CN108807899B - Preparation method of multilevel spherical sodium vanadium phosphate composite anode material - Google Patents
Preparation method of multilevel spherical sodium vanadium phosphate composite anode material Download PDFInfo
- Publication number
- CN108807899B CN108807899B CN201810594100.XA CN201810594100A CN108807899B CN 108807899 B CN108807899 B CN 108807899B CN 201810594100 A CN201810594100 A CN 201810594100A CN 108807899 B CN108807899 B CN 108807899B
- Authority
- CN
- China
- Prior art keywords
- sodium
- vanadium
- source
- spherical
- anode material
- 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.)
- Expired - Fee Related
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
- 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
-
- 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
- H01M4/625—Carbon or graphite
-
- 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
-
- 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)
- Composite Materials (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Secondary Cells (AREA)
Abstract
The invention relates to a preparation method of a multilevel spherical sodium vanadium phosphate composite anode material. The method comprises the steps of taking oxalic acid, a vanadium source, a sodium source and a phosphorus source as main raw materials, taking urea as a balling agent and a carbon source, forming a spherical sodium vanadium phosphate precursor by a hydrothermal method, drying the precursor, and then carrying out two-step heat treatment in a nitrogen atmosphere to obtain the spherical sodium vanadium phosphate precursor. The vanadium phosphate sodium composite anode material obtained by the invention has a multi-stage spherical shape, the diameter of microsphere particles is 1-5 mu m, the vanadium phosphate sodium composite anode material can be used as an anode material for sodium ion batteries, the first round specific discharge capacity can reach 116.47mAh/g within the working voltage range of 2.5V-4.3V and under the 0.1C multiplying power, the first round specific discharge capacity is 95mAh/g under the 10C multiplying power, and the capacity retention rate is more than 98% after 100 cycles of circulation. Compared with the prior art, the method not only improves the electrochemical performance of the anode material, but also is simple and effective in synthesizing the spherical morphology.
Description
Technical Field
The invention relates to a preparation method of a multilevel spherical vanadium sodium phosphate composite anode material, belonging to the technical field of anode materials of sodium-ion batteries.
Background
At present, compared with lithium ion batteries, sodium ion batteries have multiple advantages of rich element sources, uniform regional distribution, obvious cost reduction and the like, and are considered as important substitutes of the lithium ion batteries. In addition, sodium ions and lithium ions belong to the first main group element of the periodic table of elements and have similar nuclear outer electron shell structures, and the radius of the sodium ions is larger and the mass is heavier, and the increased ionic radius has two decisive advantages: one is that the polarization caused by the larger radius of the sodium ions is small, so that the solubility of the sodium ions in the electrolyte is small, thereby reducing the transfer resistance of the sodium ions; more importantly, the ion radius is large, and the formed solid structure can provide a larger ion transmission channel, but the structures cannot be realized by lithium.
Among the numerous materials, Na3V2(PO4)3(NVP) is a very potential positive electrode material of a sodium ion battery, and has an NASION framework structure, the unique structure can provide an open three-dimensional framework to facilitate the migration of sodium ions, and during the process of embedding/extracting the sodium ions, the NVP can show a charge-discharge platform at about 3.4V, which corresponds to V3+/V4+A redox couple of (a). However, the low electronic conductivity of the phosphate material can cause low coulombic efficiency and poor cycle performance, thereby affecting the practicability of the phosphate material, which is a main obstacle faced by NVP.
Because the electrode material has morphology dependency, the NVP has spherical morphology through morphology control, the specific surface area of the electrode material is increased, the contact area of the electrolyte and the electrode material is further increased, and more reaction sites are provided for the charge-discharge reaction of the electrode material; and the spherical shape can effectively regulate and control the volume change in the charging and discharging process, prevent the electrode material pulverization failure phenomenon generated by the volume change and directly improve the cycle performance of NVP. In addition, the carbon layer is coated on the surface of the material, so that the conductivity of the sodium vanadium phosphate can be improved, and the preparation of NVP/C with spherical morphology is considered to be an effective method for developing the positive electrode material of the sodium vanadium phosphate ion battery.
In the current research, most of the carbon sources are selectively introduced to form a carbon coating so as to obtain a porous spherical structure, thereby improving the specific surface area and the conductivity. However, this method has many problems, such as uneven carbon coating, difficulty in controlling the thickness, and poor material properties. Publication No. CN106898752A discloses a preparation method of a porous spherical sodium vanadium phosphate/carbon tube composite positive electrode material, but the synthesis of carbon nanotubes used in the method is not easy, and the cycling stability needs to be further improved. Publication No. CN107845796A discloses a carbon-doped sodium vanadium phosphate positive electrode material and a preparation method thereof, wherein sol-gel is combined with high-temperature calcination to obtain a precursor, a buffer solution is prepared, the precursor is mixed and dispersed with dopamine hydrochloride, and then solid-liquid separation and drying are carried out; finally, calcining the mixture for two sections to obtain the anode material; but the method has complex process, poor performance of the synthesized material under high multiplying power and poor industrialization prospect. The publication No. CN107611367A discloses a porous spherical carbon-coated vanadium sodium phosphate composite positive electrode material and a preparation method thereof, the method needs to add an organic solvent with polarity greater than that of water for hydrothermal treatment, the reaction cost is increased, centrifugation and washing precipitation are needed, and the steps are complicated. The publication number CN105244503A discloses a preparation method of a graded graphene modified spherical sodium ion electrode material, which adopts spray drying and high-temperature treatment to obtain a graded graphene modified spherical material, but the method has a complex pelletizing mechanism, high cost and needs to further improve the cycle performance.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a multilevel spherical vanadium sodium phosphate composite anode material aiming at the defects in the prior art, and the vanadium sodium phosphate composite anode material prepared by the method has a multilevel spherical shape and can be used as an anode material of a sodium-ion battery.
A preparation method of a multilevel spherical sodium vanadium phosphate composite anode material mainly comprises the following steps:
(1) mixing a sodium source, deionized water and urea, and stirring and dissolving in water bath at 50-70 ℃ to prepare a colorless solution A; wherein the molar ratio of sodium element to urea in the sodium source is 3: 1-5;
(2) according to Na3V2(PO4)3The stoichiometric ratio of Na: v: p is 3: 2: 3, the molar ratio of oxalic acid to vanadium in the vanadium source is 1-3: 1, the vanadium source, the phosphorus source and the oxalic acid are weighed and dissolved in deionized water, and the solution is stirred and dissolved in a water bath at the temperature of 50-70 ℃ to prepare a blue solution B;
(3) according to Na3V2(PO4)3The stoichiometric ratio of Na: v: p is 3: 2: 3, dropwise and slowly adding the solution B prepared in the step (2) into the solution A prepared in the step (1), and stirring and dissolving to form a mixed solution;
(4) putting the mixed solution prepared in the step (3) into a hydrothermal kettle, carrying out hydrothermal reaction for 6-18 h at 120-180 ℃, drying and grinding to obtain precursor powder;
(5) and (4) carrying out secondary heat treatment on the precursor powder prepared in the step (4) for 9-15 h under a protective atmosphere, and naturally cooling to obtain the multistage spherical vanadium sodium phosphate composite anode material.
Preferably, according to the invention, Na is present in the colorless solution A+The concentration is in the range of 0.1mol/L to 1 mol/L.
Preferably, according to the present invention, the sodium source is one of trisodium citrate, sodium carbonate, sodium acetate, and the like.
Preferably, according to the present invention, the vanadium source is one of vanadium pentoxide, ammonium metavanadate, and the like.
Preferably, according to the present invention, the phosphorus source is one of ammonium dihydrogen phosphate, phosphoric acid, and the like.
Preferably, in the step (3), the stirring and dissolving are carried out in a water bath at 50-70 ℃ for 15-45 min.
Preferably, in step (4), the hydrothermal reaction is carried out at 120-180 ℃ for 6-18 h.
Preferably, in step (5), the secondary heat treatment is specifically: firstly heating to 300-400 ℃ for heat treatment for 4-6 h, naturally cooling, taking out, fully grinding, and then placing the sample in an atmosphere furnace to heat to 600-800 ℃ for heat treatment for 5-7 h.
According to the present invention, in the step (5), the protective atmosphere is preferably nitrogen, inert gas, or the like.
The vanadium phosphate sodium composite anode material can be applied as an anode material of a sodium-ion battery, and the specific method comprises the following steps:
1) fully grinding and mixing the prepared vanadium phosphate sodium composite positive electrode material with a conductive agent and a binder, adding an N-methyl pyrrolidone solvent, and uniformly stirring to obtain a precoated refined slurry;
2) coating the precoated refined slurry obtained in the step 1) on an aluminum foil, drying an electrode plate to obtain a positive electrode plate of the sodium-ion battery, and using the obtained positive electrode plate of the sodium-ion battery for a button-type battery.
Compared with the prior art, the invention has the following beneficial effects:
firstly, the invention applies organic chemistry to the preparation of phosphorus with spherical morphologyIn the vanadium sodium acid composite anode material, the raw material uses anhydrous oxalic acid and a vanadium source to form VOC2O4Further, amino groups and VOCs in urea2O4The carboxyl in the sodium vanadium phosphate undergoes condensation reaction to form peptide bond-CO-NH-to enable urea to be combined on the surface of the sodium vanadium phosphate, the urea is self-assembled into a spherical shape due to the characteristics of a surfactant, and in-situ carbon coating is performed by pyrolysis of the urea in the heat treatment process, so that Na is coated3V2(PO4)3Controlling the shape of the/C material and finishing compact carbon coating. During the synthesis process, the urea not only plays the roles of a balling agent and providing a carbon source, but also is combined in the VOC2O4The surface can also effectively control Na3V2(PO4)3Grain size, realization of nanocrystallization, and shortening of transmission path of sodium ions in the anode material, thereby increasing Na content3V2(PO4)3The conductivity and specific capacity of the positive electrode material.
Secondly, a hydrothermal method is adopted to create a high-temperature high-pressure environment, crystal growth is in a non-compression state, and the prepared crystal powder has the advantages of complete crystal grain development, small granularity, light particle agglomeration and the like, and special equipment is not needed in the method; after secondary heat treatment, the vanadium phosphate sodium composite anode material with excellent performance is synthesized, the first discharge specific capacity can reach 116.47mAh/g at 0.1 ℃ in the voltage range of 2.5V-4.3V, and the first discharge specific capacity is close to Na3V2(PO4)3The theoretical specific capacity and the 10C multiplying power can reach 95mAh/g in first discharge specific capacity, the capacity retention rate is more than 98% after 100 cycles of circulation, and the material can be used as a positive electrode material for preparing a sodium ion battery, so that the electrochemical performance of the positive electrode material of the sodium ion battery is improved, and the preparation difficulty and the preparation cost are reduced.
Drawings
FIG. 1 is an XRD pattern of a vanadium sodium phosphate composite positive electrode material synthesized in example 1; where the ordinate is the diffraction intensity and the abscissa is the diffraction angle (2 θ).
Fig. 2 is an SEM image of the vanadium sodium phosphate composite positive electrode material synthesized in example 1.
FIG. 3 is a first round charge-discharge curve diagram of the vanadium phosphate sodium composite positive electrode material synthesized in example 1; wherein the ordinate is the voltage and the abscissa is the specific capacity.
FIG. 4 is a graph of the high rate cycle performance of the vanadium sodium phosphate composite positive electrode material synthesized in example 1; wherein the ordinate is the specific discharge capacity and the abscissa is the cycle number.
Detailed Description
The present invention will now be described in further detail with reference to the following examples and the accompanying drawings, which are illustrative and not restrictive.
Example 1
A preparation method of a multilevel spherical sodium vanadium phosphate composite anode material comprises the following specific steps:
(1) 2.941g of trisodium citrate dihydrate and 1.5015g of urea are weighed and dissolved in 40ml of deionized water, stirred in a water bath at the temperature of 60 ℃, and fully dissolved to prepare a colorless solution A;
(2) weighing 2.3398g of ammonium metavanadate, 3.4509g of ammonium dihydrogen phosphate and 2.7009g of anhydrous oxalic acid, dissolving in 40ml of deionized water, stirring in a water bath at 60 ℃, and fully dissolving to obtain a blue solution B;
(3) slowly adding the solution B into the solution A drop by drop, and stirring in a water bath at 60 ℃ for 30min to form a mixed solution;
(4) putting the mixed solution obtained in the step (3) into a hydrothermal kettle, carrying out hydrothermal reaction for 12 hours at 160 ℃, drying and grinding to obtain precursor powder;
(5) heating the precursor powder to 350 ℃ for heat treatment for 5h under the protection of nitrogen, naturally cooling, taking out, fully grinding, and then placing in an atmosphere furnace to heat to 700 ℃ for heat treatment for 6 h. And naturally cooling to obtain the multilevel spherical vanadium sodium phosphate composite anode material.
As shown in FIG. 1, the obtained electrode material was mixed with Na3V2(PO4)3The PDF #45-0319 cards are good in contrast, and consistent crystalline phase diffraction peaks appear, indicating that the obtained material is sodium vanadium phosphate. In addition, SEM test is carried out on the particle, as shown in figure 2, the morphology of the multilevel spheres can be observed under a scanning electron microscope, and the particle size of the particles is 1-5 μm.
And, the multilevel spherical vanadium sodium phosphate composite positive electrode material prepared in the embodiment 1 is subjected to electrochemical performance test. The specific process is as follows:
and preparing the vanadium phosphate sodium composite electrode material into an electrode by adopting a coating method. Fully grinding and mixing a vanadium sodium phosphate composite positive electrode material, acetylene black and polyvinylidene fluoride (PVDF) according to a mass ratio of 80:10:10, adding an N-methyl pyrrolidone solvent, and uniformly stirring to obtain pre-coating refined slurry; and respectively coating the pre-coating refined slurry on an aluminum foil, performing vacuum drying at 110 ℃ for 12h, naturally cooling, and cutting into a wafer with the diameter of 10mm by using a sheet punching machine to obtain the positive electrode plate of the sodium-ion battery.
And sequentially assembling the negative electrode shell, the stainless steel net, the sodium sheet, the electrolyte, the diaphragm, the electrolyte, the positive electrode sheet, the stainless steel net and the positive electrode shell, and sealing the battery by using a sealing machine to obtain the CR2016 type button sodium half-battery. The charging and discharging test of the battery is carried out by a charging and discharging instrument of a blue current CT 2001A. The test results are shown in fig. 3, and it can be seen that: the vanadium phosphate sodium composite positive electrode material with the multilevel spherical morphology prepared in the embodiment 1 has a first discharge specific capacity of 116.47mAh/g at 0.1 ℃ in a voltage range of 2.5V-4.3V; as can be seen from FIG. 4, the material has a specific discharge capacity of 95mAh/g at 10C within a voltage range of 2.5V-4.3V, and after 100 cycles, the capacity retention rate is more than 98%.
Example 2
A preparation method of a multilevel spherical sodium vanadium phosphate composite anode material comprises the following specific steps:
(1) 2.941g of trisodium citrate dihydrate and 0.75075g of urea are weighed and dissolved in 40ml of deionized water, stirred in a water bath at 50 ℃, and fully dissolved to prepare a colorless solution A;
(2) weighing 2.3398g of ammonium metavanadate, 3.4509g of ammonium dihydrogen phosphate and 2.7009g of anhydrous oxalic acid, dissolving in 40ml of deionized water, stirring in a water bath at 50 ℃, and fully dissolving to obtain a blue solution B;
(3) slowly adding the solution B into the solution A drop by drop, stirring in a water bath at 50 ℃ for 15min to form a mixed solution;
(4) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 6h at 140 ℃, drying and grinding to obtain precursor powder;
(5) heating the precursor powder to 300 ℃ for heat treatment for 4h under the protection of nitrogen, naturally cooling, taking out, fully grinding, and then placing in an atmosphere furnace to heat to 600 ℃ for heat treatment for 5 h. And naturally cooling to obtain the multilevel spherical vanadium sodium phosphate composite anode material.
Electrochemical performance tests were performed according to the procedure described in example 1, and the first discharge specific capacity was 106mAh/g at 0.1C over a voltage range of 2.5V to 4.3V.
Example 3
A preparation method of a multilevel spherical sodium vanadium phosphate composite anode material comprises the following specific steps:
(1) 2.941g of trisodium citrate dihydrate and 3.003g of urea are weighed and dissolved in 40ml of deionized water, and are stirred in a water bath at the temperature of 80 ℃ to be fully dissolved to prepare a colorless solution A;
(2) weighing 2.3398g of ammonium metavanadate, 3.4509g of ammonium dihydrogen phosphate and 2.7009g of anhydrous oxalic acid, dissolving in 40ml of deionized water, stirring in a water bath at 80 ℃, and fully dissolving to obtain a blue solution B;
(3) slowly adding the solution B into the solution A drop by drop, and stirring in a water bath at 80 ℃ for 45min to form a mixed solution;
(4) putting the mixed solution into a hydrothermal kettle, carrying out hydrothermal reaction for 18h at 180 ℃, drying and grinding to obtain precursor powder;
(5) heating the precursor powder to 400 ℃ under the protection of nitrogen for heat treatment for 6h, naturally cooling, taking out, fully grinding, and then placing in an atmosphere furnace to heat to 800 ℃ for heat treatment for 7 h. And naturally cooling to obtain the multilevel spherical vanadium sodium phosphate composite anode material.
Electrochemical performance tests were performed according to the procedure described in example 1, with a first discharge specific capacity of 111mAh/g at 0.1C over a voltage range of 2.5V to 4.3V.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, many modifications and changes can be made without departing from the inventive concept of the present invention, and these modifications and changes are within the protection scope of the present invention.
Claims (7)
1. A preparation method of a multilevel spherical sodium vanadium phosphate composite anode material is characterized by mainly comprising the following steps:
(1) mixing a sodium source, water and urea, and stirring for dissolving to obtain a colorless solution A; wherein the molar ratio of sodium element in the sodium source to urea is 3: 1-5;
(2) weighing a vanadium source, a phosphorus source and oxalic acid according to the molar ratio of the oxalic acid to vanadium in the vanadium source of 1-3: 1, dissolving the vanadium source, the phosphorus source and the oxalic acid in water, and stirring to dissolve the vanadium source, the phosphorus source and the oxalic acid to prepare a blue solution B;
(3) dropwise adding the solution B prepared in the step (2) into the solution A prepared in the step (1), stirring and dissolving to form a mixed solution;
(4) putting the mixed solution prepared in the step (3) into a hydrothermal kettle for hydrothermal reaction, and then drying and grinding to obtain precursor powder; wherein the hydrothermal reaction is carried out for 6 to 18 hours at the temperature of between 120 and 180 ℃;
(5) carrying out secondary heat treatment on the precursor powder prepared in the step (4) for 9-15 h under a protective atmosphere, and naturally cooling to obtain a multistage spherical vanadium sodium phosphate composite anode material; wherein, the secondary heat treatment specifically comprises the following steps: firstly heating to 300-400 ℃ for heat treatment for 4-6 h, naturally cooling, taking out, fully grinding, and then placing the sample in an atmosphere furnace to heat to 600-800 ℃ for heat treatment for 5-7 h.
2. The preparation method of the multilevel spherical vanadium phosphate sodium composite positive electrode material according to claim 1, wherein the diameter of the microsphere particle of the multilevel spherical vanadium phosphate sodium composite positive electrode material is 1-5 μm.
3. The preparation method of the multi-stage spherical vanadium-sodium phosphate composite cathode material as claimed in claim 1, wherein the Na source, the V source and the P source are Na3V2(PO4)3The stoichiometric ratio of Na: v: p = 3: 2: 3, feeding; na in colorless solution A+The concentration is in the range of 0.1mol/L to 1 mol/L.
4. The method for preparing the multi-stage spherical vanadium sodium phosphate composite cathode material according to claim 1, wherein the sodium source is one of trisodium citrate, sodium carbonate and sodium acetate; the vanadium source is one of vanadium pentoxide and ammonium metavanadate; the phosphorus source is one of ammonium dihydrogen phosphate and phosphoric acid.
5. The preparation method of the multi-stage spherical vanadium sodium phosphate composite cathode material according to claim 1, wherein the stirring and dissolving temperatures in the steps (1), (2) and (3) are both 50-70 ℃; in the step (3), the stirring and dissolving are carried out in a water bath at 50-70 ℃ for 15-45 min.
6. The multi-stage spherical vanadium sodium phosphate composite cathode material prepared by the method of any one of claims 1 to 5.
7. The application of the multilevel spherical sodium vanadium phosphate composite cathode material of claim 6 as a cathode material of a sodium-ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810594100.XA CN108807899B (en) | 2018-06-11 | 2018-06-11 | Preparation method of multilevel spherical sodium vanadium phosphate composite anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810594100.XA CN108807899B (en) | 2018-06-11 | 2018-06-11 | Preparation method of multilevel spherical sodium vanadium phosphate composite anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108807899A CN108807899A (en) | 2018-11-13 |
| CN108807899B true CN108807899B (en) | 2020-11-24 |
Family
ID=64088257
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810594100.XA Expired - Fee Related CN108807899B (en) | 2018-06-11 | 2018-06-11 | Preparation method of multilevel spherical sodium vanadium phosphate composite anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108807899B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092366B (en) * | 2019-04-25 | 2023-03-31 | 西北工业大学 | Complex-phase vanadium sodium phosphate electrode material and preparation method thereof |
| CN110518214B (en) * | 2019-09-02 | 2020-08-04 | 齐鲁工业大学 | Nitrogen-hydrogen in-situ double-doped soft carbon/sodium vanadium phosphate composite material and preparation method and application thereof |
| CN114975992A (en) * | 2022-05-31 | 2022-08-30 | 西安交通大学 | Preparation method of transition metal ion doped sodium vanadium phosphate cathode material |
| CN115966691A (en) * | 2022-12-20 | 2023-04-14 | 济南大学 | Micro co-doped modified sodium vanadium phosphate monocrystal micro-flower and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393982A (en) * | 2008-10-28 | 2009-03-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
| CN102723489A (en) * | 2012-06-27 | 2012-10-10 | 北京化工大学 | Nitrogen-doped carbon-coated Li3V2(PO4)3 cathode material and preparation method thereof |
| CN105304879A (en) * | 2015-11-18 | 2016-02-03 | 中南大学 | Preparation method of composite cathode material Li3V(MoO4)3/LiVOMoO4 |
| CN106981642A (en) * | 2017-05-22 | 2017-07-25 | 中南大学 | A kind of spherical vanadium phosphate manganese sodium composite of nitrating carbon coating and preparation method thereof and the application in sodium-ion battery |
-
2018
- 2018-06-11 CN CN201810594100.XA patent/CN108807899B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101393982A (en) * | 2008-10-28 | 2009-03-25 | 南京海泰纳米材料有限公司 | Method for producing carbon coated nano stage lithium iron phosphate by precipitation |
| CN102723489A (en) * | 2012-06-27 | 2012-10-10 | 北京化工大学 | Nitrogen-doped carbon-coated Li3V2(PO4)3 cathode material and preparation method thereof |
| CN105304879A (en) * | 2015-11-18 | 2016-02-03 | 中南大学 | Preparation method of composite cathode material Li3V(MoO4)3/LiVOMoO4 |
| CN106981642A (en) * | 2017-05-22 | 2017-07-25 | 中南大学 | A kind of spherical vanadium phosphate manganese sodium composite of nitrating carbon coating and preparation method thereof and the application in sodium-ion battery |
Non-Patent Citations (2)
| Title |
|---|
| "Superior sodium intercalation of honeycomb-structured hierarchical porous Na3V2(PO4)(3)/C microballs prepared by a facile one-pot synthesis";Wang Qiuyue et al.;《Journal of materials chemistry A》;20150421;第3卷(第15期);pages:7669-8216 * |
| "纳米磷酸钒钠锂复合正极材料的合成及改性研究";王朝阳;《中国优秀硕士学位论文全文数据库 工程科技Ⅱ辑》;20180415;第2018年/卷(第4期);第C042-1173页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108807899A (en) | 2018-11-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP4654686B2 (en) | Carbon-coated Li-containing powder and method for producing the same | |
| CN108807899B (en) | Preparation method of multilevel spherical sodium vanadium phosphate composite anode material | |
| CN111029569B (en) | Lithium ion battery lithium supplementing additive, battery electrode, preparation method and application thereof | |
| CN108878877B (en) | Positive electrode active material for aqueous zinc ion secondary battery and aqueous zinc ion secondary battery | |
| CN101290986B (en) | Preparing method of Li3V2(PO4)3/C positive pole and prepared positive pole material | |
| CN110931781A (en) | Preparation method and application of biomass carbon/sodium iron fluorophosphate composite material | |
| CN103165896A (en) | Method for preparing lithium iron phosphate/carbon composite material by thickener doping modification | |
| CN111162256A (en) | Mixed polyanion type sodium ion battery positive electrode material and preparation thereof | |
| CN107369827A (en) | A kind of preparation method of phosphoric acid vanadium lithium/carbon composite anode material of flower-like structure | |
| Li et al. | Synthesis and electrochemical properties of LiFePO4 cathode material by ionic thermal method using eutectic mixture of tetramethyl ammonium chloride–urea | |
| CN111009659A (en) | Preparation method and application of biomass carbon/poly-sodium manganese fluorophosphate composite material | |
| CN112421040A (en) | Phosphate anode material and preparation method and application thereof | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN104401957B (en) | A kind of hydrothermal preparing process of positive electrode material of lithium secondary cell fluorophosphoric acid cobalt lithium | |
| Ding et al. | Modified solid-state reaction synthesized cathode lithium iron phosphate (LiFePO4) from different phosphate sources | |
| CN113540410A (en) | Preparation method and application of lithium iron phosphate cathode material synthesized by rapid high-temperature thermal shock method | |
| CN110534721B (en) | Method for repairing ternary cathode material with degraded performance and ternary cathode material obtained by same | |
| CN110790248B (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof | |
| ZHONG et al. | Synthesis of LiMnPO4/C composite material for lithium ion batteries by sol-gel method | |
| CN115084465B (en) | Pre-lithiated binary topological structure phosphorus/carbon composite material and preparation method and application thereof | |
| CN104916840A (en) | Three-dimensional porous grading carbon modified LMP-LVP/C electrode material, and preparation method and application thereof | |
| CN113328071B (en) | Lithium vanadium phosphate/carbon battery positive electrode material and preparation method thereof | |
| CN106058247B (en) | Monodisperse lithium iron phosphate nanometer rods and its preparation method and application | |
| CN106611846A (en) | Synthesis method of alpha-LiFeO2/porous carbon composite material of lithium-ion battery anode | |
| CN109461897B (en) | Preparation method of spindle-shaped carbon-coated vanadium-based positive electrode 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201124 Termination date: 20210611 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |