CN114094066A - Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery - Google Patents
Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery Download PDFInfo
- Publication number
- CN114094066A CN114094066A CN202111279788.0A CN202111279788A CN114094066A CN 114094066 A CN114094066 A CN 114094066A CN 202111279788 A CN202111279788 A CN 202111279788A CN 114094066 A CN114094066 A CN 114094066A
- Authority
- CN
- China
- Prior art keywords
- sodium
- vanadium
- cathode material
- fluorophosphate
- carbon cathode
- 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 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- CHQMXRZLCYKOFO-UHFFFAOYSA-H P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F Chemical compound P(=O)([O-])([O-])F.[V+5].[Na+].P(=O)([O-])([O-])F.P(=O)([O-])([O-])F CHQMXRZLCYKOFO-UHFFFAOYSA-H 0.000 title claims abstract description 42
- 239000010406 cathode material Substances 0.000 title claims abstract description 30
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 17
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 22
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical compound OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims abstract description 19
- 150000007524 organic acids Chemical class 0.000 claims abstract description 19
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 18
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 17
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052786 argon Inorganic materials 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 15
- 238000005245 sintering Methods 0.000 claims abstract description 14
- 239000011734 sodium Substances 0.000 claims abstract description 14
- 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 claims abstract description 13
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 238000001816 cooling Methods 0.000 claims abstract description 12
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 9
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000005303 weighing Methods 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 8
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical group [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 claims description 4
- 229940120146 EDTMP Drugs 0.000 claims description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 4
- 229930003268 Vitamin C Natural products 0.000 claims description 4
- KIDJHPQACZGFTI-UHFFFAOYSA-N [6-[bis(phosphonomethyl)amino]hexyl-(phosphonomethyl)amino]methylphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCCCCCN(CP(O)(O)=O)CP(O)(O)=O KIDJHPQACZGFTI-UHFFFAOYSA-N 0.000 claims description 4
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 claims description 4
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 4
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008103 glucose Substances 0.000 claims description 4
- 235000019154 vitamin C Nutrition 0.000 claims description 4
- 239000011718 vitamin C Substances 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- 238000003786 synthesis reaction Methods 0.000 abstract description 7
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000010452 phosphate Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000011056 performance test Methods 0.000 description 6
- 239000002131 composite material Substances 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000002228 NASICON Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000010416 ion conductor Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910003481 amorphous carbon Inorganic materials 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000001308 synthesis method Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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
- H01M4/582—Halogenides
-
- 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
- H01M4/36—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
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a vanadium sodium fluorophosphate/carbon cathode material, a synthetic method thereof and a sodium-ion battery, which comprises the following steps: weighing sodium fluoride, a vanadium source, organic phosphonic acid and organic acid according to the molar ratio of sodium to vanadium to phosphonic acid group to organic acid of 3:2:2, adding a proper amount of deionized water into the organic acid, the vanadium source, the organic phosphonic acid and the sodium fluoride, stirring and dissolving the mixture, stirring and heating the obtained solution to evaporate the solution to obtain gel-like solid, and drying the obtained gel-like solid; and grinding the obtained solid, presintering under the protection of argon, naturally cooling, taking out, grinding again, sintering under the protection of argon, and naturally cooling to obtain the product sodium-ion battery anode material sodium vanadium fluorophosphate/carbon. According to the invention, organic phosphonic acid and organic sodium are used as phosphate radicals and carbon sources required by synthesis of sodium vanadium fluorophosphate/carbon, the types of raw materials are reduced, the synthesis process is simplified, and the obtained electrode material has high specific capacity, good rate performance and long cycle life.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a vanadium sodium fluorophosphate/carbon cathode material, a synthetic method thereof and a sodium ion battery.
Background
Sodium ion batteries are considered to be large-scale storage batteries because of their abundant sodium resources, low cost, and similar energy storage principle to lithium ion batteriesOne of ideal choices of energy fields. The development of advanced positive electrode materials for sodium ion batteries has become the key to the practical application of the positive electrode materials. Sodium vanadium fluorophosphate (Na)3V2(PO4)2F3) The material has higher working voltage, higher theoretical specific capacity and larger sodium ion transmission channel, and is considered to be one of the ideal choices of the positive electrode material of the sodium ion battery. However, the materials have low intrinsic electronic conductivity and insufficient cycle performance. Carbon coating is one of the effective means for modifying such materials. However, the current preparation method of the carbon-coated vanadium sodium fluorophosphate composite cathode material has the problems of various raw material types, complex process flow and the like, and the sodium storage performance of the obtained vanadium sodium fluorophosphate/carbon composite material is to be further improved. Therefore, the development of an advanced method for preparing the sodium vanadium fluorophosphate/carbon composite material has important significance for the scale application of the sodium vanadium fluorophosphate/carbon composite material in the aspect of sodium ion batteries.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a sodium vanadium fluorophosphate/carbon anode material and a synthesis method thereof, which are used for efficiently preparing a sodium vanadium fluorophosphate/carbon composite material, organic phosphonic acid and organic acid are used as phosphate radicals and carbon sources required by the synthesis of the sodium vanadium fluorophosphate/carbon, so that the variety of raw materials is reduced, the synthesis process is simplified, meanwhile, the electrode material obtained by the method has high specific capacity, good rate capability and long cycle life, and the problems of complex preparation method, poor performance and the like of the sodium vanadium fluorophosphate anode material of a sodium ion battery are solved.
The invention also provides a sodium-ion battery containing the sodium vanadium fluorophosphate/carbon cathode material.
The invention is realized by the following technical scheme:
a method for synthesizing a sodium vanadium fluorophosphate/carbon cathode material comprises the following steps:
s1, weighing sodium fluoride, a vanadium source, organic phosphonic acid and organic acid according to the molar ratio of sodium to vanadium to phosphonic acid group to organic acid of 3:2:2:2, adding deionized water into the organic acid, the vanadium source, the organic phosphonic acid and the sodium fluoride, stirring and dissolving the mixture, heating, stirring and evaporating the obtained solution to obtain a gel-like solid, and drying the obtained gel-like solid;
and S2, grinding the solid obtained in the step S1, presintering under the protection of argon, naturally cooling, taking out, grinding again, sintering under the protection of argon, and naturally cooling to obtain the product of the sodium vanadium fluorophosphate/carbon cathode material.
In the above scheme, the organic phosphonic acid in step S1 is aminotrimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, or hexamethylenediamine tetramethylene phosphonic acid.
In the above scheme, the organic acid in step S1 is citric acid, glucose or vitamin C.
In the foregoing scheme, the vanadium source in step S1 is ammonium metavanadate or vanadium pentoxide.
In the above scheme, the solution in step S1 is heated and stirred at 80-100 ℃ until the water is evaporated to dryness.
In the above embodiment, the drying conditions in step S1 are as follows: drying the mixture in an oven at the temperature of between 80 and 100 ℃ for 5 to 12 hours.
In the above scheme, the conditions for the pre-sintering in step S2 are: and pre-sintering for 4-8 h at the temperature of 300-400 ℃ under the protection of argon or nitrogen.
In the above scheme, the sintering conditions in step S2 are: sintering for 8-12 h at 650-750 ℃ under the protection of argon.
A sodium vanadium fluorophosphate/carbon cathode material is obtained according to a synthesis method of the sodium vanadium fluorophosphate/carbon cathode material.
A sodium ion battery comprising the sodium vanadium fluorophosphate/carbon cathode material.
Compared with the prior art, the invention has the beneficial effects that:
the sodium vanadium fluorophosphate/carbon anode material for the sodium-ion battery has the advantages that the molar ratio of sodium to vanadium to phosphonic acid groups to organic acid is 3:2:2:2, and the selected organic phosphonic acid contains phosphonic acid groups and carbon-containing groups, so that the sodium-ion battery anode material has multifunctional characteristics, namely, phosphate groups required by synthesis of sodium vanadium fluorophosphate/carbon are provided, and amorphous carbon for coating is formed; the selected organic acid has a carbon-containing group and a reducing agent, so that the organic acid has multifunctional characteristics, namely, the organic acid not only forms amorphous carbon for coating, but also can be used as a reducing agent to reduce vanadium with a valence of +5 to vanadium with a valence of +4 at low temperature; the whole synthesis process has no wastewater, the synthesis process is simple and efficient, and the electrode material obtained by the method has high specific capacity, good rate performance and long cycle life.
Drawings
FIG. 1 is an XRD pattern of a sample prepared according to example 1 of the present invention.
FIG. 2 is an SEM photograph of a sample prepared in example 1 of the present invention.
Fig. 3(a) is a first charge and discharge curve at a rate of 1C for a sample prepared in example 1 of the present invention; fig. 3(b) is a graph of its cycle performance at 5C magnification.
FIG. 4 is a graph of rate capability of samples prepared in example 1 of the present invention.
Fig. 5 is an XRD pattern of a sample prepared in example 2 of the present invention.
FIG. 6 is an SEM photograph of a sample prepared in example 2 of the present invention.
Fig. 7(a) is a first charge and discharge curve at a rate of 1C for a sample prepared in example 2 of the present invention; fig. 7(b) is a graph of its cycle performance at 5C magnification.
FIG. 8 is a graph of rate capability for samples prepared in example 2 of the present invention.
Fig. 9 is an XRD pattern of a sample prepared in example 3 of the present invention.
FIG. 10 is an SEM photograph of a sample prepared in example 3 of the present invention.
Fig. 11(a) is a first charge and discharge curve at a rate of 1C for a sample prepared in example 3 of the present invention; fig. 11(b) is a graph of its cycle performance at 5C magnification.
FIG. 12 is a graph of rate capability for samples prepared in example 3 of the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, but the scope of the invention is not limited thereto.
Example 1
A method for synthesizing a sodium vanadium fluorophosphate/carbon cathode material comprises the following steps:
step S1, weighing sodium fluoride, vanadium pentoxide, aminotrimethylene phosphonic acid and citric acid according to the molar ratio of sodium to vanadium to phosphonic acid group to organic acid of 3:2:2:2, adding a proper amount of deionized water into aminotrimethylene phosphonic acid and citric acid, stirring and dissolving, then adding vanadium pentoxide, stirring and dissolving to obtain a clear solution. Heating and stirring the solution at 80 ℃, putting the solution into an oven when the water is evaporated to dryness and the sample is gelatinous, and drying the solution for 12 hours at 80 ℃;
and step S2, grinding the obtained solid, and presintering for 5 hours at 300 ℃ under the protection of argon. Naturally cooling to room temperature, taking out and grinding again, sintering for 8 hours at 700 ℃ under the protection of argon, and naturally cooling to obtain the product of the sodium vanadium fluorophosphate/carbon cathode material.
FIG. 1 is an XRD pattern of the product prepared in this example, showing that the product is a single ordered sodium super ion conductor (NASICON) structure without any impurity phase. According to the SEM image shown in FIG. 2, the resulting material exhibited a porous morphology.
Example 2
A method for synthesizing a sodium vanadium fluorophosphate/carbon cathode material comprises the following steps:
and step S1, weighing sodium fluoride, ammonium metavanadate, ethylenediamine tetramethylene phosphonic acid and glucose according to the molar ratio of sodium to vanadium to phosphonic acid group to organic acid of 3:2:2:2, adding a proper amount of deionized water into ethylenediamine tetramethylene phosphonic acid and glucose, stirring and dissolving, then adding ammonium metavanadate, stirring and dissolving to obtain a clear solution. Heating and stirring the solution at 100 ℃, putting the solution into an oven when the water is evaporated to dryness and the sample is gelatinous, and drying the solution for 5 hours at 100 ℃.
And step S2, grinding the obtained solid, and presintering for 6 hours at 400 ℃ under the protection of argon. Naturally cooling to room temperature, taking out and grinding again, sintering for 12h at 750 ℃ under the protection of argon, and naturally cooling to obtain the product of the sodium vanadium fluorophosphate/carbon cathode material.
FIG. 5 is an XRD pattern of the product made in this example, showing that the product is a single ordered sodium super ion conductor (NASICON) structure without any hetero-phase. According to the SEM image shown in FIG. 6, the resulting material exhibited a porous morphology.
Example 3
A method for synthesizing a sodium vanadium fluorophosphate/carbon cathode material comprises the following steps:
and step S1, weighing sodium fluoride, ammonium metavanadate, hexamethylenediamine tetramethylene phosphonic acid and vitamin C according to the molar ratio of sodium to vanadium to phosphonic acid group to organic acid of 3:2:2:2, adding a proper amount of deionized water into the hexamethylenediamine tetramethylene phosphonic acid and the vitamin C, stirring and dissolving, then adding ammonium metavanadate, stirring and dissolving to obtain a clear solution. Heating and stirring the solution at 90 ℃, putting the solution into an oven when the water is evaporated to dryness and the sample is gelatinous, and drying the solution for 8 hours at 90 ℃.
And step S2, grinding the obtained solid, and presintering for 4 hours at 350 ℃ under the protection of argon. Naturally cooling to room temperature, taking out and grinding again, sintering for 10 hours at 650 ℃ under the protection of argon, and naturally cooling to obtain the product of the sodium vanadium fluorophosphate/carbon cathode material.
FIG. 9 is an XRD pattern of the product made in this example, showing that the product is a single ordered sodium super ion conductor (NASICON) structure without any impurity phase. According to the SEM image shown in FIG. 10, the resulting material exhibited a particulate morphology.
The results of testing the charge-discharge specific capacity and the cycle performance of the experimental button-type half cell assembled by the products obtained in the embodiments 1, 2 and 3 are shown in table 1, and it can be seen that the electrode material obtained by the method of the present invention has high specific capacity, good rate performance and long cycle life.
The product obtained in example 1 was assembled into an experimental button half cell to measure its specific charge-discharge capacity and cycle performance, the result is shown in fig. 3, charge and discharge were carried out at a rate of 1C, the first charge-discharge curve is shown in fig. 3(a), and the specific discharge capacity of the first loop was about 105mAh g-1. The cycle performance test was carried out at a rate of 5C, and the result is shown in FIG. 3(b), where the first-turn specific discharge capacity was 96.7mAh g-1The capacity retention after 500 cycles was 92.1%. The rate performance test is carried out under different rates, and the result is shown in figure 4, and the material shows good rate performance.
The product obtained in example 2 was assembled into an experimental button half cell to measure its charge-discharge specific capacity and cycle performance, and the result is shown in fig. 7, where charge-discharge was performed at a rate of 1C, and the first charge-discharge curveAs shown in FIG. 7(a), the first-turn specific discharge capacity was about 110mAh g-1. The cycle performance test was carried out at a rate of 5C, and the result is shown in FIG. 7(b), where the first-turn specific discharge capacity was 93.5mAh g-1After 1000 cycles, the capacity retention rate was 87.8%. The rate performance test is carried out under different rates, and the result is shown in figure 8, and the material shows good rate performance.
The product obtained in example 3 was assembled into an experimental button half cell to measure its specific charge-discharge capacity and cycle performance, the result is shown in fig. 11, charge and discharge were carried out at a rate of 1C, the first charge-discharge curve is shown in fig. 11(a), and the specific discharge capacity of the first loop was about 103mAh g-1. The result of the cycle performance test at a rate of 5C is shown in FIG. 11(b), and the specific discharge capacity of the first turn is 92.4mAh g-1After 800 cycles, the capacity retention rate was 91.9%. The rate performance test is carried out under different rates, and the result is shown in figure 12, and the material shows good rate performance.
TABLE 1 specific charge-discharge capacity and cyclability
| Specific discharge capacity of first loop under multiplying power of 1C | Specific discharge capacity of first loop under 5C multiplying power | Number of cycles | Capacity retention rate | |
| Example 1 | 105mAh g-1 | 96.7 |
500 times (times) | 92.1％ |
| Example 2 | 110mAh g-1 | 93.5 |
1000 times (one time) | 87.8％ |
| Example 3 | 103mAh g-1 | 92.4 |
800 times | 91.9％ |
It should be understood that although the present description has been described in terms of various embodiments, not every embodiment includes only a single embodiment, and such description is for clarity purposes only, and those skilled in the art will recognize that the embodiments described herein may be combined as suitable to form other embodiments, as will be appreciated by those skilled in the art.
The above-listed detailed description is only a specific description of a possible embodiment of the present invention, and they are not intended to limit the scope of the present invention, and equivalent embodiments or modifications made without departing from the technical spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. A method for synthesizing a sodium vanadium fluorophosphate/carbon cathode material is characterized by comprising the following steps of:
s1, weighing sodium fluoride, a vanadium source, organic phosphonic acid and organic acid according to the molar ratio of sodium to vanadium to phosphonic acid group to organic acid of 3:2:2:2, adding deionized water into the organic acid, the vanadium source, the organic phosphonic acid and the sodium fluoride, stirring and dissolving the mixture, heating, stirring and evaporating the obtained solution to obtain a gel-like solid, and drying the obtained gel-like solid;
and S2, grinding the solid obtained in the step S1, presintering under the protection of argon, naturally cooling, taking out, grinding again, sintering under the protection of argon, and naturally cooling to obtain the product of the sodium vanadium fluorophosphate/carbon cathode material.
2. The method for synthesizing a vanadium sodium fluorophosphate/carbon cathode material according to claim 1, wherein the organic phosphonic acid in step S1 is aminotrimethylene phosphonic acid, ethylenediamine tetramethylene phosphonic acid, or hexamethylenediamine tetramethylene phosphonic acid.
3. The method for synthesizing the sodium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein the organic acid in the step S1 is citric acid, glucose or vitamin C.
4. The method for synthesizing sodium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein in the step S1, the vanadium source is ammonium metavanadate or vanadium pentoxide.
5. The method for synthesizing the sodium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein the solution in the step S1 is heated and stirred at 80-100 ℃ until the water is evaporated to dryness.
6. The method for synthesizing a sodium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein the conditions of the drying treatment in step S1 are as follows: drying the mixture in an oven at the temperature of between 80 and 100 ℃ for 5 to 12 hours.
7. The method for synthesizing a sodium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein the pre-sintering conditions in the step S2 are as follows: and pre-sintering for 4-8 h at the temperature of 300-400 ℃ under the protection of argon.
8. The method for synthesizing a sodium vanadium fluorophosphate/carbon cathode material according to claim 1, wherein the sintering conditions in the step S2 are as follows: sintering for 8-12 h at 650-750 ℃ under the protection of argon.
9. A sodium vanadium fluorophosphate/carbon cathode material, characterized in that the sodium vanadium fluorophosphate/carbon cathode material is obtained by the method for synthesizing the sodium vanadium fluorophosphate/carbon cathode material according to any one of claims 1 to 8.
10. A sodium-ion battery comprising the sodium vanadium fluorophosphate/carbon cathode material according to claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111279788.0A CN114094066A (en) | 2021-10-29 | 2021-10-29 | Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111279788.0A CN114094066A (en) | 2021-10-29 | 2021-10-29 | Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114094066A true CN114094066A (en) | 2022-02-25 |
Family
ID=80298690
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111279788.0A Pending CN114094066A (en) | 2021-10-29 | 2021-10-29 | Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114094066A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115196610A (en) * | 2022-07-19 | 2022-10-18 | 江苏大学 | Sodium ion battery anode material ferric sodium phosphate pyrophosphate/carbon, synthesis method thereof and sodium ion battery |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013077517A (en) * | 2011-09-30 | 2013-04-25 | Gs Yuasa Corp | Secondary battery active material, secondary battery active material electrode, and secondary battery using the same |
| CN103594716A (en) * | 2013-11-21 | 2014-02-19 | 天津工业大学 | Method for preparing cathode material of sodium-ion battery, namely sodium vanadium fluorophosphates |
| CN104733731A (en) * | 2015-03-25 | 2015-06-24 | 天津大学 | Method for preparing uniform carbon-coated vanadium phosphate sodium material |
| 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 |
| CN106374104A (en) * | 2016-10-10 | 2017-02-01 | 济南大学 | Method for preparing sodium fluorine vanadium phosphate material in air atmosphere |
| CN106920946A (en) * | 2017-04-15 | 2017-07-04 | 三峡大学 | A kind of preparation method of aluminum oxide and carbon compound coating fluorophosphoric acid vanadium sodium positive electrode |
| CN109755489A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院大连化学物理研究所 | A kind of fluorophosphoric acid vanadium sodium/preparation of carbon complex and the application of compound |
| CN110518238A (en) * | 2019-08-27 | 2019-11-29 | 江苏大学 | Sodium-ion battery positive material Na is synthesized based on organic phospho acid3V2(PO4)3/ nitrogen-doped carbon and preparation method |
| CN111540900A (en) * | 2020-05-13 | 2020-08-14 | 中南大学 | Preparation method of sodium vanadium fluorophosphate cathode material |
| CN111606314A (en) * | 2020-06-04 | 2020-09-01 | 哈尔滨工业大学 | Preparation method of sodium vanadium sodium triphosphate as positive electrode material of sodium-ion battery |
| WO2020174487A1 (en) * | 2019-02-28 | 2020-09-03 | International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) | Microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials and the product thereof |
| US20210167387A1 (en) * | 2018-08-07 | 2021-06-03 | Shanghai Zijian Chemical Technology Co., Ltd | Vanadium sodium phosphate positive electrode material, sodium ion battery, preparation method therefor, and use thereof |
-
2021
- 2021-10-29 CN CN202111279788.0A patent/CN114094066A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013077517A (en) * | 2011-09-30 | 2013-04-25 | Gs Yuasa Corp | Secondary battery active material, secondary battery active material electrode, and secondary battery using the same |
| CN103594716A (en) * | 2013-11-21 | 2014-02-19 | 天津工业大学 | Method for preparing cathode material of sodium-ion battery, namely sodium vanadium fluorophosphates |
| CN104733731A (en) * | 2015-03-25 | 2015-06-24 | 天津大学 | Method for preparing uniform carbon-coated vanadium phosphate sodium material |
| CN106374104A (en) * | 2016-10-10 | 2017-02-01 | 济南大学 | Method for preparing sodium fluorine vanadium phosphate material in air atmosphere |
| 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 |
| CN106920946A (en) * | 2017-04-15 | 2017-07-04 | 三峡大学 | A kind of preparation method of aluminum oxide and carbon compound coating fluorophosphoric acid vanadium sodium positive electrode |
| CN109755489A (en) * | 2017-11-08 | 2019-05-14 | 中国科学院大连化学物理研究所 | A kind of fluorophosphoric acid vanadium sodium/preparation of carbon complex and the application of compound |
| US20210167387A1 (en) * | 2018-08-07 | 2021-06-03 | Shanghai Zijian Chemical Technology Co., Ltd | Vanadium sodium phosphate positive electrode material, sodium ion battery, preparation method therefor, and use thereof |
| WO2020174487A1 (en) * | 2019-02-28 | 2020-09-03 | International Advanced Research Centre For Powder Metallurgy And New Materials (Arci) | Microwave assisted sol-gel process for preparing in-situ carbon coated electrode materials and the product thereof |
| CN110518238A (en) * | 2019-08-27 | 2019-11-29 | 江苏大学 | Sodium-ion battery positive material Na is synthesized based on organic phospho acid3V2(PO4)3/ nitrogen-doped carbon and preparation method |
| CN111540900A (en) * | 2020-05-13 | 2020-08-14 | 中南大学 | Preparation method of sodium vanadium fluorophosphate cathode material |
| CN111606314A (en) * | 2020-06-04 | 2020-09-01 | 哈尔滨工业大学 | Preparation method of sodium vanadium sodium triphosphate as positive electrode material of sodium-ion battery |
Non-Patent Citations (4)
| Title |
|---|
| QIANG LIU ET AL.: "Carbon-coated Na3V2(PO4)2F3 nanoparticles embedded in a mesoporous carbon matrix as a potential cathode material for sodium-ion batteries with superior rate capability and long-term cycle life", 《JOURNAL OF MATERIALS CHEMISTRY A》, pages 21478 - 21485 * |
| 朱永明等: "《动力锂离子电池正极材料——锰酸锂的设计合成与性能调控》", 哈尔滨工业大学出版社, pages: 170 - 173 * |
| 邓茁: "聚阴离子型钠离子电池正极材料合成与电化学性能研究", 《中国优秀硕士论文全文数据库》, pages 1 - 63 * |
| 陈栋;张香华;任能;芮先宏;: "溶胶―凝胶法制备钠离子电池正极材料Na_3V_2(PO_4)_3", 钢铁钒钛, no. 02, pages 50 - 54 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115196610A (en) * | 2022-07-19 | 2022-10-18 | 江苏大学 | Sodium ion battery anode material ferric sodium phosphate pyrophosphate/carbon, synthesis method thereof and sodium ion battery |
| CN115196610B (en) * | 2022-07-19 | 2024-03-26 | 湖州英钠新能源材料有限公司 | Sodium ion battery anode material sodium ferric pyrophosphate/carbon, synthesis method thereof and sodium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110061229B (en) | High-power-density long-cycle-life sodium ion battery positive electrode material and preparation method and application thereof | |
| CN102201576B (en) | Porous carbon in situ composite lithium iron phosphate cathode material and preparation method thereof | |
| CN105692576B (en) | Method for preparing battery-grade FePO4 from industrial iron-containing waste | |
| CN103208626B (en) | A kind of method adopting aniline to prepare lithium iron phosphate/carbon composite material | |
| CN110518238B (en) | Synthesis of sodium ion battery anode material Na based on organic phosphonic acid3V2(PO4)3Nitrogen-doped carbon and preparation method thereof | |
| CN110350198B (en) | Preparation method of sodium phosphate surface modified sodium ion battery positive electrode material | |
| CN113526483B (en) | Ferro-phosphorus sodalite type cathode material and preparation method and application thereof | |
| CN112701282B (en) | Large-radius ion-doped modified sodium vanadium fluorophosphate cathode material and preparation method thereof | |
| CN115196610B (en) | Sodium ion battery anode material sodium ferric pyrophosphate/carbon, synthesis method thereof and sodium ion battery | |
| CN113745505B (en) | Sodium ion battery positive electrode material, synthesis method thereof and sodium ion battery | |
| CN111916703A (en) | In-situ synthesis method of lithium iron manganese phosphate/carbon @ graphene composite material | |
| CN107492635B (en) | Composite positive electrode material Na of sodium-ion battery3V2(PO4)3/C and preparation method thereof | |
| CN113629242A (en) | Preparation method of polyanionic vanadium iron sodium phosphate positive electrode material | |
| CN110790248B (en) | Iron-doped cobalt phosphide microsphere electrode material with flower-shaped structure and preparation method and application thereof | |
| CN107069029B (en) | A kind of lithium battery high-voltage anode material and preparation method thereof | |
| CN114725375A (en) | One-step solvothermal method for preparing VS2Method for preparing negative electrode material of sodium ion battery | |
| CN114094066A (en) | Sodium vanadium fluorophosphate/carbon cathode material, synthetic method thereof and sodium-ion battery | |
| CN115939361B (en) | Copper phosphide doped hard carbon composite material and preparation method thereof | |
| CN116443836A (en) | Method for synthesizing sodium ion battery anode material sodium ferric pyrophosphate/carbon | |
| CN107492656B (en) | Self-supporting NaVPO4F/C sodium ion composite anode and preparation method thereof | |
| CN111900382B (en) | Preparation method and application of manganese pyrophosphate electrode material | |
| CN104332612A (en) | Phosphorus-modified carbon-coated lithium ion battery positive composite material, and preparation method and use thereof | |
| CN104347854A (en) | Method for preparing nano LiFePO4/C electrode material | |
| CN110289411B (en) | Zirconium fluoride manganese sodium phosphate/carbon composite material, positive electrode, sodium ion battery and preparation method thereof | |
| CN110021752B (en) | Lithium, aluminum and fluorine co-doped lithium iron phosphate cathode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20220608 Address after: 313199 No. 66, Luhui Road, Taihu street, Changxing County, Huzhou City, Zhejiang Province Applicant after: Huzhou Yingna new energy materials Co.,Ltd. Address before: Zhenjiang City, Jiangsu Province, 212013 Jingkou District Road No. 301 Applicant before: JIANGSU University |
|
| TA01 | Transfer of patent application right | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220225 |
|
| RJ01 | Rejection of invention patent application after publication |