CN109841800B - Sodium vanadium fluorophosphate and carbon compound and preparation and application thereof - Google Patents
Sodium vanadium fluorophosphate and carbon compound and preparation and application thereof Download PDFInfo
- Publication number
- CN109841800B CN109841800B CN201711213837.4A CN201711213837A CN109841800B CN 109841800 B CN109841800 B CN 109841800B CN 201711213837 A CN201711213837 A CN 201711213837A CN 109841800 B CN109841800 B CN 109841800B
- Authority
- CN
- China
- Prior art keywords
- sodium
- carbon
- phosphate
- vanadium
- fluoride
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to a vanadium sodium fluorophosphate and carbon compound, a preparation method and application thereof, wherein the positive electrode material comprises Na3V2(PO4)2F3Carbon complex, Na3V2(PO4)2F3The carbon compound is prepared by using low-temperature green solvothermal one-step method, and Na is synthesized by solvothermal synthesis3V2(PO4)2F3In the process of (1), adding a carbon source, and carrying out in-situ carbonization on the carbon source in Na3V2(PO4)2F3Forming a carbon layer on the surface to obtain Na3V2(PO4)2F3A carbon composite. Compared with the common solvothermal method, the method is characterized in that a carbon source is introduced under the same reaction condition and Na3V2(PO4)2F3A carbon layer is formed on the surface, so that Na is effectively increased3V2 (PO4)2F3And the particles are reduced, thereby improving the rate capability of the material. Prepared Na3V2(PO4)2F3The carbon composite shows a discharge specific capacity close to a theoretical specific capacity and excellent rate capability through electrochemical performance test, and has good application prospect in portable electronic equipment and equipment for rapid charge and discharge.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to the field of positive electrode materials of sodium ion batteries.
Background
Energy is an important driving force for social development, and currently used energy is mainly divided into renewable energy (wind energy, hydroenergy, solar energy and the like) and non-renewable energy (coal, petroleum, natural gas and the like). Due to the shortage of non-renewable energy resources and serious pollution to the environment, the development of renewable energy is more and more concerned by people, but the renewable energy is discontinuous and unstable, and the direct grid connection of the renewable energy can generate great impact on a power grid. The energy storage technology is a key technology for solving the problems of discontinuity and instability of renewable energy sources. Among many energy storage technologies, lithium ion batteries have the advantages of high energy density, long cycle life and the like, and are widely applied to various portable electronic devices and electric automobiles, but the lithium ion batteries have limited storage capacity and uneven distribution of lithium resources, so that the large-scale development of the lithium ion batteries is limited.
The sodium and the lithium have similar chemical and physical properties, the Na storage is rich (the abundance of Na is 1000 times that of Li), the distribution is wide, the cost is low, and the development of the sodium-ion battery can effectively relieve the problem of limited lithium resources. The capacity of the sodium ion battery is limited by a positive electrode material, the development of the positive electrode material is the key point for realizing the large-scale application of the sodium ion battery, and the sodium vanadium fluorophosphate has an NASICON (sodium ion superconductor) structure, has high sodium ion deintercalation speed and stable structure, has higher voltage platform and theoretical specific capacity, and is a positive electrode material with great application potential. From the current reports, the preparation method of the sodium vanadium fluorophosphate is mainly a sol-gel method and a ball milling method, and the two methods have high energy consumption and complex preparation process because the two methods need to be subjected to medium-high temperature pre-sintering (300-400 ℃) and high temperature calcining phase. In order to realize the large-scale application of the sodium vanadium fluorophosphate, a green and simple method and low energy consumption must be found, and the solvothermal method can form a subcritical or critical state at a low temperature (100-. Thermal synthesis of Na in solvent3V2(PO4)2F3In the process of (1), adding a carbon source, and carrying out in-situ carbonization on the carbon source in Na3V2(PO4)2F3Forming a carbon layer on the surface to obtain Na3V2(PO4)2F3The carbon composite effectively improves the conductivity of the material. Simultaneously, Na is thermally synthesized in a solvent3V2(PO4)2F3The carbon source is added in the process of (1), so that the agglomeration among particles can be effectively prevented, and smaller particles of Na are generated3V2(PO4)2F3A carbon composite. The particle reduction shortens the desorption path and the electron conduction path of sodium ions, the desorption speed and the electron conduction speed of the sodium ions are greatly improved, the particle reduction enables the material to have a large specific surface area, the contact area of the material with carbon and electrolyte is increased, the transmission resistance of electrons and ions on the material interface is reduced, the transmission speed is increased, and therefore the rate capability of the material is improved. Prepared Na3V2(PO4)2F3The carbon composite shows a discharge specific capacity close to a theoretical specific capacity and excellent rate capability through electrochemical performance test, and has good application prospect in portable electronic equipment and rapid charge and discharge equipment.
Disclosure of Invention
The invention relates to a method for preparing a high-performance vanadium sodium fluorophosphate carbon composite by low-temperature in-situ carbonization and application of the high-performance vanadium sodium fluorophosphate carbon composite in a sodium ion battery.
The composition of the sodium vanadium fluorophosphate/carbon composite is Na3V2(PO4)2F3A carbon composite;
1) according to the mol ratio of sodium, vanadium, phosphate radical, fluorine, reducing agent, carbon and additive being 3:2:2:3: 0-2: 1 × 10-5Weighing sodium salt, a vanadium source, phosphate, villiaumite, a reducing agent, a carbon source and an additive in a ratio of-5: 0-2 to obtain a mixture;
2) adding the mixture obtained in the step 1) into a hydrothermal kettle at the temperature of 100 ℃ and 300 ℃, adding a solvent, and reacting for 3-72 h;
3) filtering the mixed solution obtained in the step 2), respectively washing with deionized water and ethanol for 2-5 times, and keeping at 100-150 ℃ for 1-20h to obtain Na3V2(PO4)2F3A carbon composite.
The sodium salt in the step 1) is one or more than two of sodium acetate, sodium sulfate, sodium oxalate, sodium citrate, sodium nitrate, sodium fluoride, sodium carbonate, sodium bicarbonate and sodium hydroxide,
the vanadium source is one or more than two of vanadium phosphate, ammonium metavanadate, vanadium acetylacetonate and vanadium pentoxide,
the phosphate is one or more of ammonium dihydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, potassium phosphate, sodium phosphate and vanadium phosphate,
the fluoride salt is one or more of ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride and hydrofluoric acid.
The reducing agent in the step 1) is one or two or more of oxalic acid, ascorbic acid, citric acid, formic acid, malic acid, oxalic acid and adipic acid.
The solvent in the step 2) is one or more than two of water, acetone, ethanol and glycol, and the solute mixture is a solvent of 1: (1-20) g/ml.
The carbon source in the step 1) is one or two or more of sucrose, glucose, starch, oxalic acid and cellulose.
The additive in the step 1) is one or more than two of PEG, sodium dodecyl benzene sulfonate, ammonia water, sodium hydroxide, oxalic acid, citric acid and hydrochloric acid.
The Na is3V2(PO4)2F3The carbon composite is used as a positive electrode material to be applied to a sodium ion battery. The prepared Na3V2(PO4)2F3The carbon composite is used as a positive electrode, the metal sodium sheet is used as a negative electrode, the glass fiber membrane is used as a diaphragm, and the solute is 1MNaClO4The sodium ion battery is assembled by sequentially stacking and compressing a mixture (mass ratio is 1:1) of solvents EC (ethylene carbonate) and DEC (diethyl carbonate), an additive FEC (forward-forward) with the mass fraction of 2% as an electrolyte and an aluminum foil as a current collecting plate through a CR2016 button shell according to the sequence of a negative electrode shell, a negative electrode, the electrolyte, a diaphragm, the electrolyte, a positive electrode and a current collector positive electrode shell.
The invention has the advantages of
Na of the invention3V2(PO4)2F3Is synthesized by using low-temperature green solvothermal one-step synthesis, compared with the common solvothermal method, by introducing a carbon source under the same reaction condition and Na3V2(PO4)2F3A carbon layer is formed on the surface, so that Na is effectively increased3V2(PO4)2F3Is used for the electrical conductivity of (1). Simultaneously, Na is thermally synthesized in a solvent3V2(PO4)2F3The carbon source is added in the process of (1), so that the agglomeration among particles can be effectively prevented, and smaller particles of Na are generated3V2(PO4)2F3A carbon composite. The particle reduction shortens the desorption path and the electron conduction path of sodium ions, the desorption speed and the electron conduction speed of the sodium ions are greatly improved, the particle reduction enables the material to have a large specific surface area, the contact area of the material with carbon and electrolyte is increased, the transmission resistance of electrons and ions on the material interface is reduced, the transmission speed is increased, and therefore the rate capability of the material is improved. Prepared Na3V2(PO4)2F3The carbon composite shows a discharge specific capacity close to a theoretical specific capacity and excellent rate capability through electrochemical performance test, and has good application prospect in portable electronic equipment and rapid charge and discharge equipment.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of comparative example, example 1, example 2, and example 3.
FIG. 2 is a graph of the rate capability of comparative example, example 1, example 2, and example 3.
Detailed Description
Example 1: (VPO)4Preparation of Na by low-temperature in-situ carbonization3V2(PO4)2F3Carbon composite)
0.315g of sodium fluoride (both as a fluorine source and a sodium source), 0.649g of vanadium phosphate (both as a vanadium source and a phosphate), and 0.3g of SDS (twelve sodium dodecyl sulfate) were weighedSodium alkyl sulfate), 1.2g glucose, was added to a 100mL hydrothermal kettle, 25mL ethanol and 25mL deionized water were added, and the reaction was carried out at 180 ℃ for 48 h. Filtering the obtained mixed solution with filter paper, washing with deionized water and ethanol for 3 times, and placing in a 120 deg.C oven for 8 hr to obtain Na3V2(PO4)2F3A carbon composite. The prepared Na3V2(PO4)2F3The carbon composite is used as a positive electrode, the metal sodium sheet is used as a negative electrode, the glass fiber membrane is used as a diaphragm, and the solute is 1MNaClO4The sodium ion battery is assembled by sequentially stacking and compressing a mixture (mass ratio is 1:1) of solvents EC (ethylene carbonate) and DEC (diethyl carbonate), an additive FEC (forward-forward) with the mass fraction of 2% as an electrolyte and an aluminum foil as a current collecting plate through a CR2016 button shell according to the sequence of a negative electrode shell, a negative electrode, the electrolyte, a diaphragm, the electrolyte, a positive electrode and a current collector positive electrode shell.
Example 2: (NH)4VO3Preparation of Na by low-temperature in-situ carbonization3V2(PO4)2F3Carbon composite)
0.315g of sodium fluoride (both as a fluorine source and a sodium source), 0.585g of ammonium metavanadate, 0.5752g of ammonium dihydrogen phosphate, 1.0507g of citric acid monohydrate, 0.3g of PEG-6000 and 0.9g of starch are weighed into a 100mL hydrothermal kettle, 25mL of acetone and 25mL of deionized water are added, and the mixture is reacted at 140 ℃ for 36 hours. Filtering the obtained mixed solution with filter paper, washing with deionized water and ethanol for 3 times, and placing in a 120 deg.C oven for 8 hr to obtain Na3V2(PO4)2F3A carbon composite.
Example 3: (V)2O5Preparation of Na by low-temperature in-situ carbonization3V2(PO4)2F3Carbon composite)
0.278g of ammonium fluoride, 0.300g of sodium hydroxide, 0.455g of vanadium pentoxide, 0.5752g of ammonium dihydrogen phosphate, 1.0507g of citric acid monohydrate and 1.5g of sucrose were weighed into a 100mL hydrothermal kettle, and 25mL of acetone and 25mL of deionized water were added to react at 120 ℃ for 48 hours. The resulting mixed solution was filtered using filter paper and then usedWashing with ionized water and ethanol for 3 times, and placing into a 120 deg.C oven for 8 hr to obtain Na3V2(PO4)2F3A carbon composite.
Comparative example (NH)4VO3Solvothermal preparation of Na3V2(PO4)2F3)
0.315g of sodium fluoride (both as a fluorine source and a sodium source), 0.585g of ammonium metavanadate, 0.5752g of ammonium dihydrogen phosphate and 1.0507g of citric acid monohydrate were weighed into a 100mL hydrothermal kettle, and 25mL of acetone and 25mL of deionized water were added and reacted at 180 ℃ for 48 hours. Filtering the obtained mixed solution with filter paper, washing with deionized water and ethanol for 3 times, and placing in a 120 deg.C oven for 8 hr to obtain Na3V2(PO4)2F3。
As can be seen from fig. 1, compared with the comparative example, the particles of examples 1, 2 and 3 are smaller, which is mainly due to the fact that carbon sources (glucose, starch and sucrose) are added in the hydrothermal process in examples 1, 2 and 3, and the carbon sources are carbonized in the hydrothermal process and coated on the surface of the particles, so that the further growth of the particles is prevented, and the particles are smaller. Meanwhile, the additives (SDS, PEG-6000) modified in the examples 1 and 2 can also reduce the size of the particles. The smaller particles make the specific surface area of the embodiment 1, the embodiment 2 and the embodiment 3 larger, and the electrons are transferred between the material interface and the electrolyte more quickly. In addition, the smaller particles reduce the diffusion path of sodium ions in examples 1, 2, and 3, shorten the diffusion time of sodium ions, and increase the desorption rate of sodium ions. Meanwhile, because the conductive carbon exists in the embodiment 1, the embodiment 2 and the embodiment 3, the conductivity of the conductive carbon is better than that of the comparative example. These reasons all contribute well to the rate capability of the embodiments.
As can be seen from fig. 2, the rate performance of examples 1, 2, 3 is significantly better than that of the comparative example. At 0.2C, the comparative example shows 105mAh g-1The specific capacity of (2) was determined, and example 1, example 2 and example 3 each showed 135mAh g-1、106mAh g-1、113mAh g-1The specific capacity of (A). At a high rate of 10C, the comparative example shows 17mAh g-1The specific capacity of (A) was 74mAh g in example 1, example 2 and example 3-1、76mAh g-1、67mAh g-1The specific capacity of the example under 10C is obviously better than that of the comparative example. Further, at a high rate of 40C, the comparative example has almost no capacity, whereas example 1, example 2, and example 3 each show 50mAh g-1、72mAh g-1、27mAh g-1The specific capacity, high rate performance of the examples is apparently due to the comparative examples.
Claims (5)
1. A preparation method of a sodium vanadium fluorophosphate and carbon compound is characterized by comprising the following steps: the preparation method comprises the following steps:
1) according to the mol ratio of sodium, vanadium, phosphate radical, fluorine, reducing agent, carbon and additive being 3:2:2:3 (0-2) to (1 × 10)-55) weighing sodium salt, a vanadium source, phosphate, fluoride salt, a reducing agent, a carbon source and an additive according to the proportion of 0.416-2 to obtain a mixture;
2) adding the mixture obtained in the step 1) into a hydrothermal kettle at the temperature of 100 ℃ and 300 ℃, adding a solvent, and reacting for 3-72 h;
3) filtering the mixed solution obtained in the step 2), respectively washing with deionized water and ethanol for 2-5 times, and keeping at 100-150 ℃ for 1-20h to obtain Na3V2(PO4)2F3A carbon composite;
the carbon source in the step 1) is one or two or more of sucrose, glucose and starch;
the reducing agent in the step 1) is one or two or more of oxalic acid, ascorbic acid, citric acid, formic acid, malic acid, oxalic acid and adipic acid;
the additive in the step 1) is one or two of sodium dodecyl benzene sulfonate and citric acid.
2. The method of claim 1, wherein:
the sodium salt in the step 1) is one or more than two of sodium acetate, sodium sulfate, sodium oxalate, sodium citrate, sodium nitrate, sodium fluoride, sodium carbonate, sodium bicarbonate and sodium hydroxide,
the vanadium source is one or more than two of vanadium phosphate, ammonium metavanadate, vanadium acetylacetonate and vanadium pentoxide,
the phosphate is one or more of ammonium dihydrogen phosphate, sodium dihydrogen phosphate, diammonium hydrogen phosphate, disodium hydrogen phosphate, potassium phosphate, sodium phosphate and vanadium phosphate,
the fluoride salt is one or more of ammonium fluoride, sodium fluoride, potassium fluoride, lithium fluoride and hydrofluoric acid.
3. The method of claim 1, wherein: the solvent in the step 2) is one or more than two of water, acetone, ethanol and glycol, and the solute of the mixture is that the solvent = 1: (1-20) g/ml.
4. A complex obtained by the process of any one of claims 1 to 3, which is Na3V2(PO4)2F3A carbon composite.
5. Use of the complex of claim 4, said Na3V2(PO4)2F3The carbon composite is used as a positive electrode material to be applied to a sodium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711213837.4A CN109841800B (en) | 2017-11-28 | 2017-11-28 | Sodium vanadium fluorophosphate and carbon compound and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711213837.4A CN109841800B (en) | 2017-11-28 | 2017-11-28 | Sodium vanadium fluorophosphate and carbon compound and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109841800A CN109841800A (en) | 2019-06-04 |
| CN109841800B true CN109841800B (en) | 2022-07-05 |
Family
ID=66880900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711213837.4A Active CN109841800B (en) | 2017-11-28 | 2017-11-28 | Sodium vanadium fluorophosphate and carbon compound and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109841800B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN114031063B (en) * | 2021-11-04 | 2023-02-28 | 湖南工程学院 | Sodium vanadium fluorophosphate nanocomposite and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105206831A (en) * | 2015-08-05 | 2015-12-30 | 北京工业大学 | Preparation method for sodium-ion battery cathode material Na3V2O2x(PO4)2F3-2x microspheres |
| CN105390690A (en) * | 2015-10-20 | 2016-03-09 | 合肥工业大学 | Preparation method for ultra-thin Li4Ti5O12 nanosheet assisted by surfactant, and use method for ultra-thin Li4Ti5O12 nanosheet in lithium battery and sodium battery |
| CN105932277A (en) * | 2016-03-01 | 2016-09-07 | 马鞍山宇驰新能源材料有限公司 | Preparation method of three-dimensional porous vanadium phosphate sodium / carbon anode material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105762356B (en) * | 2014-12-15 | 2019-10-11 | 中国科学院过程工程研究所 | A kind of fluorophosphoric acid vanadium sodium salt, preparation method and its usage |
| CN107154493B (en) * | 2016-03-02 | 2020-04-07 | 中国科学院过程工程研究所 | Sodium vanadium fluorophosphate, and preparation method and application thereof |
| CN105914352B (en) * | 2016-04-19 | 2019-03-12 | 上海紫剑化工科技有限公司 | A kind of sodium-ion battery positive material Na3V2(PO4)3The preparation method of/C |
| CN106654218A (en) * | 2017-01-11 | 2017-05-10 | 湖南文理学院 | Lithium ion battery positive electrode material lithium vanadium phosphate/carbon, preparation method thereof and lithium ion battery |
-
2017
- 2017-11-28 CN CN201711213837.4A patent/CN109841800B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105206831A (en) * | 2015-08-05 | 2015-12-30 | 北京工业大学 | Preparation method for sodium-ion battery cathode material Na3V2O2x(PO4)2F3-2x microspheres |
| CN105390690A (en) * | 2015-10-20 | 2016-03-09 | 合肥工业大学 | Preparation method for ultra-thin Li4Ti5O12 nanosheet assisted by surfactant, and use method for ultra-thin Li4Ti5O12 nanosheet in lithium battery and sodium battery |
| CN105932277A (en) * | 2016-03-01 | 2016-09-07 | 马鞍山宇驰新能源材料有限公司 | Preparation method of three-dimensional porous vanadium phosphate sodium / carbon anode material |
Non-Patent Citations (1)
| Title |
|---|
| A High Power−High Energy Na3V2(PO4)2F3 Sodium Cathode: Investigation of Transport Parameters, Rational Design and Realization;Changbao Zhu etal.;《Chemistry of Materials》;20170530;第5207-5215页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109841800A (en) | 2019-06-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109755489B (en) | Preparation of sodium vanadium fluorophosphate/carbon compound and application of compound | |
| CN102201576B (en) | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof | |
| CN113104828B (en) | Preparation method of porous carbon modified sodium iron pyrophosphate phosphate/sodium carbonate ion battery positive electrode material | |
| CN110416503B (en) | Soft carbon coated sodium titanium phosphate mesoporous composite material and preparation method and application thereof | |
| CN111293307B (en) | Carbon-supported sodium vanadium fluorophosphate and preparation and application thereof | |
| CN113839038A (en) | MOF-derived Bi @ C nano composite electrode material and preparation method thereof | |
| CN108615855A (en) | Titanium phosphate sodium material prepared by a kind of carbon coating and preparation and application | |
| CN108777294B (en) | Carbon-supported porous spherical MoN composed of nanosheets and application of carbon-supported porous spherical MoN as negative electrode material in lithium battery | |
| CN107732203B (en) | Preparation method of nano cerium dioxide/graphene/sulfur composite material | |
| CN108878826B (en) | Sodium manganate/graphene composite electrode material and preparation method and application thereof | |
| CN104362316A (en) | Lithium-sulfur battery composite cathode material, and preparation method and application thereof | |
| WO2024011862A1 (en) | Iron-based sodium ion full battery and preparation method therefor | |
| CN109301191A (en) | A kind of novel lithium sulfur battery anode material and preparation method thereof | |
| CN111106316B (en) | Carbon-supported monoclinic vanadium potassium fluorophosphate and preparation and application thereof | |
| CN112117444A (en) | Carbon-coated cobalt sulfide positive electrode material, preparation method, positive electrode and aluminum ion battery | |
| CN111559741B (en) | Preparation method of polyanion composite material | |
| CN110467170B (en) | High-potential positive electrode material of potassium ion battery and preparation method thereof | |
| CN109841800B (en) | Sodium vanadium fluorophosphate and carbon compound and preparation and application thereof | |
| CN113299897B (en) | Na (Na) 3 V 2 (PO 4 ) 3 Mixed ion full battery with @ C as positive electrode material | |
| CN108923027B (en) | Organic acid modified Si/TiO2Negative electrode material of/rGO @ C lithium ion battery and preparation method and application thereof | |
| CN110649263A (en) | Nickel-ion battery lithium vanadium phosphate positive electrode material, sol-gel preparation method and application | |
| CN116741972A (en) | Carbon-compounded mixed polyanion compound for sodium ion battery anode material and preparation method thereof | |
| CN109244417B (en) | Preparation method of composite positive electrode material of lithium-sulfur battery with nanosheet layered structure | |
| CN115498183A (en) | Modified vanadium manganese sodium phosphate cathode material, preparation and application thereof | |
| CN112768768B (en) | Battery electrolyte containing ammonium iodide additive and preparation method thereof |
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 |