CN112978702A - Preparation method and application of carbon-coated sodium vanadium phosphate - Google Patents
Preparation method and application of carbon-coated sodium vanadium phosphate Download PDFInfo
- Publication number
- CN112978702A CN112978702A CN201911276157.6A CN201911276157A CN112978702A CN 112978702 A CN112978702 A CN 112978702A CN 201911276157 A CN201911276157 A CN 201911276157A CN 112978702 A CN112978702 A CN 112978702A
- Authority
- CN
- China
- Prior art keywords
- carbon
- vanadium phosphate
- coated sodium
- preparation
- vanadium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 49
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 15
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000001354 calcination Methods 0.000 claims abstract description 14
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 14
- 239000011574 phosphorus Substances 0.000 claims abstract description 14
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 13
- 239000001509 sodium citrate Substances 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 8
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims description 12
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 4
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 4
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 239000013078 crystal Substances 0.000 claims description 2
- 235000011007 phosphoric acid Nutrition 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 239000002228 NASICON Substances 0.000 claims 1
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 claims 1
- 238000010668 complexation reaction Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 12
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 abstract description 10
- 229910001415 sodium ion Inorganic materials 0.000 abstract description 10
- 230000000536 complexating effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- 239000012300 argon atmosphere Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 239000008139 complexing agent Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 229910021550 Vanadium Chloride Inorganic materials 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000012863 analytical testing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000011127 sodium aluminium sulphate Nutrition 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- -1 vanadium oxalate hydrate Chemical compound 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/45—Phosphates containing plural metal, or metal and ammonium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
本申请公开了一种碳包覆磷酸矾钠的制备方法，包括以下步骤：a)将含有磷源、钒源和柠檬酸钠的水溶液，经加热络合，得到凝胶；b)将所述凝胶干燥，得到前驱体；c)将所述前驱体研磨后，非活性气氛下煅烧，得到所述碳包覆磷酸矾钠。该碳包覆磷酸钒钠的制备工艺简单，原料组成精简，适合大批量生产。同时，该碳包覆磷酸钒钠材料应用于钠离子电池正极中，可以表现出优异的长循环性能和倍率性能。The present application discloses a preparation method of carbon-coated sodium vanadium phosphate, comprising the following steps: a) heating and complexing an aqueous solution containing a phosphorus source, a vanadium source and sodium citrate to obtain a gel; b) mixing the The gel is dried to obtain a precursor; c) after grinding the precursor, calcining in an inactive atmosphere to obtain the carbon-coated sodium vanadium phosphate. The preparation process of the carbon-coated sodium vanadium phosphate is simple, the composition of raw materials is simplified, and it is suitable for mass production. At the same time, the carbon-coated sodium vanadium phosphate material can be used in the cathode of sodium-ion battery, and can exhibit excellent long-cycle performance and rate performance.
Description
Technical Field
The invention relates to the field of sodium ion batteries, and in particular relates to a preparation method of a carbon-coated vanadium sodium phosphate positive electrode material of a sodium ion battery.
Background
Due to the low cost and wide availability of sodium resources, and the similarities between sodium ion batteries and lithium ion batteries in terms of chemical properties, intercalation characteristics and the like, battery technologies based on sodium ion batteries are rapidly developed and become one of the most promising alternatives for lithium ion batteries.
However, sodium ion batteries also have certain disadvantages, the most important of which is the relatively low energy density. Sodium has a greater relative atomic mass (Mw 23.0g mol) than lithium-1) And higher redox potential (psi Na)+/Na＝-2.71V vs.SHE；ψLi+-3.04V vs. she). In order to improve the energy density of the battery, obtaining a proper cathode material is the key point for improving the specific capacity.
Among all positive electrode materials for sodium ion batteries, polyanionic phosphates having NASICON (Na super ion conductor) structure are due to their rapid Na during electrochemical charge and discharge+Diffusion and stable structures are of great interest. Among them, sodium vanadium phosphate has a high specific capacity (117.6mAh/g) and a high voltage plateau (-3.4V), and is considered to be one of the most promising positive electrode materials for sodium ion batteries.
However, pure sodium vanadium phosphate has significant drawbacks, such as poor electronic conductivity, which severely hampers its practical application.
Disclosure of Invention
According to one aspect of the application, the preparation method of the carbon-coated sodium vanadium phosphate is provided, the carbon-coated sodium vanadium phosphate with good crystallinity and excellent electrochemical performance is obtained, and the preparation method is simple and is easy for large-scale production.
The preparation method of the carbon-coated sodium alum phosphate is characterized by comprising the following steps:
a) heating and complexing an aqueous solution containing a phosphorus source, a vanadium source and sodium citrate to obtain gel;
b) drying the gel to obtain a precursor;
c) and grinding the precursor, and calcining in an inactive atmosphere to obtain the carbon-coated sodium vanadium phosphate.
Optionally, the inert atmosphere is selected from at least one of nitrogen, helium, neon, argon. The non-reactive atmosphere acts as a protective atmosphere.
Optionally, the sodium citrate simultaneously functions as a sodium source, a carbon source, a complexing agent, and a reducing agent, without using other additional carbon sources, complexing agents, and reducing agents or reducing atmospheres.
Optionally, the carbon-coated sodium phosphate has a NASICON structure;
the sodium vanadium phosphate in the carbon-coated sodium vanadium phosphate is a crystal.
Optionally, the carbon-coated sodium vanadium phosphate has a 3D porous structure.
Optionally, the pore diameter of the pore structure in the carbon-coated sodium vanadium phosphate is 10-800 nm.
Optionally, in step a), the phosphorus source comprises at least one of diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and phosphoric acid.
Optionally, in step a), the vanadium source includes at least one of ammonium metavanadate, vanadium pentoxide, vanadium oxalate hydrate, and vanadium chloride.
Optionally, in the step a), the molar ratio of the sodium citrate to the vanadium source to the phosphorus source in the aqueous solution containing the phosphorus source, the vanadium source and the sodium citrate is 3.0-3.6: 2: 3.
optionally, in the step a), the molar ratio of the sodium citrate to the vanadium source to the phosphorus source in the aqueous solution containing the phosphorus source, the vanadium source and the sodium citrate is 3.0-3.2: 2: 3.
optionally, in the aqueous solution containing the phosphorus source, the vanadium source and the sodium citrate in the step a), the content of water may be selected according to actual conditions, and the phosphorus source, the vanadium source and the sodium citrate may be dissolved.
Optionally, in step a), the heat complexing conditions are: stirring at 60-100 ℃; the stirring speed is 300-1000 rpm.
As an embodiment, the step a) includes: and (3) using sodium citrate to match a phosphorus source and a vanadium source, and heating and stirring in an oil bath in an aqueous solution to obtain the gel.
Optionally, the oil bath temperature is 60-180 ℃, and the stirring speed is 300-1000 rpm.
Optionally, in the step b), the drying temperature is 100-180 ℃.
Alternatively, in step c), the calcination is a two-stage calcination; pre-burning for the first period at 350-450 ℃ for 4-8 hours; and the second stage of calcination is carried out at the temperature of 750-950 ℃ for 6-12 hours.
Optionally, in step c), the upper limit of the temperature of the first stage pre-firing is selected from 400 ℃ or 450 ℃; the lower limit is selected from 350 ℃ or 450 ℃.
Optionally, in step c), the upper limit of the first burn-in period is selected from 6h or 8 h; the lower limit is selected from 4h or 6 h.
Optionally, in step c), the upper limit of the temperature of the second stage calcination is selected from 750 ℃, 800 ℃, 850 ℃, 900 ℃ or 950 ℃; the lower limit is selected from 750 deg.C, 800 deg.C, 850 deg.C or 900 deg.C.
Alternatively, in step c), the upper limit of the time for the second stage calcination is selected from 6h, 8h, 10h or 12 h; the lower limit is selected from 6h, 8h or 10 h.
In one embodiment, in step c), the atmosphere for protecting the calcination is argon, and a reducing atmosphere such as hydrogen is not required. The calcination mode is divided into two sections, pre-sintering is firstly carried out at the temperature of 350-450 ℃ for 4-8 hours, and then calcination is carried out at the temperature of 750-950 ℃ for 6-12 hours.
According to another aspect of the present application, there is provided a use of the carbon-coated sodium vanadium phosphate prepared according to any one of the above-described preparation methods in a battery.
Optionally, the battery is a sodium ion battery.
The beneficial effects that this application can produce include:
the preparation method provided by the application is simple, the raw material composition is simple, an additional carbon source, a complexing agent and a reducing agent or reducing atmosphere are not needed, and the prepared carbon-coated sodium vanadium phosphate has good crystallinity, excellent cycle performance and rate capability.
Drawings
Fig. 1 is a scanning electron microscope image of carbon-coated sodium vanadium phosphate prepared in example 1 of the present invention.
Fig. 2 is an XRD pattern of carbon-coated sodium vanadium phosphate prepared in example 1 of the present invention.
Fig. 3 is a graph of the cycle performance of the carbon-coated sodium vanadium phosphate half-cell prepared in example 1 of the present invention at a current density of 1C, wherein the voltage window is 2.5-3.8V, and 1C is 117.6 mAh/g.
Fig. 4 is a rate cycle curve of the carbon-coated sodium vanadium phosphate half-cell prepared in example 1 of the present invention, wherein the voltage window is 2.5-3.8V, and 1C is 117.6 mAh/g.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
The analysis method in the examples of the present application is as follows:
the analysis and test of the sample morphology were carried out using scanning electron microscopy (SEM, JSM-7800F).
Analytical testing of the composition of the crystalline phases of the samples was carried out using an X-ray diffractometer (XRD, X' pert Pro).
Constant current charge/discharge tests were performed using a battery system (blue electronic, inc., wuhan) using the LAND CT 2001A. .
Example 1
0.02mol of ammonium metavanadate is added into 40mL of deionized water, and the mixture is heated and stirred for 1h at 80 ℃. Then, 0.03mol of ammonium dihydrogen phosphate and 0.01mol of sodium citrate dihydrate were added thereto, and stirred at 80 ℃ for 2 hours at a stirring speed of 300 rpm. Then, the temperature was raised to 120 ℃ and the stirring speed was 500rpm, and the mixture was stirred until the solution became gel-like. Then the mixture is moved into an oven and dried at 120 ℃. And uniformly grinding the dried precursor. Then, the sample is subjected to heat treatment by using an argon atmosphere, and the sample is treated by using a sectional heating mode. Heating to 350 deg.C, holding for 4 hr, heating to 800 deg.C, and holding for 8 hr. Obtaining the carbon-coated sodium vanadium phosphate product.
As can be seen from a Scanning Electron Microscope (SEM) image shown in the attached figure 1, the prepared carbon-coated sodium vanadium phosphate has a 3D porous structure, and the pore diameter of the porous structure is 10-800 nm. As can be seen from the X-ray diffraction pattern (XRD) of FIG. 2, the prepared carbon-coated sodium vanadium phosphate has a NASICON structure and has good crystallinity.
The carbon-coated sodium vanadium phosphate prepared in the embodiment is used as the positive electrode of the sodium ion battery, and forms a half battery with the sodium metal negative electrode, and the electrochemical performance of the prepared carbon-coated sodium vanadium phosphate is tested. As can be seen from the attached figure 3, under the current density of 1C, the first discharge specific capacity of the prepared carbon-coated sodium vanadium phosphate is 92.8mAh/g, after 500 cycles, the capacity is still 85.8mAh/g, the capacity retention rate is 92.46%, and the carbon-coated sodium vanadium phosphate has excellent cycle stability. The rate test is carried out on the prepared carbon-coated sodium vanadium phosphate half-cell, and the specific discharge capacity of the cell under the current densities of 1C, 2C, 5C, 10C, 20C, 30C and 50C is 91.01, 90.38, 86.34, 82.19, 76.83, 72.31 and 68.07mAh/g respectively as can also be seen in the attached figure 4. The prepared carbon-coated vanadium sodium phosphate has excellent rate performance.
Example 2
0.2mol of ammonium metavanadate is added into 100mL of deionized water, and the mixture is heated and stirred for 1h at 80 ℃. Then, 0.3mol of ammonium dihydrogen phosphate and 0.12mol of sodium citrate dihydrate were added and stirred at 80 ℃ for 2 hours at a stirring speed of 500 rpm. Then, the temperature was raised to 120 ℃ and the stirring speed was 500rpm, and the mixture was stirred until the solution became gel-like. Then the mixture is moved into an oven and dried at 120 ℃. And uniformly grinding the dried precursor. Then, the sample is subjected to heat treatment by using an argon atmosphere, and the sample is treated by using a sectional heating mode. Heating to 350 deg.C, holding for 4 hr, heating to 800 deg.C, and holding for 8 hr. Obtaining the carbon-coated sodium vanadium phosphate product. SEM, XRD and electrical property measurements of the product prepared in example 2 were similar to those of the sample prepared in example 1.
Example 3
0.1mol of vanadium pentoxide is added into 100mL of deionized water, and the mixture is heated and stirred for 1h at 90 ℃. Then, 0.3mol of diammonium hydrogen phosphate and 0.12mol of sodium citrate dihydrate were added and stirred at 90 ℃ for 2 hours at a stirring speed of 500 rpm. Then, the temperature was raised to 120 ℃ and the stirring speed was 500rpm, and the mixture was stirred until the solution became gel-like. Then the mixture is moved into an oven and dried at 120 ℃. And uniformly grinding the dried precursor. Then, the sample is subjected to heat treatment by using an argon atmosphere, and the sample is treated by using a sectional heating mode. Heating to 400 deg.C, holding for 4 hr, heating to 850 deg.C, and holding for 8 hr. Obtaining the carbon-coated sodium vanadium phosphate product.
SEM, XRD and electrical property measurements of the product prepared in example 3 were all similar to those of the sample prepared in example 1.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911276157.6A CN112978702A (en) | 2019-12-12 | 2019-12-12 | Preparation method and application of carbon-coated sodium vanadium phosphate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911276157.6A CN112978702A (en) | 2019-12-12 | 2019-12-12 | Preparation method and application of carbon-coated sodium vanadium phosphate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112978702A true CN112978702A (en) | 2021-06-18 |
Family
ID=76331774
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911276157.6A Pending CN112978702A (en) | 2019-12-12 | 2019-12-12 | Preparation method and application of carbon-coated sodium vanadium phosphate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112978702A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526485A (en) * | 2021-09-15 | 2021-10-22 | 中南大学 | A kind of porous sodium vanadium fluorophosphate composite material controlled by carbon quantum dots and its preparation method and application |
| CN114300660A (en) * | 2021-12-23 | 2022-04-08 | 大连博融新材料有限公司 | Polypyrrole coated carbon-doped sodium vanadium phosphate positive electrode material, and preparation method and application thereof |
| CN115275194A (en) * | 2022-01-28 | 2022-11-01 | 上海华起睿智新能源科技有限公司 | Preparation method of porous conductive framework sodium-ion battery positive electrode material with controllable grain size |
| CN115881906A (en) * | 2022-09-27 | 2023-03-31 | 惠州亿纬锂能股份有限公司 | Positive electrode active material, preparation method thereof and sodium ion battery |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106058202A (en) * | 2016-07-29 | 2016-10-26 | 华南理工大学 | Carbon-coated metal ion-doped sodium vanadium phosphate composite cathode material prepared by freeze drying method, as well as preparation method and application thereof |
| CN106328911A (en) * | 2016-11-30 | 2017-01-11 | 合肥工业大学 | Material with mixture of ions with sodium vanadium phosphate cathode material coated by carbon and preparing method thereof |
| CN107845796A (en) * | 2017-10-27 | 2018-03-27 | 东北大学秦皇岛分校 | A kind of carbon doping vanadium phosphate sodium positive electrode and its preparation method and application |
| EP3310937A1 (en) * | 2015-06-19 | 2018-04-25 | Centre National De La Recherche Scientifique | Method for production of sodium-based electroactive material by ball milling while using metallic sodium |
| CN108365218A (en) * | 2018-02-28 | 2018-08-03 | 广东工业大学 | A kind of simple preparation method of three-dimensional porous structure vanadium phosphate sodium composite positive pole |
| CN108417815A (en) * | 2018-04-26 | 2018-08-17 | 浙江大学 | A carbon-coated sodium vanadium phosphate three-dimensional mesoporous nanomaterial and its preparation method and application |
-
2019
- 2019-12-12 CN CN201911276157.6A patent/CN112978702A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3310937A1 (en) * | 2015-06-19 | 2018-04-25 | Centre National De La Recherche Scientifique | Method for production of sodium-based electroactive material by ball milling while using metallic sodium |
| CN106058202A (en) * | 2016-07-29 | 2016-10-26 | 华南理工大学 | Carbon-coated metal ion-doped sodium vanadium phosphate composite cathode material prepared by freeze drying method, as well as preparation method and application thereof |
| CN106328911A (en) * | 2016-11-30 | 2017-01-11 | 合肥工业大学 | Material with mixture of ions with sodium vanadium phosphate cathode material coated by carbon and preparing method thereof |
| CN107845796A (en) * | 2017-10-27 | 2018-03-27 | 东北大学秦皇岛分校 | A kind of carbon doping vanadium phosphate sodium positive electrode and its preparation method and application |
| CN108365218A (en) * | 2018-02-28 | 2018-08-03 | 广东工业大学 | A kind of simple preparation method of three-dimensional porous structure vanadium phosphate sodium composite positive pole |
| CN108417815A (en) * | 2018-04-26 | 2018-08-17 | 浙江大学 | A carbon-coated sodium vanadium phosphate three-dimensional mesoporous nanomaterial and its preparation method and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113526485A (en) * | 2021-09-15 | 2021-10-22 | 中南大学 | A kind of porous sodium vanadium fluorophosphate composite material controlled by carbon quantum dots and its preparation method and application |
| CN113526485B (en) * | 2021-09-15 | 2021-12-28 | 中南大学 | A kind of porous sodium vanadium fluorophosphate composite material controlled by carbon quantum dots and its preparation method and application |
| CN114300660A (en) * | 2021-12-23 | 2022-04-08 | 大连博融新材料有限公司 | Polypyrrole coated carbon-doped sodium vanadium phosphate positive electrode material, and preparation method and application thereof |
| CN115275194A (en) * | 2022-01-28 | 2022-11-01 | 上海华起睿智新能源科技有限公司 | Preparation method of porous conductive framework sodium-ion battery positive electrode material with controllable grain size |
| CN115881906A (en) * | 2022-09-27 | 2023-03-31 | 惠州亿纬锂能股份有限公司 | Positive electrode active material, preparation method thereof and sodium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cai et al. | Boosting the potassium-ion storage performance enabled by engineering of hierarchical MoSSe nanosheets modified with carbon on porous carbon sphere | |
| Xing et al. | Novel KV-Fe Prussian blue analogues nanocubes for high-performance aqueous ammonium ion batteries | |
| Bian et al. | A novel process to recycle spent LiFePO4 for synthesizing LiFePO4/C hierarchical microflowers | |
| CN112978702A (en) | Preparation method and application of carbon-coated sodium vanadium phosphate | |
| CN107316979B (en) | Molybdenum disulfide/carbon fiber network flexible electrode and preparation method and application thereof | |
| Zou et al. | Mixed-carbon-coated LiMn0. 4Fe0. 6PO4 nanopowders with excellent high rate and low temperature performances for lithium-ion batteries | |
| Liu et al. | Carbon coated Li3VO4 microsphere: Ultrafast solvothermal synthesis and excellent performance as lithium-ion battery anode | |
| KR101673300B1 (en) | Method for preparing polyanion-carbon nanofibers composites applicable to the cathode of sodium ion batteries through electrospinning | |
| Lu et al. | In situ electrochemically transforming VN/V2O3 heterostructure to highly reversible V2NO for excellent zinc ion storage | |
| Wang et al. | Chrysanthemum-like TiO 2 nanostructures with exceptional reversible capacity and high coulombic efficiency for lithium storage | |
| Feng et al. | Designed synthesis of a unique single-crystal Fe-doped LiNiPO 4 nanomesh as an enhanced cathode for lithium ion batteries | |
| Örnek | Positive effects of a particular type of microwave-assisted methodology on the electrochemical properties of olivine LiMPO4 (M= Fe, Co and Ni) cathode materials | |
| Liu et al. | Multifunctional sulfate-assistant synthesis of seaweed-like N, S-doped carbons as high-performance anodes for K-ion capacitors | |
| WO2015007169A1 (en) | Preparation method for positive electrode material of lithium-ion battery | |
| CN109775680B (en) | Sodium vanadium phosphate nanosheet and preparation method and application thereof | |
| WO2025102446A1 (en) | Lithium manganese iron phosphate material and preparation method therefor, positive electrode sheet, and lithium ion battery | |
| Wang et al. | High rate and cyclic performance of Na3–2 x Mg x V2 (PO4) 3/C cathode for sodium-ion batteries | |
| CN108565131B (en) | Method for preparing nitrogen-doped graphitized carbon | |
| Ren et al. | Effect of solvent on the crystal phase, morphology, and sodium storage performance of FeSe 2 | |
| Xiao et al. | Sponge-like graphene cubes: S reservoir with large polysulfide diffusion resistance for lithium-sulfur batteries | |
| Zhou et al. | Manipulating amorphous and crystalline hybridization of Na3V2 (PO4) 3/C for enhancing sodium-ion diffusion kinetics | |
| Guo et al. | Stabilized covalent interfacial coupling design of Li 3 V 2 (PO 4) 3 with carbon framework for boosting lithium storage kinetics | |
| KR102559521B1 (en) | Vanadium Carbide Nanowire and Preparing Method thereof | |
| Sun et al. | Carbon-coated LiFePO 4 synthesized by a simple solvothermal method | |
| Zhao et al. | Capacitive contribution to lithium storage capacity in porous MoO3 films |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210618 |