CN110350198B - Preparation method of sodium phosphate surface modified sodium ion battery positive electrode material - Google Patents
Preparation method of sodium phosphate surface modified sodium ion battery positive electrode material Download PDFInfo
- Publication number
- CN110350198B CN110350198B CN201910666226.8A CN201910666226A CN110350198B CN 110350198 B CN110350198 B CN 110350198B CN 201910666226 A CN201910666226 A CN 201910666226A CN 110350198 B CN110350198 B CN 110350198B
- Authority
- CN
- China
- Prior art keywords
- sodium
- ion battery
- surface modified
- phosphate
- sodium 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.)
- Active
Links
Images
Classifications
-
- 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
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- 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
- 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
- H01M4/624—Electric conductive fillers
-
- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to the technical field of sodium ion battery materials, in particular to a preparation method of a sodium phosphate surface modified sodium ion battery anode material. The invention provides a preparation method of a sodium phosphate surface modified sodium ion battery anode material, which comprises the following steps of 1: adding a reducing agent and a dispersing agent into a sodium source, a vanadium source and a phosphorus source, mixing and ball-milling to obtain mixture powder; step 2: pre-sintering the mixture powder to obtain a vanadium sodium phosphate precursor; and step 3: dispersing the vanadium sodium phosphate precursor in a deionized water solution for ultrasonic treatment to obtain a suspension, and adding a phosphorus source solution into the suspension; and 4, step 4: and performing ball milling, mixing and sintering on the product, the sodium source and the dispersing agent to obtain the sodium phosphate surface modified sodium ion battery anode material. The invention provides a preparation method of a sodium phosphate surface modified sodium ion battery anode material, which can effectively solve the technical problem that the surface modification method of the existing sodium ion battery anode material is few in types.
Description
Technical Field
The invention relates to the technical field of sodium ion battery materials, in particular to a preparation method of a sodium phosphate surface modified sodium ion battery anode material.
Background
In recent years, sodium ion batteries, which are becoming mature day by day, are becoming a research hotspot in the field of energy storage because sodium has the advantages of abundant resources, wide distribution, low cost and the like. The positive electrode material of the sodium-ion battery is an important component of the sodium-ion battery, wherein the polyanion compound vanadium sodium phosphate Na3V2(PO4)3The lithium ion battery positive electrode material has ideal specific capacity, voltage plateau and cycling stability, thereby receiving wide attention. Na (Na)3V2(PO4)3Belongs to sodium super-ion conductor materialThe structure framework of the ion exchange membrane forms a stable sodium storage vacancy, and an open three-dimensional ion migration channel is beneficial to improving the diffusion of sodium ions.
Na3V2(PO4)3Despite the above advantages, the electron conductivity is low, which seriously affects the electrochemical performance. To solve Na3V2(PO4)3Inherent poor conductivity, an effective method is to synthesize Na having a nanostructure3V2(PO4)3Many researches improve the material performance by synthesizing nano materials such as nano particles, one-dimensional nano fibers, three-dimensional porous structures and the like, and the material with the special nano structure can improve the electronic conductivity of the material, shorten an ion transmission path and is beneficial to the embedding and the separation of sodium ions. In addition, Na can be improved by modifying the surface with a material having good electronic conductivity, such as carbon coating3V2(PO4)3The material has conductivity, and meanwhile, the direct contact between the material and electrolyte can be reduced, the volume change of the electrode material in the charge-discharge process is inhibited, and the rate capability and the cycling stability of the material are improved. Sodium phosphate is a good sodium ion conductor material and is beneficial to the deintercalation of sodium ions, but the research on the surface modification of sodium phosphate to the sodium vanadium phosphate of the sodium ion battery anode material is not reported yet.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a sodium phosphate surface modified sodium ion battery anode material, which can effectively solve the technical problem that the surface modification method of the existing sodium ion battery anode material has fewer types.
The invention provides a preparation method of a sodium phosphate surface modified sodium ion battery anode material, which comprises the following steps:
step 1: adding a reducing agent and a dispersing agent into a sodium source, a vanadium source and a phosphorus source, mixing, ball-milling for 5-15h, drying, and grinding to obtain mixture powder;
step 2: pre-sintering the mixture powder in an inert gas atmosphere, and cooling to room temperature to obtain a sodium vanadium phosphate precursor;
and step 3: dispersing the sodium vanadium phosphate precursor in a deionized water solution for ultrasonic treatment to obtain a suspension, adding a phosphorus source solution into the suspension, evaporating deionized water at 80-100 ℃, and drying at 100-120 ℃ for 8-20 hours to obtain a product;
and 4, step 4: and ball-milling and mixing the product, the sodium source and the dispersing agent, sintering in an inert gas atmosphere, and cooling to room temperature to obtain the sodium phosphate surface modified sodium ion battery cathode material.
Preferably, the sodium source is one or more of sodium acetate, sodium carbonate, sodium nitrate and sodium hydroxide.
Preferably, the vanadium source in step 1 is one or more of vanadium pentoxide, ammonium metavanadate, vanadyl sulfate, vanadyl acetylacetonate and vanadyl oxalate.
Preferably, the phosphorus source in step 1 and step 3 is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid and hypophosphorous acid, and the concentration range of the phosphorus source solution in step 3 is 0.0002-0.1 mol/L.
Preferably, the reducing agent in the step 1 is one or more of oxalic acid, citric acid, tartaric acid and ascorbic acid;
the molar ratio of the sodium vanadium phosphate to the reducing agent is 1: (1-5).
Preferably, the dispersant is one of water, ethanol and acetone;
the molar ratio of the sodium vanadium phosphate to the dispersant is 1: (0.1-5).
Preferably, the pre-sintering temperature is 300-600 ℃;
the pre-sintering time is 3-8 h.
Preferably, the sintering temperature is 400-900 ℃;
the sintering time is 5-15 h.
Preferably, the molar ratio of the sodium source to the phosphorus source in the step 4 is (3-3.15): 1.
preferably, the inert gas in step 2 and step 4 is one of nitrogen, argon, a mixture of nitrogen and hydrogen, or a mixture of argon and hydrogen.
Compared with the prior art, the invention has the following advantages and technical effects:
the sodium phosphate surface-modified sodium ion battery positive electrode material is prepared through simple solid-phase ball milling, surface modification and high-temperature solid-phase sintering reaction, and the sodium phosphate has good sodium ion conductivity and is more favorable for the desorption of sodium ions after surface modification. Compared with the traditional carbon coating layer, the sodium phosphate surface modification layer can not only reduce the electrochemical impedance of a material interface, but also be used as a sacrificial agent to react with trace amounts of HF and H in electrolyte2O reacts to reduce HF and H in electrolyte2The content of O, thus reducing the side reaction of the electrode material and the electrolyte, keeping the structure stable and improving the cycle performance and rate capability. In addition, the preparation method has the advantages of easily available raw materials, simple operation, low cost and good reproducibility, can meet various requirements of practical application of the sodium-ion battery, and can realize industrial large-scale production.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below.
FIG. 1 is an X-ray diffraction diagram of the sodium phosphate surface-modified sodium ion battery positive electrode material prepared in example 1 of the present invention;
FIG. 2 is an SEM image of the sodium phosphate surface modified sodium ion battery cathode material prepared in example 1 of the present invention;
FIG. 3 is a comparison curve of the first charge-discharge cycle at 1C rate of the sodium phosphate surface modified sodium ion battery positive electrode material prepared in the example of the present invention and the comparative example;
FIG. 4 is a multiple charge-discharge cycle curve at 1C rate for sodium phosphate surface-modified sodium ion battery positive electrode material prepared in an example of the present invention and a comparative example;
FIG. 5 is a charging and discharging curve of the sodium phosphate surface modified sodium ion battery anode material prepared in example 1 of the present invention and a comparative example under different multiplying power;
fig. 6 is an SEM image of the sodium phosphate surface-modified sodium ion battery positive electrode material prepared in comparative example 1.
Detailed Description
The embodiment of the invention provides a preparation method of a sodium phosphate surface modified sodium ion battery anode material, which can effectively solve the technical problem that the surface modification method of the existing sodium ion battery anode material is few in types.
The technical solutions in the embodiments of the present invention will be clearly and completely described below.
Example 1
(1) According to the synthesis 0.1mol Na3V2(PO4)3Weighing 15.90g of sodium carbonate, 23.40g of ammonium metavanadate and 34.51g of ammonium dihydrogen phosphate, adding 19.21g of citric acid, dispersing in 50mL of absolute ethyl alcohol, ball-milling for 10h, and drying to obtain mixture powder.
(2) And putting the mixture powder into a tube furnace, presintering for 4h at 350 ℃ in the atmosphere of nitrogen-hydrogen mixed gas, cooling to room temperature, and grinding to obtain the sodium vanadium phosphate precursor.
(3) Dispersing a sodium vanadium phosphate precursor in 100mL of deionized water solution, carrying out ultrasonic treatment for 1 hour to obtain a suspension, weighing 0.1g of ammonium dihydrogen phosphate, adding the ammonium dihydrogen phosphate into the deionized water to prepare 0.05mol/L of phosphorus source solution, dropwise adding the prepared phosphorus source solution into the suspension, evaporating the deionized water to dryness at 80 ℃, and drying at 100 ℃ for 8 hours.
(4) Ball-milling and mixing the product obtained in the step (3) with 0.14g of sodium carbonate, then adding 50mL of ethanol, mixing and ball-milling for 8 hours, drying, then placing the mixture into a tube furnace, sintering at 700 ℃ for 12 hours in the atmosphere of nitrogen-hydrogen mixed gas, and cooling to room temperature to obtain the sodium phosphate surface modified sodium ion battery positive electrode material Na3V2(PO4)3/Na3PO4。
Fig. 1 is an X-ray diffraction diagram of the sodium phosphate surface-modified sodium ion battery positive electrode material prepared in example 1 of the present invention, and it can be seen from fig. 1 that the product obtained in this example maintains the structure of sodium vanadium phosphate, and has high crystallinity and no impurity phase.
Fig. 2 is an SEM image of the sodium phosphate surface-modified sodium ion battery positive electrode material prepared in example 1 of the present invention, and it can be seen from fig. 2 that the particle size distribution is uniform and the surface is rough, which indicates that the surface is successfully modified with sodium phosphate.
Fig. 3 is a first charge-discharge cycle curve of the sodium phosphate surface-modified sodium ion battery positive electrode material prepared in example 1 of the present invention at a 1C rate, and as shown in fig. 3, when charge-discharge cycles are performed at 25 ℃ and at a 1C rate within a voltage range of 2.0 to 4.0V, the first discharge capacity of the sodium phosphate surface-modified sodium ion battery positive electrode material vanadium sodium phosphate is 106.4 mAh/g.
Fig. 4 is a multiple charge-discharge cycle curve of the sodium phosphate surface-modified sodium ion battery positive electrode material prepared in example 1 of the present invention at a 1C rate, as shown in fig. 4, the discharge capacity after 500 cycles is 101.2mAh/g, the capacity retention rate is 95.1%, and excellent cycle stability is shown.
Fig. 5 is a charge-discharge curve of the sodium phosphate surface modified sodium ion battery positive electrode material prepared in example 1 of the present invention at different magnifications, as shown in fig. 5, charge and discharge at 0.5C, 1C, 2C, 5C, 10C, and 15C magnifications, the specific discharge capacities of the sodium phosphate surface modified sodium ion battery positive electrode material vanadium sodium phosphate are 122.6, 106.3, 94.6, 80.7, 62.8, and 45.0mAh/g, respectively, and good rate capability is exhibited.
Example 2
(1) According to the synthesis 0.05mol Na3V2(PO4)3The element molar ratio of (A) is that 20.41g of sodium acetate trihydrate, 9.1g of vanadium pentoxide and 19.81g of diammonium hydrogen phosphate are weighed, 9.00g of oxalic acid is added, the mixture is dispersed in 25mL of acetone, and the mixture is ball-milled for 5 hours and dried to obtain mixture powder.
(2) And putting the mixture powder into a tube furnace, presintering for 5h at 400 ℃ in a nitrogen atmosphere, cooling to room temperature, and grinding to obtain the sodium vanadium phosphate precursor.
(3) Dispersing a sodium vanadium phosphate precursor in 80mL of deionized water solution, performing ultrasonic treatment for 0.5 hour to obtain a suspension, weighing 0.2g of diammonium phosphate, adding the diammonium phosphate into the deionized water to prepare 0.01mol/L phosphorus source solution, dropwise adding the prepared phosphorus source solution into the suspension, evaporating the deionized water at 90 ℃, and drying at 110 ℃ for 8 hours;
(4) and (3) performing ball milling mixing on the product obtained in the step (3) and 0.62g of sodium acetate trihydrate, then adding 100mL of deionized water, mixing and ball milling for 6 hours, drying, then placing the mixture into a tube furnace, sintering for 15 hours at 750 ℃ in an inert or reducing atmosphere, and cooling to room temperature to obtain the sodium phosphate surface modified sodium ion battery cathode material sodium vanadium phosphate.
When charging and discharging circulation is carried out at 25 ℃ and the 1C multiplying power within the voltage range of 2.0-4.0V, the first discharge capacity of the sodium phosphate surface modified sodium-ion battery positive material vanadium sodium phosphate is 105.9mAh/g, the discharge capacity after 500 cycles of circulation is 103.5mAh/g, the capacity retention rate is 97.7%, and excellent circulation stability is shown. The sodium phosphate surface modified sodium ion battery positive electrode material vanadium sodium phosphate is charged and discharged under the multiplying power of 0.5C, 1C, 2C, 5C, 10C and 15C, the specific discharge capacity of the sodium phosphate surface modified sodium ion battery positive electrode material vanadium sodium phosphate is 120.5, 105.3, 97.6, 89.7, 75.8 and 60.5mAh/g respectively, and good multiplying power performance is shown.
Example 3
(1) According to the synthesis 0.2mol Na3V2(PO4)3Weighing 24.00g of sodium hydroxide, 106.06g of vanadyl acetylacetonate, 89.45g of ammonium phosphate, adding 35.22g of ascorbic acid, dispersing in 100mL of deionized water, ball-milling for 15h, and drying to obtain mixture powder.
(2) And putting the mixture powder into a tube furnace, presintering for 8h at 500 ℃ in an argon atmosphere, cooling to room temperature, and grinding to obtain the sodium vanadium phosphate precursor.
(3) Dispersing a sodium vanadium phosphate precursor in 150mL of deionized water, carrying out ultrasonic treatment for 2 hours to obtain a suspension, weighing 1g of ammonium phosphate, adding the ammonium phosphate into the deionized water to prepare a 0.1mol/L phosphorus source solution, dropwise adding the prepared phosphorus source solution into the suspension, evaporating the deionized water at 100 ℃, and drying at 120 ℃ for 8 hours;
(4) and (3) performing ball milling mixing on the product obtained in the step (3) and 0.80g of sodium hydroxide, then adding 150mL of absolute ethyl alcohol, mixing and ball milling for 20 hours, drying, then placing the mixture into a tube furnace, sintering for 10 hours at 800 ℃ in an argon atmosphere, and cooling to room temperature to obtain the sodium phosphate surface modified sodium ion battery cathode material.
When charging and discharging circulation is carried out at 25 ℃ and the 1C multiplying power within the voltage range of 2.0-4.0V, the first discharge capacity of the sodium phosphate surface modified sodium ion battery anode material is 110.5mAh/g, the discharge capacity after 500 cycles of circulation is 106.7mAh/g, the capacity retention rate is 96.5%, and excellent circulation stability is shown. The sodium phosphate surface modified sodium ion battery positive electrode material is charged and discharged under the multiplying power of 0.5C, 1C, 2C, 5C, 10C and 15C, the specific discharge capacity of the sodium phosphate surface modified sodium ion battery positive electrode material is respectively 125.7, 110.8, 100.5, 91.2, 75.6 and 66.1mAh/g, and the sodium phosphate surface modified sodium ion battery positive electrode material has good multiplying power performance.
Comparative example 1
(1) According to the synthesis 0.1mol Na3V2(PO4)3Weighing 15.90g of sodium carbonate, 23.40g of ammonium metavanadate and 34.51g of ammonium dihydrogen phosphate, adding 19.21g of citric acid, dispersing in 50mL of ethanol, ball-milling for 10h, and drying to obtain mixture powder.
(2) Placing the mixture powder into a tube furnace, presintering for 4h at 350 ℃ and sintering for 12h at 700 ℃ in the atmosphere of nitrogen-hydrogen mixed gas, and cooling to room temperature to obtain the positive electrode material Na of the sodium-ion battery3V2(PO4)3。
Fig. 6 is an SEM image of the sodium phosphate surface-modified sodium ion battery positive electrode material prepared in comparative example 1, and it can be seen from fig. 6 that the particle size distribution is uniform.
When the charge and discharge cycle is carried out at 25 ℃ and the 1C multiplying power within the voltage range of 2.0-4.0V, the initial discharge capacity of the sodium vanadium phosphate of the positive electrode material of the sodium-ion battery is 95.5mAh/g (shown in figure 3), the discharge capacity after 500 cycles is only 76.7mAh/g, and the capacity retention rate is 80.3% (shown in figure 4). The sodium vanadium phosphate positive electrode material of the sodium ion battery is charged and discharged under the multiplying power of 0.5C, 1C, 2C, 5C, 10C and 15C, and the specific discharge capacity of the sodium vanadium phosphate positive electrode material of the sodium ion battery is 109.7, 92.5, 80.2, 62.7, 38.7 and 7.7mAh/g (shown in figure 5).
It is to be understood that, as described above, the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A preparation method of a sodium phosphate surface modified sodium ion battery positive electrode material is characterized by comprising the following steps:
step 1: adding a reducing agent and a dispersing agent into a sodium source, a vanadium source and a phosphorus source, mixing, ball-milling for 5-15h, drying, and grinding to obtain mixture powder;
step 2: pre-sintering the mixture powder in a protective gas atmosphere, and cooling to room temperature to obtain a sodium vanadium phosphate precursor;
and step 3: dispersing the sodium vanadium phosphate precursor in a deionized water solution for ultrasonic treatment to obtain a suspension, adding a phosphorus source solution into the suspension, evaporating deionized water at 80-100 ℃, and drying at 100-120 ℃ for 8-20 hours to obtain a product;
and 4, step 4: and ball-milling and mixing the product, the sodium source and the dispersing agent, sintering in a protective gas atmosphere, and cooling to room temperature to obtain the sodium phosphate surface modified sodium ion battery cathode material.
2. The preparation method of the sodium phosphate surface modified sodium ion battery positive electrode material as claimed in claim 1, wherein the sodium source is one or more of sodium acetate, sodium carbonate, sodium nitrate and sodium hydroxide.
3. The method for preparing the sodium phosphate surface modified sodium ion battery cathode material according to claim 1, wherein the vanadium source in the step 1 is one or more of vanadium pentoxide, ammonium metavanadate, vanadyl sulfate, vanadyl acetylacetonate and vanadyl oxalate.
4. The method for preparing the sodium phosphate surface modified sodium ion battery cathode material according to claim 1, wherein the phosphorus source in the steps 1 and 3 is one or more of ammonium dihydrogen phosphate, diammonium hydrogen phosphate, ammonium phosphate, phosphoric acid and hypophosphorous acid, and the concentration of the phosphorus source solution in the step 3 is 0.0002-0.1 mol/L.
5. The preparation method of the sodium phosphate surface modified sodium ion battery cathode material according to claim 1, wherein the reducing agent in the step 1 is one or more of oxalic acid, citric acid, tartaric acid and ascorbic acid;
the molar ratio of the sodium vanadium phosphate to the reducing agent is 1: (1-5).
6. The method for preparing the sodium phosphate surface modified sodium ion battery cathode material according to claim 1, wherein the dispersant is one of water, ethanol and acetone;
the molar ratio of the sodium vanadium phosphate to the dispersant is 1: (0.1-5).
7. The preparation method of the sodium phosphate surface modified sodium ion battery positive electrode material according to claim 1, wherein the pre-sintering temperature is 300-600 ℃;
the pre-sintering time is 3-8 h.
8. The preparation method of the sodium phosphate surface modified sodium ion battery positive electrode material according to claim 1, wherein the sintering temperature is 400-900 ℃;
the sintering time is 5-15 h.
9. The preparation method of the sodium phosphate surface modified sodium ion battery positive electrode material as claimed in claim 1, wherein the molar ratio of the sodium source in step 4 to the phosphorus source in step 3 is (3-3.15): 1.
10. the method for preparing the sodium phosphate surface modified sodium ion battery positive electrode material as claimed in claim 1, wherein the protective gas in the steps 2 and 4 is one of nitrogen, argon, a nitrogen-hydrogen mixed gas or an argon-hydrogen mixed gas.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910666226.8A CN110350198B (en) | 2019-07-23 | 2019-07-23 | Preparation method of sodium phosphate surface modified sodium ion battery positive electrode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910666226.8A CN110350198B (en) | 2019-07-23 | 2019-07-23 | Preparation method of sodium phosphate surface modified sodium ion battery positive electrode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110350198A CN110350198A (en) | 2019-10-18 |
| CN110350198B true CN110350198B (en) | 2020-11-17 |
Family
ID=68179889
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910666226.8A Active CN110350198B (en) | 2019-07-23 | 2019-07-23 | Preparation method of sodium phosphate surface modified sodium ion battery positive electrode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110350198B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111082058B (en) * | 2019-12-20 | 2023-03-21 | 华南理工大学 | Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material and preparation method thereof |
| CN111009661B (en) * | 2019-12-24 | 2022-02-08 | 攀枝花学院 | Flexible self-supporting Na3(VO)2(PO4)2F material and preparation method and application thereof |
| CN111439737B (en) * | 2020-03-10 | 2021-11-30 | 西安交通大学 | Vanadium-based sodium oxyfluorophosphate type sodium battery positive electrode material and preparation method thereof |
| CN114335529B (en) * | 2021-11-05 | 2024-01-26 | 四川龙蟒磷化工有限公司 | Preparation method of vanadium sodium phosphate type sodium battery positive electrode material |
| CN116262635B (en) * | 2021-12-15 | 2024-07-05 | 浙江钠创新能源有限公司 | Modified sodium nickel manganese oxide electrode material, sodium ion battery, preparation method and application |
| CN116081594B (en) * | 2023-02-23 | 2024-07-09 | 武汉工程大学 | Preparation method of sodium ion battery anode material |
| WO2024197434A1 (en) * | 2023-03-24 | 2024-10-03 | 广东邦普循环科技有限公司 | Modified sodium ion positive electrode material, preparation method therefor, and use thereof |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102163721B (en) * | 2006-12-15 | 2013-03-27 | 东京应化工业株式会社 | Negative electrode base member |
| CN103000884A (en) * | 2011-09-16 | 2013-03-27 | 中国科学院物理研究所 | Vanadium sodium phosphate composite material as well as preparation method and application thereof |
| CN103151493A (en) * | 2013-03-12 | 2013-06-12 | 北京理工大学 | Lithium phosphate coated lithium iron phosphate electrode and preparation method thereof |
| CN105140468A (en) * | 2015-06-26 | 2015-12-09 | 武汉大学 | Preparation method for cathode material Na3V2(PO4)3/C of sodium ion battery |
| JP6338115B2 (en) * | 2015-11-04 | 2018-06-06 | トヨタ自動車株式会社 | Non-aqueous electrolyte secondary battery |
| CN107611367B (en) * | 2017-08-04 | 2020-08-18 | 中南大学 | Porous spherical carbon-coated vanadium sodium phosphate composite positive electrode material and preparation method thereof |
-
2019
- 2019-07-23 CN CN201910666226.8A patent/CN110350198B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN110350198A (en) | 2019-10-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110350198B (en) | Preparation method of sodium phosphate surface modified sodium ion battery positive electrode material | |
| CN112768673B (en) | Na4Fe3-x(PO4)2P2O7Positive electrode material of/C sodium ion battery and preparation method and application thereof | |
| CN110061229B (en) | High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof | |
| EP2125615B1 (en) | Method for preparing lithium iron phosphate as a positive electrode active material for a lithium ion secondary battery | |
| CN111082058B (en) | Nasicon structure sodium titanium phosphate surface modified P2 type manganese-based sodium ion battery positive electrode material and preparation method thereof | |
| CN101348243B (en) | Lithium iron phosphate anode active material and preparation thereof | |
| CN110299528B (en) | Fluorinated phosphate ferric sodium pyrophosphate @ C @ RGO composite material, preparation method thereof and application thereof in sodium ion battery | |
| CN111162256A (en) | Mixed polyanion type sodium ion battery positive electrode material and preparation thereof | |
| CN101752562B (en) | Compound doped modified lithium ion battery anode material and preparation method thereof | |
| CN107978738B (en) | Manganese sodium pyrophosphate/carbon composite cathode material and preparation and application thereof | |
| CN111082059A (en) | V-doped P2 type sodium ion battery positive electrode material and preparation method thereof | |
| CN110611080B (en) | Transition metal doped titanium manganese phosphate sodium/carbon composite positive electrode material, preparation thereof and application thereof in sodium ion battery | |
| EP4391112A1 (en) | Composite coating method for highly-compacted nickelic layered positive electrode material of solid-state battery | |
| CN115101738A (en) | Carbon-coated iron-vanadium bimetallic sodium pyrophosphate phosphate composite material and preparation method and application thereof | |
| CN111099569B (en) | Preparation method of reduced graphene oxide/carbon material coated lithium iron phosphate material | |
| CN116682946A (en) | Doped modified ferric sodium pyrophosphate positive electrode material and preparation method thereof | |
| CN110085854B (en) | Lithium vanadium phosphate cathode material and preparation method thereof | |
| CN116281922A (en) | Sodium-rich fluorine-doped ferric sodium pyrophosphate composite material, and preparation method and application thereof | |
| CN116169260A (en) | β”-Al 2 O 3 And N-doped C composite coated Na 3 V 2 (PO 4 ) 2 F 3 Electrode material | |
| CN114824205A (en) | Titanium-based fast ion conductor modified sodium iron phosphate positive electrode material, preparation method thereof and battery prepared from positive electrode material | |
| CN114284476A (en) | Preparation method of carbon composite sodium-ion battery positive electrode material | |
| FR3143209A1 (en) | LITHIUM-MANGANESE-IRON PHOSPHATE CATHODE MATERIAL AND PREPARATION METHOD THEREFOR | |
| CN116706056A (en) | Based on ultra-small particles Na x Fe y M z (SO 4 ) 3 Non-destructive quick-charging positive electrode material, and preparation method and application thereof | |
| CN117012925A (en) | Rare earth metal or transition metal doped lithium molybdate/carbon composite material, and preparation method and application thereof | |
| CN115863632A (en) | Preparation method of lithium iron phosphate carbon aerogel composite material |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |