 3) shows that the prepared material only has the phase of lithium vanadium fluorophosphate, which indicates that the doped sodium ions replace part of lithium ions. From the SEM image (as shown in fig. 4), it was found that the resulting sodium-doped lithium vanadium fluorophosphate was irregular in shape formed by agglomeration of primary particles.
The charge and discharge test is carried out at a voltage of 3.0-4.5V,
FIG. 1 is a charge-discharge curve of pure-phase vanadium lithium fluorophosphate at a multiplying power of 0.2C, and the charge-discharge specific capacities are 118mAh/g and 115mAh/g respectively. As shown in FIG. 2, when a charge-discharge test was performed at a voltage of 3.0-4.5V, the specific charge capacity of the sodium-doped lithium vanadium fluorophosphate was 123mAh/g and the discharge capacity was 120mAh/g at a rate of 0.2C.
Example 2
The embodiment discloses a sodium-doped lithium vanadium fluorophosphate material, and the general formula of the material is Li0.85/Na0.15VPO4F。
The preparation method of the sodium-doped lithium vanadium fluorophosphate material comprises the following steps:
mixing ammonium metavanadate and ammonium dihydrogen phosphate in a ratio of V: mixing P-1, adding glucose accounting for 30% of the total weight to obtain a vanadium phosphate precursor, discharging, drying at 60 ℃ for 4h, heating to 900 ℃ in a tube furnace under the protection of nitrogen atmosphere at the heating rate of 5 ℃/min, keeping the temperature for 10 hours, then cooling to room temperature to obtain vanadium phosphate, and mixing vanadium phosphate, lithium fluoride and sodium fluoride according to the molar ratio V: li: na is 1: mixing 0.85:0.15, heating to 600 ℃ at the heating rate of 4 ℃/min under the nitrogen protection atmosphere, preserving the heat for 6 hours, and cooling to room temperature along with a tubular furnace to obtain the sodium-doped lithium vanadium fluorophosphate.
The lithium sheet is used as a counter electrode to assemble the lithium ion button cell, the charging specific capacity is 123mAh/g under the multiplying power of 0.2C, and the discharging capacity is 118 mAh/g.
Example 3
The embodiment discloses a sodium-doped lithium vanadium fluorophosphate material, and the general formula of the material is Li0.9/Na0.1VPO4F。
The preparation method of the sodium-doped lithium vanadium fluorophosphate material comprises the following steps:
mixing ammonium metavanadate and concentrated phosphoric acid in a ratio of V: mixing P-1, adding fructose accounting for 40 percent of the total weight to obtain a vanadium phosphate precursor, discharging, drying at 80 ℃ for 3 hours, heating to 800 ℃ in a tube furnace under the protection of nitrogen atmosphere at the heating rate of 5 ℃/min, keeping the temperature for 10 hours, then cooling to room temperature to obtain vanadium phosphate, and adding vanadium phosphate, lithium fluoride and sodium fluoride according to the molar ratio of Li: na: v: and (3) mixing the materials in a ratio of P to 0.9:0.1:1:1, heating to 600 ℃ at a heating rate of 4 ℃/min under the nitrogen protection atmosphere, keeping the temperature for 6 hours, and cooling to room temperature along with a tubular furnace to obtain the sodium-doped lithium vanadium fluorophosphate.
The lithium sheet is used as a counter electrode to assemble the lithium ion button cell, the charging specific capacity is 125mAh/g under the multiplying power of 0.2C, and the discharging capacity is 123 mAh/g.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A sodium-doped lithium vanadium fluorophosphate material is characterized in that the general formula is as follows: li(1-x)/NaxVPO4F, wherein x is more than 0 and less than or equal to 0.3.
2. A method for preparing the sodium-doped lithium vanadium fluorophosphate material of claim 1, which is characterized by comprising the following steps:
step 1, mixing a vanadium source, a phosphorus source and a carbon source at 60-100 ℃ for 10-30 min, and drying;
step 2, placing the product dried in the step 1 in an inert atmosphere for calcining to obtain carbon-doped vanadium phosphate; the calcining temperature is 700-900 ℃, and the calcining time is 6-10 h;
step 3, mixing the carbon-doped vanadium phosphate, LiF and a sodium source, and performing dry ball milling to obtain powder;
and 4, calcining the powder obtained in the step 3, and grinding to obtain the sodium-doped lithium vanadium fluorophosphate material, wherein the calcining temperature is as follows: the calcination time is 1-6h at 650-800 ℃.
3. The method for preparing the sodium-doped lithium vanadium fluorophosphate material according to claim 2, wherein the molar ratio of vanadium to phosphorus in the vanadium source and the phosphorus source is 1:0.9-1.1, and the addition amount of the carbon source is 20-80 wt% of the total weight.
4. The method for preparing the sodium-doped lithium vanadium fluorophosphate material according to claim 2 or 3, wherein the vanadium source is vanadyl sulfate, ammonium polyvanadate, vanadyl oxalate, V2O4、V2O5And one or more of ammonium metavanadate; the phosphorus source is concentrated phosphoric acid and/or ammonium dihydrogen phosphate; the carbon source is one or more of glucose, polyacrylamide, fructose and sucroseAnd (4) mixing.
5. The preparation method of the sodium-doped lithium vanadium fluorophosphate material according to claim 2, wherein the drying temperature in the step 1 is 60-100 ℃, and the drying time is 3-8 h.
6. The method for preparing the sodium-doped lithium vanadium fluorophosphate material according to claim 2, wherein the inert atmosphere in the step 2 is argon.
7. The method of claim 2, wherein the sodium source is NaCl, NaOH, and CH3COONa or a mixture of several of COONa.
8. The method for preparing the sodium-doped lithium vanadium fluorophosphate material according to claim 2, wherein the molar ratio of vanadium, lithium and sodium elements in the carbon-doped vanadium fluorophosphate, LiF and sodium source in step 3 is 1: 1-x: x is more than 0 and less than or equal to 0.3.
9. The method for preparing the sodium-doped lithium vanadium fluorophosphate material according to claim 2, wherein the ball-milling conditions in the step 3 are as follows: 200-400 r/min, and running for 6-15 h.
10. Use of the sodium-doped lithium vanadium fluorophosphate material according to claim 1 in the field of battery cathode materials.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911325644.7A CN111072004A (en) | 2019-12-20 | 2019-12-20 | Sodium-doped lithium vanadium fluorophosphate material, and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911325644.7A CN111072004A (en) | 2019-12-20 | 2019-12-20 | Sodium-doped lithium vanadium fluorophosphate material, and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111072004A true CN111072004A (en) | 2020-04-28 |
Family
ID=70316275
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911325644.7A Pending CN111072004A (en) | 2019-12-20 | 2019-12-20 | Sodium-doped lithium vanadium fluorophosphate material, and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111072004A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807691A (en) * | 2010-04-19 | 2010-08-18 | 湘西自治州矿产与新材料技术创新服务中心 | Method for preparing lithium position sodium-doped oxygen lithium vanadium phosphate anode material of lithium ion battery |
| CN104577120A (en) * | 2015-01-04 | 2015-04-29 | 合肥国轩高科动力能源股份公司 | Preparation method of lithium vanadium phosphate and fluorination lithium vanadium phosphate composite positive pole material |
| CN105655586A (en) * | 2016-03-24 | 2016-06-08 | 复旦大学 | Low-energy-consumption method for preparing lithium vanadium fluorophosphate as positive electrode material for lithium-ion battery |
| CN108134081A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | The sodium-ion battery positive electrode of rare earth metal doping and its preparation and application |
| CN109755514A (en) * | 2018-12-27 | 2019-05-14 | 大连博融新材料有限公司 | A kind of carbon coating lithium vanadium fluorophosphates lithium ionic cell anode material and preparation method thereof |
| CN109755568A (en) * | 2019-02-27 | 2019-05-14 | 湖北锂诺新能源科技有限公司 | The preparation method of potassium and cobalt codope fluorophosphoric acid vanadium lithium anode material |
-
2019
- 2019-12-20 CN CN201911325644.7A patent/CN111072004A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101807691A (en) * | 2010-04-19 | 2010-08-18 | 湘西自治州矿产与新材料技术创新服务中心 | Method for preparing lithium position sodium-doped oxygen lithium vanadium phosphate anode material of lithium ion battery |
| CN104577120A (en) * | 2015-01-04 | 2015-04-29 | 合肥国轩高科动力能源股份公司 | Preparation method of lithium vanadium phosphate and fluorination lithium vanadium phosphate composite positive pole material |
| CN105655586A (en) * | 2016-03-24 | 2016-06-08 | 复旦大学 | Low-energy-consumption method for preparing lithium vanadium fluorophosphate as positive electrode material for lithium-ion battery |
| CN108134081A (en) * | 2016-12-01 | 2018-06-08 | 中国科学院大连化学物理研究所 | The sodium-ion battery positive electrode of rare earth metal doping and its preparation and application |
| CN109755514A (en) * | 2018-12-27 | 2019-05-14 | 大连博融新材料有限公司 | A kind of carbon coating lithium vanadium fluorophosphates lithium ionic cell anode material and preparation method thereof |
| CN109755568A (en) * | 2019-02-27 | 2019-05-14 | 湖北锂诺新能源科技有限公司 | The preparation method of potassium and cobalt codope fluorophosphoric acid vanadium lithium anode material |
Non-Patent Citations (1)
| Title |
|---|
| ZHAOMENG LIU ET AL.: "Mechanical activation assisted soft chemical synthesis of Na-doped lithium vanadium fluorophosphates with improved lithium storage properties", 《CERAMICS INTERNATIONAL》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107819115B (en) | Doped modified sodium vanadium fluorophosphate cathode material and preparation method thereof | |
| CN110061229B (en) | High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof | |
| CN109755514B (en) | Carbon-coated lithium vanadium fluorophosphate lithium-ion battery positive electrode material and preparation method thereof | |
| CN110350198B (en) | Preparation method of sodium phosphate surface modified sodium ion battery positive electrode material | |
| CN106602044B (en) | Preparation of doped modified LiVPO4Method for preparing cathode material of F lithium ion battery | |
| CN111564622A (en) | Lithium manganese iron phosphate cathode material and preparation method thereof | |
| CN105552324A (en) | Preparation method for lithium iron phosphate coated lithium nickel cobalt manganese composite material | |
| CN103594708B (en) | One is appraised at the current rate iron-based composite positive pole and preparation method thereof | |
| CN112701282B (en) | Large-radius ion-doped modified sodium vanadium fluorophosphate cathode material and preparation method thereof | |
| CN103840157A (en) | Preparation method for nano sheet-shaped lithium ion battery positive electrode material fluorine lithium vanadium phosphate | |
| CN103078113A (en) | Vanadium-titanium ion-codoped lithium iron phosphate material and preparation method thereof | |
| CN103367746A (en) | Multi-ion-doped carbon-coated lithium iron phosphate battery material and preparation method thereof | |
| CN114388772B (en) | Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery | |
| CN101339992A (en) | Preparation of lithium ionic cell positive electrode material vanadium lithium silicate | |
| CN107452950A (en) | The anode material for lithium-ion batteries and method of a kind of stable circulation | |
| CN113629242A (en) | Preparation method of polyanionic vanadium iron sodium phosphate positive electrode material | |
| CN104393291A (en) | LiFePO4 positive electrode material modified jointly by doping and coating and preparation method thereof | |
| CN101593831A (en) | Process for preparing sol-gel based on the lithium iron phosphate cathode material of ferric phosphate | |
| CN110931770A (en) | Cr-doped modified high-voltage spinel cathode material and preparation method thereof | |
| CN114171729A (en) | Preparation method of graphene-based lithium iron phosphate positive electrode material | |
| CN109980221B (en) | High-voltage lithium ion battery positive electrode material and preparation method and application thereof | |
| CN106207166A (en) | A kind of method that full solid state reaction prepares non-stoichiometric phosphoric acid vanadium lithium | |
| CN101369659B (en) | Novel lithium iron phosphate anode material used for lithium ion battery and method of manufacturing the same | |
| CN115092962B (en) | Molybdenum dioxide/carbon composite electrode material and preparation method and application thereof | |
| CN113140816B (en) | P2 type layered oxide positive electrode and ether electrolyte system for long-life and high-rate performance sodium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20200428 |
|
| WD01 | Invention patent application deemed withdrawn after publication |