CN108269988A - The preparation method of sodium-ion battery positive material calcium potassium codope vanadium phosphate sodium/carbon - Google Patents
The preparation method of sodium-ion battery positive material calcium potassium codope vanadium phosphate sodium/carbon Download PDFInfo
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- CN108269988A CN108269988A CN201810099867.5A CN201810099867A CN108269988A CN 108269988 A CN108269988 A CN 108269988A CN 201810099867 A CN201810099867 A CN 201810099867A CN 108269988 A CN108269988 A CN 108269988A
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- 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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
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- 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
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- 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
- H01M4/625—Carbon or graphite
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- H—ELECTRICITY
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- 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
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- 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 discloses the preparation methods of sodium-ion battery positive material calcium potassium codope vanadium phosphate sodium/carbon, prepare presoma using hydro-thermal reaction, presoma obtains calcium potassium codope vanadium phosphate sodium/carbon composite by the pyroreaction under inert atmosphere.The present invention realizes the uniform mixing on reaction raw materials molecular level using chelating agent, the advantages of easily chelating agent being made to be carbonized using hydro-thermal reaction, precursor product surface is made to form equally distributed carbon, be conducive in lower temperature and carbothermic reduction reaction is completed under conditions of the short period, the tiny codope vanadium phosphate sodium/carbon composite of generation particle.The codope of potassium calcium ion can both expand insertion/deintercalation channel of vanadium phosphate sodium, the concentration in sodium vacancy can be improved again, conducive to fast transferring of the sodium ion in active material particle, it is obviously improved the ionic conductivity of material, and carbon coating is remarkably improved the electronic conductivity of material, thus calcium potassium codope vanadium phosphate sodium/carbon has excellent chemical property.
Description
Technical field
The invention belongs to technical field of energy material, more particularly to a kind of high performance sodium ion positive electrode calcium potassium is co-doped with
The preparation method of miscellaneous vanadium phosphate sodium/carbon.
Background technology
Sodium-ion battery positive material vanadium phosphate sodium (Na3V2(PO4)3) it is a kind of fast-ionic conductor, there is ionic conductivity
Can higher, excellent heat stability, permissible sodium ion quickly through big channel, stable structure, operating voltage is high, capacity is high
The advantages that, it is considered to be a kind of sodium-ion battery positive material of most application prospect.But since its electronic conductivity compares
Low and thus cause the shortcomings of activation polarization is bigger, cycle performance is poor, the chemical property for causing it practical is poor,
It is difficult to industrialization.For the disadvantages mentioned above of vanadium phosphate sodium, researcher has carried out a large amount of fruitful research work.By drawing
Enter the carbon of highly electron conductive, prepare vanadium phosphate sodium/carbon composite, improve the electronic conductivity of material, reduce electrification
Polarization is learned, so as to improve the chemical property of vanadium phosphate sodium；By adulterating electro-chemical activity or non-electrical in the vanadium position of vanadium phosphate sodium
Chemically active ion, improves the structural stability of material, and expands the channel of ion, improves ionic conductivity, so as to
Improve the chemical property of vanadium phosphate sodium.Above two method improves the electrochemistry of vanadium phosphate sodium to a certain extent
Can, but its chemical property still needs to further improve by other methods.
Chen Quanqi etc. proves to improve chemical property (the Journal of Power of phosphoric acid vanadium lithium by adulterating in lithium position
Sources, 2012,201,267-273), but raising vanadium phosphate sodium chemical property is adulterated by sodium position and is had not been reported.The present invention
Using the strategy being carried out at the same time in the doping of the sodium position of vanadium phosphate sodium and carbon coating, it is compound to prepare calcium potassium codope vanadium phosphate sodium/carbon
Material develops the serial vanadium phosphate sodium with excellent electrochemical performance with important scientific research meaning and application value.
Invention content
The purpose of the present invention is to provide a kind of sodium ion positive electrode calcium potassium codope vanadium phosphate sodium and preparation method thereof,
This method is simple for process, and the sodium-ion battery positive material of preparation has sodium vacancy, and in the process of sodium ion insertion/deintercalation
Middle holding structure is stablized, which has the advantages that capacity is high, it is high with energy density to have extended cycle life.
In order to achieve the above objectives, the technical solution adopted by the present invention is：
A kind of sodium-ion battery positive material calcium potassium codope vanadium phosphate sodium/carbon composite, the material have three dimensional network
Network frame structure, can allow for Na+Quickly through and can be in Na+Stable structure is maintained in deintercalation and telescopiny.Sodium ion electricity
Calcium potassium codope vanadium phosphate sodium in pond positive electrode calcium potassium codope vanadium phosphate sodium/carbon is with Na3-x-2yKxCayV2(PO4)3It represents,
The preparation method of the positive electrode, includes the following steps：
1) vanadium source compound, P source compound, sodium source compound, potassium resource compound, calcium source compound, chelating agent are massaged
You compare V：P：Na：K：Ca：C=2：3：(3-x-2y)：x：y：6 weigh (wherein x+2y≤0.3), and be transferred to hydrothermal reaction kettle
In, distilled water or deionized water are added in, and reaction kettle is heated to 120 DEG C~180 DEG C, constant temperature 2h~12h is then naturally cold
But, the reaction product in reaction kettle is all poured out, and moisture evaporation is complete, obtains black product；
2) black product in (1) is placed in 100~180 DEG C of baking oven and dried；
3) by (2) dry after product be transferred in tube furnace, under inert atmosphere conditions, with 2 DEG C/min~10 DEG C/
The heating rate of min is heated to 700 DEG C~800 DEG C, constant temperature 2h~8h, then cools to room temperature with the furnace to get to the sodium of black
Ion battery positive electrode Na3-x-2yKxCayV2(PO4)3/ C composite.
The vanadium source compound is one or both of vanadic anhydride, ammonium metavanadate；Phosphorus source compound is phosphorus
It is one or more in acid dihydride ammonium, diammonium hydrogen phosphate, ammonium phosphate, phosphorus pentoxide；The sodium source compound for sodium hydroxide,
It is one or more in sodium acetate, sodium nitrate, sodium carbonate, sodium bicarbonate；The potassium resource compound for potassium hydroxide, potassium carbonate,
It is one or more in saleratus, potassium nitrate, potassium acetate；The calcium source compound is calcium acetate, in calcium nitrate, calcium hydroxide
It is one or more；The chelating agent is citric acid, one or more in oxalic acid, tartaric acid, ethylenediamine tetra-acetic acid；It is described lazy
Property atmosphere be nitrogen, one or both of argon gas.The sodium-ion battery that the sodium-ion battery positive material is assembled into is by sodium
Ion battery positive plate, negative plate, diaphragm, electrolyte assemble, wherein positive plate by sodium-ion battery positive material with leading
It is made after electric agent and binding agent mixing, negative plate is sodium metal, and diaphragm is fibreglass diaphragm, electrolyte NaPF6Poly- carbon
Acid esters solution.
The present invention is water-soluble by vanadium source compound, P source compound, sodium source compound, potassium resource compound, calcium source compound etc.
Property substance and chelating agent act on, there is powerful chelation using chelating agent, reactant is made to reach uniform on molecular level
Distribution is conducive to reaction in lower temperature and is completed in the short period, and obtain the smaller product of particle size.Utilize chelating agent
It is easy to the process of carbonization under hydrothermal conditions, carbon is made to be formed and be uniformly distributed in the surface in situ of hydro-thermal reaction product, is conducive to
Subsequent further high temperature carbonization, forms the carbon of highly electron conductive, and carbon coating can both play pyrocarbon heat in reaction-ure surface
Reduction reaction generates the effect of doping phosphoric acid vanadium sodium, can also play and doping phosphoric acid vanadium sodium product grain is inhibited to reunite and grow up,
Be conducive to obtain the smaller carbon coating doping phosphoric acid vanadium sodium of size.The carbon coating layer of residual in the product has high electronic conductance
Rate, is conducive to significantly improve the electronic conductivity of material, and the vacancy that Doped ions generate sodium is introduced in sodium position, be conducive to sodium from
The deintercalation and insertion of son, so as to obtain doping phosphoric acid vanadium sodium/carbon composite of electrochemical performance.
Description of the drawings
Fig. 1 is the x-ray diffraction pattern of calcium potassium codope vanadium phosphate sodium/carbon prepared by case study on implementation 1 of the present invention.
Fig. 2 is the x-ray diffraction pattern of calcium potassium codope vanadium phosphate sodium/carbon prepared by case study on implementation 2 of the present invention
Fig. 3 is the scanning electron microscope (SEM) photograph of calcium potassium codope vanadium phosphate sodium/carbon prepared by case study on implementation 2 of the present invention.
Fig. 4 be sodium ion positive electrode prepared by case study on implementation 2 of the present invention in the voltage range of 2.5~4.0V, electric current
Density is 0.2C (23.6mAg-1) under the conditions of first charge-discharge curve.
Fig. 5 be sodium ion positive electrode prepared by case study on implementation 2 of the present invention in the voltage range of 2.5~4.0V, electric current
Density is 0.2C (23.6mAg-1) under the conditions of cycle performance curve.
Specific embodiment
Case study on implementation of the present invention is described further below.
Case study on implementation 1：Weigh 0.015mol vanadic anhydrides, 0.045mol ammonium dihydrogen phosphates, 0.04365mol sodium acetates,
The reactants such as 0.00045mol potassium acetates, 0.00045mol calcium acetates and 0.09mol citric acids, and it is all added in into liner and is
In the reaction kettle of 100mL, 80mL distilled water is then added in, reaction kettle liner is sealed and screws reaction kettle cover.By what is be sealed
It is in 120 DEG C of convection oven that reaction kettle, which is placed in temperature, reacts 8h, then by reaction kettle cooled to room temperature, by reaction kettle
In precipitation and solution all down in beaker, and heat removing moisture content.It is 120 DEG C that hydrothermal product after being evaporated is placed in temperature
Convection oven in, dry 8h.Dried mixture is transferred in tube furnace, under argon gas atmosphere protection, with 2 DEG C/min
Heating rate be heated to 700 DEG C, constant temperature 2h, cool to room temperature with the furnace to get to sodium-ion battery positive material
Na2.91K0.03Ca0.03V2(PO4)3/ C composite.Fig. 1 is the X-ray diffracting spectrum of the material.
The sodium ion positive electrode Na that will be prepared2.91K0.03Ca0.03V2(PO4)3/ C composite, acetylene black and PVDF
It is 8 in mass ratio:1:1 ratio ground and mixed is uniform, suitable NMP is added dropwise, electrode slurry is made, then again by slurry in aluminium
It is uniform that mill is applied on foil, is placed in 120 DEG C of vacuum drying chambers fully dry, is cut into the paillon of a diameter of 15mm as Electrode,
It is compacted with twin rollers.Using the positive plate being prepared as positive electrode, using metallic sodium piece as cathode, with 1molL-1NaPF6
Polycarbonate solution as electrolyte, diaphragm is Whatman fibreglass diaphragms, in the gloves full of dry high-purity argon gas
CR2016 type button cells are dressed up in case (moisture and oxygen content are both less than 0.1ppm).Button cell is placed in battery testing system
On system, it is tested in room temperature charge-discharge performance, when current density is 0.2C and charging/discharging voltage ranging from 2.5~4.0V (vs.Na+/ Na) under conditions of, reversible discharge capacity is 112.7mAhg for the first time-1, after recycling 100 times, capacity remains
102.3mAh·g-1。
Case study on implementation 2：Weigh 0.03mol ammonium metavanadates, 0.045mol diammonium hydrogen phosphates, 0.04305mol sodium acetates,
The reactants such as 0.00045mol potassium acetates, 0.00075mol calcium acetates and 0.09mol citric acids, and it is all added in into liner and is
In the reaction kettle of 100mL, 85mL distilled water is then added in, reaction kettle liner is sealed and screws reaction kettle cover.By what is be sealed
It is in 180 DEG C of convection oven that reaction kettle, which is placed in temperature, reacts 8h, then by reaction kettle cooled to room temperature, by reaction kettle
In precipitation and solution all down in beaker, and heat removing moisture content.It is 120 DEG C that hydrothermal product after being evaporated is placed in temperature
Convection oven in, dry 8h.Dried mixture is transferred in tube furnace, under argon gas atmosphere protection, with 5 DEG C/min
Heating rate be heated to 750 DEG C, constant temperature 6h, cool to room temperature with the furnace to get to sodium-ion battery positive material
Na2.87K0.03Ca0.05V2(PO4)3/ C composite.Fig. 2 is the X-ray diffracting spectrum of the material, and Fig. 3 is the scanning of the material
Electron microscope.
The sodium ion positive electrode Na that will be prepared2.87K0.03Ca0.05V2(PO4)3/ C composite, acetylene black and PVDF
It is 8 in mass ratio:1:1 ratio ground and mixed is uniform, suitable NMP is added dropwise, electrode slurry is made, then again by slurry in aluminium
It is uniform that mill is applied on foil, is placed in 120 DEG C of vacuum drying chambers fully dry, is cut into the paillon of a diameter of 15mm as Electrode,
It is compacted with twin rollers.Using the positive plate being prepared as positive electrode, using metallic sodium piece as cathode, with 1molL-1NaPF6
Polycarbonate solution as electrolyte, diaphragm is Whatman fibreglass diaphragms, in the gloves full of dry high-purity argon gas
CR2016 type button cells are dressed up in case (moisture and oxygen content are both less than 0.1ppm).Button cell is placed in battery testing system
On system, it is tested in room temperature charge-discharge performance, when current density is 0.2C and charging/discharging voltage ranging from 2.5~4.0V (vs.Na+/ Na) under conditions of, reversible discharge capacity is 110.9mAhg for the first time-1, after recycling 100 times, capacity remains
108.3mAh·g-1.Fig. 4 and Fig. 5 is respectively the first charge-discharge curve of the material and cycle performance curve.
Case study on implementation 3：
Weigh 0.03mol ammonium metavanadates, 0.045mol ammonium phosphate, 0.042mol sodium nitrate, 0.0015mol potassium acetates,
The reactants such as 0.00075mol calcium nitrate and 0.135mol tartaric acid, and it is all added in the reaction kettle that liner is 100mL,
Then 85mL distilled water is added in, reaction kettle liner is sealed and screws reaction kettle cover.The reaction kettle being sealed is placed in temperature is
In 120 DEG C of convection oven, 8h is reacted, it is then by reaction kettle cooled to room temperature, the precipitation in reaction kettle and solution is complete
Removing moisture content is heated down in beaker in portion.Hydrothermal product after being evaporated is placed in the convection oven that temperature is 160 DEG C, done
Dry 8h.Dried mixture is transferred in tube furnace, under argon gas atmosphere protection, is heated with the heating rate of 5 DEG C/min
To 800 DEG C, constant temperature 4h, room temperature is cooled to the furnace to get to sodium-ion battery positive material Na2.8K0.1Ca0.05V2(PO4)3/ C is multiple
Condensation material.
The sodium ion positive electrode Na that will be prepared2.8K0.1Ca0.05V2(PO4)3/ C composite, acetylene black and PVDF
It is 8 in mass ratio:1:1 ratio ground and mixed is uniform, suitable NMP is added dropwise, electrode slurry is made, then again by slurry in aluminium
It is uniform that mill is applied on foil, is placed in 120 DEG C of vacuum drying chambers fully dry, is cut into the paillon of a diameter of 15mm as Electrode,
It is compacted with twin rollers.Using the positive plate being prepared as positive electrode, using metallic sodium piece as cathode, with 1molL-1NaPF6
PC solution as electrolyte, diaphragm is Whatman fibreglass diaphragms, in the glove box (water full of dry high-purity argon gas
Point and oxygen content be both less than 0.1ppm) in dress up CR2016 type button cells.Button cell is placed on battery test system,
It is tested in room temperature charge-discharge performance, when current density is 0.2C and charging/discharging voltage ranging from 2.5~4.0V (vs.Na+/Na)
Under conditions of, reversible discharge capacity is 105.8mAhg for the first time-1, after recycling 100 times, capacity remains 104.3mAh
g-1。
Case study on implementation 4：
Weigh 0.03mol ammonium metavanadates, 0.045mol ammonium phosphate, 0.042mol sodium nitrate, 0.0015mol potassium acetates,
The reactants such as 0.00075mol calcium nitrate and 0.054mol ethylenediamine tetra-acetic acids, and it is the anti-of 100mL that it is all added in liner
It answers in kettle, then adds in 85mL distilled water, reaction kettle liner is sealed and screws reaction kettle cover.The reaction kettle being sealed is placed in
Temperature is in 120 DEG C of convection oven, reacts 8h, then by reaction kettle cooled to room temperature, by the precipitation in reaction kettle and
Solution heats removing moisture content all down in beaker.Hydrothermal product after being evaporated is placed in the convection oven that temperature is 120 DEG C
In, dry 8h.Dried mixture is transferred in tube furnace, under argon gas atmosphere protection, with the heating speed of 10 DEG C/min
Rate is heated to 800 DEG C, constant temperature 6h, cools to room temperature with the furnace to get to sodium-ion battery positive material Na2.7K0.1Ca0.1V2
(PO4)3/ C composite.
The sodium ion positive electrode Na that will be prepared2.7K0.1Ca0.1V2(PO4)3/ C composite, acetylene black and PVDF are pressed
Mass ratio is 8:1:1 ratio ground and mixed is uniform, suitable NMP is added dropwise, electrode slurry is made, then again by slurry in aluminium foil
The upper mill that applies is uniform, is placed in 120 DEG C of vacuum drying chambers and fully dries, and is cut into the paillon of a diameter of 15mm as Electrode, uses
Twin rollers are compacted.Using the positive plate being prepared as positive electrode, using metallic sodium piece as cathode, with 1molL-1NaPF6's
Polycarbonate solution is as electrolyte, and diaphragm is Whatman fibreglass diaphragms, in the glove box full of dry high-purity argon gas
CR2016 type button cells are dressed up in (moisture and oxygen content are both less than 0.1ppm).Button cell is placed in battery test system
On, it is tested in room temperature charge-discharge performance, when current density is 0.2C and charging/discharging voltage ranging from 2.5~4.0V (vs.Na+/
Na under conditions of), reversible discharge capacity is 98.5mAhg for the first time-1, after recycling 100 times, capacity remains 92.3mAh
g-1。
It is numerous to list herein since embodiment of the present invention is more, in the spirit and its essence without departing substantially from the present invention
In the case of, those skilled in the art can make various corresponding changes and deformation according to the present invention, but these are corresponding
Change and deformation should all belong to the protection domain of appended claims of the invention.
Claims (1)
1. the preparation method of sodium-ion battery positive material calcium potassium codope vanadium phosphate sodium/carbon, it is characterised in that walk in detail below
Suddenly it is：
(1) by vanadium source compound, P source compound, sodium source compound, potassium resource compound, calcium source compound, chelating agent by mole
Compare V：P：Na：K：Ca：C=2：3：(3-x-2y)：x：y：6 weigh (wherein x+2y≤0.3), and be transferred in hydrothermal reaction kettle,
Distilled water or deionized water are added in, and reaction kettle is heated to 120 DEG C~180 DEG C, constant temperature 4h~12h, then natural cooling, it will
Reaction product in reaction kettle is all poured out, and moisture evaporation is complete, obtains black product；
(2) black product in (1) is placed in 100 DEG C~180 DEG C of baking oven and dried；
(3) product after (2) are dried is transferred in tube furnace, under inert atmosphere conditions, with 2 DEG C/min~10 DEG C/min's
Heating rate is heated to 700 DEG C~800 DEG C, constant temperature 2h~8h, then cools to room temperature with the furnace to get electric to the sodium ion of black
Pond positive electrode Na3-x-2yKxCayV2(PO4)3/ C composite；
The vanadium source compound is one or both of vanadic anhydride, ammonium metavanadate；
Phosphorus source compound is ammonium dihydrogen phosphate, one or more in diammonium hydrogen phosphate, ammonium phosphate, phosphorus pentoxide；
The sodium source compound is sodium hydroxide, one or more in sodium acetate, sodium nitrate, sodium carbonate, sodium bicarbonate；
The potassium resource compound is potassium hydroxide, one or more in potassium carbonate, saleratus, potassium nitrate, potassium acetate；
The calcium source compound is calcium acetate, one or more in calcium nitrate, calcium hydroxide；
The chelating agent is citric acid, one or more in oxalic acid, tartaric acid, ethylenediamine tetra-acetic acid；
The inert atmosphere is one or both of nitrogen, argon gas.
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| CN109921001A (en) * | 2019-03-25 | 2019-06-21 | 四川大学 | A kind of vanadium phosphate sodium/carbon composite anode material and its Microwave-assisted synthesis and application |
| CN110137480A (en) * | 2019-06-08 | 2019-08-16 | 桂林理工大学 | Kalium ion battery positive electrode rubidium doping phosphoric acid vanadium potassium/carbon composite preparation method |
| CN110165189A (en) * | 2019-06-08 | 2019-08-23 | 桂林理工大学 | Kalium ion battery positive electrode magnesium doping phosphoric acid vanadium potassium/carbon composite preparation method |
| CN110467170A (en) * | 2019-08-27 | 2019-11-19 | 清华大学深圳研究生院 | A kind of kalium ion battery high potential positive electrode and preparation method thereof |
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| CN111082162B (en) * | 2020-01-08 | 2021-11-23 | 中国石油大学(华东) | Aqueous sodium ion battery |
| CN111082162A (en) * | 2020-01-08 | 2020-04-28 | 中国石油大学(华东) | Aqueous sodium ion battery |
| CN111628163A (en) * | 2020-05-12 | 2020-09-04 | 青岛大学 | De-intercalation type vanadium-based negative electrode material and preparation method thereof |
| CN114256446A (en) * | 2020-09-23 | 2022-03-29 | 湖南农业大学 | Polyanion type positive electrode material and preparation method and application thereof |
| CN112701282A (en) * | 2020-12-28 | 2021-04-23 | 武汉大学 | Large-radius ion-doped modified sodium vanadium fluorophosphate cathode material and preparation method thereof |
| CN113659146A (en) * | 2021-08-12 | 2021-11-16 | 中北大学 | Potassium lanthanum silicon ternary codoped vanadium sodium phosphate electrode material and preparation method and application thereof |
| CN116364915A (en) * | 2023-05-30 | 2023-06-30 | 江苏众钠能源科技有限公司 | Positive electrode material, positive electrode plate and sodium ion battery |
| CN116364915B (en) * | 2023-05-30 | 2023-12-29 | 江苏众钠能源科技有限公司 | Positive electrode material, positive electrode plate and sodium ion battery |
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