CN115849328A - Sodium vanadium titanium phosphate, preparation method and application thereof - Google Patents
Sodium vanadium titanium phosphate, preparation method and application thereof Download PDFInfo
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- CN115849328A CN115849328A CN202211676556.3A CN202211676556A CN115849328A CN 115849328 A CN115849328 A CN 115849328A CN 202211676556 A CN202211676556 A CN 202211676556A CN 115849328 A CN115849328 A CN 115849328A
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- OKWSAPWRMTVKRE-UHFFFAOYSA-K P(=O)([O-])([O-])[O-].[Ti+4].[V+5].[Na+] Chemical compound P(=O)([O-])([O-])[O-].[Ti+4].[V+5].[Na+] OKWSAPWRMTVKRE-UHFFFAOYSA-K 0.000 title claims abstract description 113
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000002243 precursor Substances 0.000 claims abstract description 50
- 239000000243 solution Substances 0.000 claims abstract description 37
- 238000001354 calcination Methods 0.000 claims abstract description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims abstract description 24
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 21
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 21
- 238000001694 spray drying Methods 0.000 claims abstract description 19
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims abstract description 16
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims abstract description 16
- 238000001816 cooling Methods 0.000 claims abstract description 16
- 235000019837 monoammonium phosphate Nutrition 0.000 claims abstract description 16
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000012300 argon atmosphere Substances 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000002572 peristaltic effect Effects 0.000 claims description 6
- 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 description 5
- 229910052708 sodium Inorganic materials 0.000 claims description 5
- 239000011734 sodium Substances 0.000 claims description 5
- 238000003303 reheating Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 6
- 238000000576 coating method Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 239000002131 composite material Substances 0.000 description 5
- 230000001351 cycling effect Effects 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000010532 solid phase synthesis reaction Methods 0.000 description 3
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical group [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- -1 compound vanadium-titanium-sodium phosphate Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Abstract
The invention relates to the technical field of sodium-ion batteries, in particular to sodium vanadium titanium phosphate, and a preparation method and application thereof. The preparation method comprises the following steps: a) Mixing anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate, a citric acid aqueous solution and an ethanol solution of isopropyl titanate to obtain a vanadium-titanium-sodium phosphate precursor solution; b) Spray drying the vanadium-titanium-sodium phosphate precursor solution to obtain a vanadium-titanium-sodium phosphate precursor; c) Heating the vanadium-titanium-sodium phosphate precursor to 340-360 ℃ in argon atmosphere for calcination, after cooling, the mixture is heated to 750 to 850 ℃ and calcined to obtain the vanadium-titanium-sodium phosphate. According to the invention, the vanadium-titanium-sodium phosphate precursor is prepared by limiting the doping of titanium element and matching with the better effect of other components, and the vanadium-titanium-sodium phosphate precursor is prepared into the vanadium-titanium-sodium phosphate with higher specific capacity, excellent rate capability and ultra-long cycle life under a specific in-situ carbon coating process.
Description
Technical Field
The invention relates to the technical field of sodium-ion batteries, in particular to sodium vanadium titanium phosphate, and a preparation method and application thereof.
Background
The lithium ion battery has many advantages such as high specific capacity, high energy density and the like, but the market application of the lithium ion battery is limited due to low earth abundance. Compared with lithium ion batteries, sodium ion batteries have lower cost and richer earth reserves, is very suitable for the application of large-scale energy storage power stations. The development of the positive electrode material of the sodium-ion battery with high specific capacity and stable cycle is an urgent need in the current market.
Polyanionic compounds are widely favored by researchers because of their ultra-high sodium ion affinity and stable cycling performance. However, the specific capacity of polyanionic compounds is generally low, so that the improvement of the specific capacity is the main modification direction at present. Methods for synthesizing the positive electrode are generally classified into a solution method and a solid phase method, the solid phase method is widely used because of its simplicity and high repeatability. However, the solid phase method is not uniform enough for synthesizing materials, and has a lot of heterogeneous phases, and the solution method just compensates for the defect. Unfortunately, the solution method itself has a large number of factors, and thus, there is a large uncertainty in the synthesis process.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a sodium vanadium titanium phosphate, a preparation method and an application thereof, wherein the sodium vanadium titanium phosphate prepared by the present invention can be used for preparing a sodium ion battery, such that a high specific capacity, an excellent rate capability, and an ultra-long cycle life can be obtained.
The invention provides a preparation method of vanadium-titanium-sodium phosphate, which comprises the following steps:
a) Mixing anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate, a citric acid aqueous solution and an ethanol solution of isopropyl titanate to obtain a vanadium-titanium-sodium phosphate precursor solution;
b) Performing spray drying on the vanadium-titanium-sodium phosphate precursor solution to obtain a vanadium-titanium-sodium phosphate precursor;
c) And heating the vanadium-titanium-sodium phosphate precursor to 340-360 ℃ in an argon atmosphere for calcination, cooling, and then heating to 750-850 ℃ for calcination to obtain vanadium-titanium-sodium phosphate.
Preferably, in step a), the molar ratio of the anhydrous sodium carbonate, the ammonium metavanadate, the ammonium dihydrogen phosphate and the isopropyl titanate is 0.8-1.2: 0.8 to 1.2: 2.5-3.5: 0.8 to 1.2.
Preferably, in the step a), the molar ratio of sodium element to citric acid in the anhydrous sodium carbonate is 1.8-2.2: 0.8 to 1.2.
Preferably, in step a), mixing anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate, an aqueous citric acid solution, and an ethanol solution of isopropyl titanate comprises:
adding an ethanol solution of isopropyl titanate into a mixed solution of anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate and a citric acid aqueous solution, and stirring and mixing;
the stirring and mixing speed is 400-500 rpm.
Preferably, in the step B), the outlet temperature of the spray drying is 150-250 ℃, and the speed of a peristaltic pump is 15-25%.
Preferably, in the step C), the vanadium-titanium-sodium phosphate precursor is heated to 340-360 ℃ at a heating rate of 3-7 ℃/min;
the calcination time is 4 to 6 hours at the temperature of 340 to 360 ℃;
calcining at 340-360 deg.c and cooling to room temperature.
Preferably, in the step C), the heating rate of reheating to 750-850 ℃ is 3-7 ℃/min;
the calcining time is 10 to 14 hours at the temperature of between 750 and 850 ℃.
Preferably, step C), after calcination at 750-850 ℃, further comprises: and cooling to room temperature.
The invention also provides vanadium-titanium-sodium phosphate prepared by the preparation method.
The invention also provides a sodium-ion battery, the positive electrode of which comprises the sodium vanadium titanium phosphate according to claim 9.
The invention provides a preparation method of sodium vanadium titanium phosphate, which comprises the following steps: a) Mixing anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate, a citric acid aqueous solution and an ethanol solution of isopropyl titanate to obtain a vanadium-titanium-sodium phosphate precursor solution; b) Spray drying the vanadium-titanium-sodium phosphate precursor solution to obtain a vanadium-titanium-sodium phosphate precursor; c) And heating the vanadium-titanium-sodium phosphate precursor to 340-360 ℃ in an argon atmosphere for calcination, cooling, and then heating to 750-850 ℃ for calcination to obtain vanadium-titanium-sodium phosphate. According to the preparation method provided by the invention, the vanadium-titanium-sodium phosphate precursor is prepared by limiting the doping of the titanium element and matching with the better effect of other components, the polyanion compound vanadium-titanium-sodium phosphate is prepared from the vanadium-titanium-sodium phosphate precursor under a specific in-situ carbon coating process, and the vanadium-titanium-sodium phosphate has higher specific capacity, excellent rate capability and ultra-long cycle life. Meanwhile, the preparation method is simple in preparation process, excellent in cycling stability and good in application prospect in development of the sodium-ion battery with high specific capacity and stable cycling.
Drawings
FIG. 1 is an SEM image of a vanadium titanium sodium phosphate precursor and vanadium titanium sodium phosphate in example 1 of the present invention;
FIG. 2 is a charge-discharge voltage-specific capacity curve of vanadium titanium sodium phosphate in example 1 of the present invention for the first four cycles at a current density of 0.1C;
FIG. 3 is a 1C cycle performance curve for sodium vanadium titanium phosphate in example 1 of the present invention;
FIG. 4 is a graph of rate performance of sodium vanadium titanium phosphate in example 1 of the present invention;
FIG. 5 is a 10C cycle performance curve for sodium vanadium titanium phosphate in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a preparation method of vanadium-titanium-sodium phosphate, which comprises the following steps:
a) Mixing anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate, a citric acid aqueous solution and an ethanol solution of isopropyl titanate to obtain a vanadium-titanium-sodium phosphate precursor solution;
b) Performing spray drying on the vanadium-titanium-sodium phosphate precursor solution to obtain a vanadium-titanium-sodium phosphate precursor;
c) And heating the vanadium-titanium-sodium phosphate precursor to 340-360 ℃ in an argon atmosphere for calcining, cooling, and heating to 750-850 ℃ for calcining to obtain vanadium-titanium-sodium phosphate.
In step A):
mixing anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate, a citric acid aqueous solution and an ethanol solution of isopropyl titanate to obtain a vanadium-titanium-sodium phosphate precursor solution.
Specifically, the method comprises the following steps:
adding the ethanol solution of isopropyl titanate into the mixed solution of anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate and citric acid aqueous solution, stirring and mixing, and stopping stirring when the mixed solution is uniform yellowish emulsion to obtain the vanadium-titanium-sodium phosphate precursor solution.
In some embodiments of the invention, the molar ratio of the anhydrous sodium carbonate, the ammonium metavanadate, the ammonium dihydrogen phosphate and the isopropyl titanate is 0.8-1.2: 0.8 to 1.2: 2.5-3.5: 0.8 to 1.2; specifically, the ratio is 1:1:3:1.
in some embodiments of the invention, the molar ratio of sodium element to citric acid in the anhydrous sodium carbonate is 1.8-2.2: 0.8 to 1.2; specifically, the ratio is 2:1.
in certain embodiments of the invention, the ethanol solution of isopropyl titanate has a mass concentration of 1%.
The concentration of the citric acid aqueous solution is 0.01-0.03 mol/L; specifically, the concentration is 0.02mol/L.
In certain embodiments of the invention, the rate of said agitating mixing is 400 to 500rpm; specifically 450rpm.
In step B):
and carrying out spray drying on the vanadium-titanium-sodium phosphate precursor solution to obtain a vanadium-titanium-sodium phosphate precursor.
In certain embodiments of the invention, the outlet temperature of the spray drying is 150 to 250 ℃, in particular 200 ℃; the speed of the peristaltic pump is 15% -25%; specifically, it is 20%.
In some embodiments of the present invention, a spray drying mode of staged heating is adopted to spray dry a vanadium titanium sodium phosphate precursor sample, specifically including:
spray drying the vanadium-titanium-sodium phosphate precursor solution, and collecting a dried powder sample, namely a vanadium-titanium-sodium phosphate precursor; the outlet temperature of the spray drying is firstly set to be 150 ℃ and kept for 1h, and then is raised to be 200 ℃ and kept till the spraying is finished; the peristaltic pump speed was 20%.
The invention adopts a spray drying method to prepare powder with spherical morphology, namely the vanadium-titanium-sodium phosphate precursor. In certain embodiments of the present invention, the particle size of the sodium vanadium titanium phosphate precursor is 4.5 to 5.5 μm.
In step C):
step C) is carried out by an in-situ carbon coating process.
And heating the vanadium-titanium-sodium phosphate precursor to 340-360 ℃ in an argon atmosphere for calcination, cooling, and then heating to 750-850 ℃ for calcination to obtain vanadium-titanium-sodium phosphate.
In certain embodiments of the invention, step C) is performed in a vacuum tube furnace. Before the calcination, the method further comprises the following steps: and (3) pre-introducing argon to exhaust air in the tube, wherein the time of pre-introducing argon can be 0.5h.
In some embodiments of the present invention, the heating rate of heating the vanadium-titanium-sodium phosphate precursor to 340-360 ℃ is 3-7 ℃/min, specifically 5 ℃/min;
the temperature of the calcination is 350 ℃;
the calcining time is 4 to 6 hours, specifically 5 hours at the temperature of 340 to 360 ℃;
calcining at 340-360 deg.c and cooling to room temperature.
In some embodiments of the invention, the heating rate of reheating to 750-850 ℃ is 3-7 ℃/min, specifically 5 ℃/min;
the calcining temperature is 800 ℃;
the calcination time at 750-850 ℃ is 10-14 h, specifically 12h;
after calcination at 750-850 ℃, the method also comprises the following steps: and cooling to room temperature.
In some embodiments of the invention, the sodium vanadium titanium phosphate has a spherical shape, a dense carbon coating layer is formed on the surface, and the particle size is 2.5-3.5 μm.
The invention also provides vanadium-titanium-sodium phosphate prepared by the preparation method.
The invention also provides a sodium-ion battery, and the positive electrode of the sodium-ion battery comprises the vanadium-titanium-sodium phosphate.
Specifically, the sodium ion battery comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm. The positive electrode is the vanadium titanium sodium phosphate, the negative electrode is sodium metal, and the electrolyte is 1mol/L NaPF 6 The solution (solvent including PC and FEC, FEC concentration of 3% by volume in solvent) was used in an amount of 160. Mu.L, and the membrane was Glass Fiber. The cell was assembled into a C2032 button cell in an argon-protected glove box (water, oxygen content both below 0.1 ppm).
The source of the raw materials used in the present invention is not particularly limited, and the raw materials may be those generally commercially available.
According to the preparation method provided by the invention, the vanadium-titanium-sodium phosphate precursor is prepared by limiting the doping of the titanium element and matching with the better effect of other components, the polyanion compound vanadium-titanium-sodium phosphate is prepared from the vanadium-titanium-sodium phosphate precursor under a specific in-situ carbon coating process, and the vanadium-titanium-sodium phosphate has higher specific capacity, excellent rate capability and ultra-long cycle life. Meanwhile, the preparation method is simple in preparation process, excellent in cycling stability and good in application prospect in the development of the sodium ion battery with high specific capacity and stable cycling.
In order to further illustrate the present invention, the following examples are provided to describe the vanadium titanium sodium phosphate, the preparation method and the application thereof in detail, but the scope of the present invention should not be construed as being limited thereto.
Example 1
Preparing vanadium-titanium-sodium phosphate:
1) Adding an ethanol solution of isopropyl titanate with the mass concentration of 1% into a mixed solution of anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate and 0.02mol/L citric acid aqueous solution, stirring and mixing at 450rpm, and stopping stirring when the mixed solution is a uniform yellowish emulsion to obtain a vanadium-titanium-sodium phosphate precursor solution;
the molar ratio of the anhydrous sodium carbonate to the ammonium metavanadate to the ammonium dihydrogen phosphate to the isopropyl titanate is 1:1:3:1;
the molar ratio of sodium element to citric acid in the anhydrous sodium carbonate is 2:1.
2) Spray drying the vanadium-titanium-sodium phosphate precursor solution, and collecting a dried powder sample, namely a vanadium-titanium-sodium phosphate precursor;
the outlet temperature of the spray drying was 200 ℃ and the peristaltic pump speed was 20%.
3) And (3) taking a vacuum tube furnace, introducing argon for 0.5h to exhaust air in the tube, heating the vanadium-titanium-sodium phosphate precursor to 350 ℃ at a speed of 5 ℃/min under the argon atmosphere, calcining for 5h, cooling to room temperature, heating to 800 ℃, calcining for 12h, and cooling to room temperature to obtain vanadium-titanium-sodium phosphate.
4) Assembling the sodium-ion battery:
the sodium ion battery comprises a positive electrode, a negative electrode, electrolyte and a diaphragm, wherein the positive electrode is the vanadium-titanium-sodium phosphate, the negative electrode is sodium metal, and the electrolyte is 1mol/L NaPF 6 The solution (solvent comprising PC and FEC, FEC concentration in solvent was 3% by volume) was used in 160. Mu.L, and the membrane was Glass Fiber. The cell was assembled into a C2032 button cell in an argon-protected glove box (water, oxygen content both below 0.1 ppm).
FIG. 1 is a SEM picture of the vanadium titanium sodium phosphate precursor and the vanadium titanium sodium phosphate in example 1 of the present invention, wherein, fig. a in fig. 1 is an SEM image of the sodium vanadium titanium phosphate precursor in example 1 of the present invention, and fig. b in fig. 1 is an SEM image of the sodium vanadium titanium phosphate in example 1 of the present invention. As can be seen from the graph a in FIG. 1, the sodium vanadium titanium phosphate is spherical, the particle size is kept between 4.5 and 5.5 mu m; as can be seen from the graph b in FIG. 1, after high-temperature calcination, the spherical morphology is well maintained, and a compact carbon coating layer is formed on the surface, and the particle size is 2.5-3.5 μm.
FIG. 2 is a charge-discharge voltage-specific capacity curve of vanadium titanium sodium phosphate in example 1 of the present invention for the first four cycles at a current density of 0.1C. From the figure2, it can be seen that sodium vanadium titanium phosphate has three plateaus, corresponding to V respectively 3+ /V 4+ 、Ti 3+ /Ti 4+ And V 2 + /V 3+ The valence of (2). In the working range of voltage of 1.5-3.9V, the first circle of the sodium-ion battery has 146.2 mAh.g -1 Specific discharge capacity of (2).
FIG. 3 is a 1C cycle performance curve of sodium vanadium titanium phosphate in the voltage interval of 1.5-3.9V in example 1 of the present invention. As can be seen from fig. 3, the vanadium titanium sodium phosphate still maintains a specific capacity of 90.0% after 550 cycles at a current density of 1C, and simultaneously the coulombic efficiency is maintained at about 100%.
FIG. 4 is a graph showing the rate performance of sodium vanadium titanium phosphate in the voltage range of 1.5 to 3.9V in example 1 of the present invention. As can be seen from FIG. 4, the sodium vanadium titanium phosphate still maintained more than 80mAh g at a large rate of 25C -1 The specific capacity of the composite material is kept, and the coulombic efficiency is kept about 100 percent.
FIG. 5 is a 10C cycle performance curve for sodium vanadium titanium phosphate in the voltage interval of 1.5-3.9V in example 1 of the present invention. As can be seen from fig. 5, the vanadium titanium sodium phosphate still maintains 96.2% of specific capacity and coulombic efficiency of about 100% after 1000 cycles under the high current density of 10C.
Example 2
The difference from example 1 is that:
in step 3):
the continuous sintering mode is adopted in a vacuum tube furnace, and cooling treatment is not carried out. The method specifically comprises the following steps:
and (3) taking a vacuum tube furnace, introducing argon for 0.5h, exhausting air in the tube, heating the vanadium-titanium-sodium phosphate precursor to 350 ℃ at a speed of 5 ℃/min under the argon atmosphere, calcining for 5h, heating to 800 ℃ for calcining for 12h, and cooling to room temperature to obtain the vanadium-titanium-sodium phosphate.
The electrochemical performance of the prepared sodium vanadium titanium phosphate is studied in the voltage interval of 1.5-3.9V according to the method of the example 1;
the experiment result shows that the first ring of the sodium-ion battery has 146.7 mAh.g at the current density of 0.1C -1 Specific discharge capacity of (a);
under the current density of 1C, the vanadium titanium sodium phosphate still maintains 90.1 percent of specific capacity after circulating for 550 circles, and simultaneously the coulombic efficiency is maintained to be about 100 percent;
the vanadium-titanium-sodium phosphate still maintains more than 80 mAh.g at a large multiplying power of 25C -1 The specific capacity of the composite material is kept, and the coulombic efficiency is kept about 100 percent;
circulating the vanadium-titanium-sodium phosphate for 1000 circles under the heavy current density of 10C, the specific capacity of 96% is still kept, and the coulombic efficiency is kept at about 100%.
Example 3
The difference from example 1 is that:
in step 1):
the molar ratio of sodium element to citric acid in the anhydrous sodium carbonate is 3:1.
the electrochemical performance of the prepared sodium vanadium titanium phosphate was investigated in the voltage interval of 1.5-3.9V according to the method of example 1;
the experiment result shows that the first circle of the sodium-ion battery has 147mAh g under the current density of 0.1C -1 Specific discharge capacity of (a);
under the current density of 1C, the vanadium-titanium-sodium phosphate still maintains 89% of specific capacity after being circulated for 550 circles, and simultaneously the coulombic efficiency is maintained at about 100%;
the vanadium-titanium-sodium phosphate still maintains more than 82 mAh.g at a large multiplying power of 25C -1 The specific capacity of the composite material is kept, and the coulombic efficiency is kept about 100 percent;
under the high current density of 10C, after 1000 cycles, the vanadium-titanium-sodium phosphate still maintains 95.5 percent of specific capacity, and simultaneously the coulombic efficiency is maintained at about 100 percent.
Example 4
The difference from example 1 is that:
in step 2):
and carrying out spray drying treatment on the vanadium-titanium-sodium phosphate precursor sample by adopting a spray drying mode of graded heating. The method specifically comprises the following steps:
spray drying the vanadium-titanium-sodium phosphate precursor solution, and collecting a dried powder sample, namely a vanadium-titanium-sodium phosphate precursor; the outlet temperature of the spray-drying was first set at 150 ℃ and held for 1h, then raised to 200 ℃ and held until spraying was complete, with a peristaltic pump speed of 20%.
The electrochemical performance of the prepared sodium vanadium titanium phosphate is studied in the voltage interval of 1.5-3.9V according to the method of the example 1;
the experiment result shows that the first ring of the sodium-ion battery has 146.7 mAh.g at the current density of 0.1C -1 The specific discharge capacity of (a);
under the current density of 1C, the vanadium titanium sodium phosphate still maintains 91% of specific capacity after circulating for 550 circles, and simultaneously the coulombic efficiency is maintained at about 100%;
the vanadium titanium sodium phosphate still maintains over 79.5 mAh.g at a large multiplying power of 25C -1 The specific capacity of the composite material is kept, and the coulombic efficiency is kept about 100 percent;
under the high current density of 10C, after 1000 cycles, the vanadium-titanium-sodium phosphate still maintains 96.8 percent of specific capacity, and simultaneously the coulombic efficiency is maintained at about 100 percent.
The experiment result shows that the first ring of the sodium-ion battery prepared by the invention has a current density of more than 146 mAh.g under 0.1C -1 Specific discharge capacity of (a);
under the current density of 1C, the vanadium titanium sodium phosphate still maintains no less than 89% of specific capacity after circulating for 550 circles, and simultaneously the coulombic efficiency is maintained at about 100%;
the vanadium-titanium-sodium phosphate still maintains over 79.5 mAh.g at a large multiplying power of 25C -1 The specific capacity of the composite material is kept, and the coulombic efficiency is kept about 100 percent;
under the high current density of 10C, after circulating for 1000 circles, the vanadium-titanium-sodium phosphate still keeps the specific capacity of over 95 percent, and simultaneously the coulombic efficiency is kept about 100 percent.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A preparation method of sodium vanadium titanium phosphate comprises the following steps:
a) Mixing anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate, a citric acid aqueous solution and an ethanol solution of isopropyl titanate to obtain a vanadium-titanium-sodium phosphate precursor solution;
b) Performing spray drying on the vanadium-titanium-sodium phosphate precursor solution to obtain a vanadium-titanium-sodium phosphate precursor;
c) And heating the vanadium-titanium-sodium phosphate precursor to 340-360 ℃ in an argon atmosphere for calcining, cooling, and heating to 750-850 ℃ for calcining to obtain vanadium-titanium-sodium phosphate.
2. The preparation method according to claim 1, wherein in step a), the molar ratio of the anhydrous sodium carbonate, the ammonium metavanadate, the ammonium dihydrogen phosphate and the isopropyl titanate is 0.8-1.2: 0.8 to 1.2: 2.5-3.5: 0.8 to 1.2.
3. The preparation method according to claim 1, wherein in the step A), the molar ratio of sodium element to citric acid in the anhydrous sodium carbonate is 1.8-2.2: 0.8 to 1.2.
4. The method of claim 1, wherein the step a) of mixing anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate, an aqueous solution of citric acid, and an ethanol solution of isopropyl titanate comprises:
adding an ethanol solution of isopropyl titanate into a mixed solution of anhydrous sodium carbonate, ammonium metavanadate, ammonium dihydrogen phosphate and a citric acid aqueous solution, and stirring and mixing;
the stirring and mixing speed is 400-500 rpm.
5. The method according to claim 1, wherein in step B), the outlet temperature of the spray drying is 150-250 ℃ and the peristaltic pump speed is 15-25%.
6. The preparation method according to claim 1, wherein in step C), the vanadium-titanium-sodium phosphate precursor is heated to 340-360 ℃ at a heating rate of 3-7 ℃/min;
the calcination time is 4 to 6 hours at the temperature of 340 to 360 ℃;
calcining at 340-360 deg.c and cooling to room temperature.
7. The method according to claim 1, wherein in the step C), the heating rate of reheating to 750 to 850 ℃ is 3 to 7 ℃/min;
the calcining time is 10 to 14 hours at the temperature of between 750 and 850 ℃.
8. The method according to claim 1, wherein the step C) further comprises, after calcination at 750-850 ℃: and cooling to room temperature.
9. Sodium vanadium titanium phosphate obtainable by the process according to any one of claims 1 to 8.
10. A sodium-ion battery, wherein a positive electrode of the sodium-ion battery comprises the sodium vanadium titanium phosphate according to claim 9.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107871865A (en) * | 2017-11-02 | 2018-04-03 | 华中科技大学 | A kind of preparation method of the sodium-ion battery positive material of doping vario-property vanadium phosphate sodium |
| CN110556533A (en) * | 2018-06-01 | 2019-12-10 | 中南大学 | Nitrogen-doped carbon-coated spherical vanadium-titanium-sodium phosphate composite material, preparation method thereof and application of composite material in sodium ion battery |
| CN110556518A (en) * | 2018-06-01 | 2019-12-10 | 中南大学 | Fluorinated vanadium-titanium-sodium phosphate/carbon composite cathode material for sodium ion battery and preparation method thereof |
| CN112018339A (en) * | 2019-05-31 | 2020-12-01 | 中南大学 | Method for preparing sodium ion battery vanadium fluorophosphate/carbon composite positive electrode material from vanadium-containing mineral aggregate and prepared positive electrode material |
| US20210242451A1 (en) * | 2020-02-04 | 2021-08-05 | Korea Advanced Institute Of Science And Technology | Metal-Doped Sodium Vanadium Fluorophosphate/Sodium Vanadium Phosphate (Na3V2(PO4)2F3/Na3V2(PO4)3) Composite for Sodium-Ion Storage Material |
| CN115483372A (en) * | 2022-08-23 | 2022-12-16 | 江苏大学 | Ternary phosphate/carbon as positive electrode material of sodium-ion battery, synthetic method of ternary phosphate/carbon and sodium-ion battery |
-
2022
- 2022-12-26 CN CN202211676556.3A patent/CN115849328A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107871865A (en) * | 2017-11-02 | 2018-04-03 | 华中科技大学 | A kind of preparation method of the sodium-ion battery positive material of doping vario-property vanadium phosphate sodium |
| CN110556533A (en) * | 2018-06-01 | 2019-12-10 | 中南大学 | Nitrogen-doped carbon-coated spherical vanadium-titanium-sodium phosphate composite material, preparation method thereof and application of composite material in sodium ion battery |
| CN110556518A (en) * | 2018-06-01 | 2019-12-10 | 中南大学 | Fluorinated vanadium-titanium-sodium phosphate/carbon composite cathode material for sodium ion battery and preparation method thereof |
| CN112018339A (en) * | 2019-05-31 | 2020-12-01 | 中南大学 | Method for preparing sodium ion battery vanadium fluorophosphate/carbon composite positive electrode material from vanadium-containing mineral aggregate and prepared positive electrode material |
| US20210242451A1 (en) * | 2020-02-04 | 2021-08-05 | Korea Advanced Institute Of Science And Technology | Metal-Doped Sodium Vanadium Fluorophosphate/Sodium Vanadium Phosphate (Na3V2(PO4)2F3/Na3V2(PO4)3) Composite for Sodium-Ion Storage Material |
| CN115483372A (en) * | 2022-08-23 | 2022-12-16 | 江苏大学 | Ternary phosphate/carbon as positive electrode material of sodium-ion battery, synthetic method of ternary phosphate/carbon and sodium-ion battery |
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