CN115483372A - Ternary phosphate/carbon as positive electrode material of sodium-ion battery, synthetic method of ternary phosphate/carbon and sodium-ion battery - Google Patents

Ternary phosphate/carbon as positive electrode material of sodium-ion battery, synthetic method of ternary phosphate/carbon and sodium-ion battery Download PDF

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CN115483372A
CN115483372A CN202211011040.7A CN202211011040A CN115483372A CN 115483372 A CN115483372 A CN 115483372A CN 202211011040 A CN202211011040 A CN 202211011040A CN 115483372 A CN115483372 A CN 115483372A
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sodium
carbon
ion battery
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王亚平
张克琳
栗欢欢
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Huzhou Yingna New Energy Materials Co ltd
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Jiangsu University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • 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
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Abstract

The invention discloses a sodium ion battery anode material ternary phosphate/carbon, a synthesis method thereof and a sodium ion battery, wherein the sodium ion battery anode material ternary phosphate/carbon comprises the following steps: weighing organic acid sodium, a vanadium source, a manganese source, a titanium source and organic phosphonic acid according to the molar ratio of sodium to vanadium to titanium to phosphonic acid groups of 3 x (1-0.5 x) to 3, wherein x is more than or equal to 0.5 and less than or equal to 1.0; adding deionized water into the organic sodium and the organic phosphonic acid, stirring and dissolving to obtain a clear solution. Then, a vanadium source was added, and the mixture was heated and stirred to obtain a blue gel. Continuously adding a titanium source and a manganese source, heating and stirring the blue-green solution until the water is evaporated to dryness; grinding the obtained solid, presintering under the protection of nitrogen, naturally cooling, taking out, grinding again, and under the protection of nitrogenSintering and naturally cooling to obtain the product Na as the positive electrode material of the sodium-ion battery 3 V x Mn 1‑0.5x Ti 1‑0.5x (PO 4 ) 3 Carbon/carbon. The invention utilizes organic phosphonic acid and organic sodium salt as Na 3 V x Mn 1‑0.5x Ti 1‑0.5x (PO 4 ) 3 All or part of sodium source, phosphate radical and carbon source required by the carbon/carbon synthesis, the synthesis process is simple and efficient, and the obtained electrode material has good rate capability and long cycle life.

Description

Ternary phosphate/carbon as positive electrode material of sodium-ion battery, synthetic method of ternary phosphate/carbon and sodium-ion battery
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a sodium ion battery anode material ternary phosphate/carbon, a synthesis method thereof and a sodium ion battery.
Background
Sodium ion batteries are considered to be the first choice of the next generation of energy storage batteries because of abundant sodium resources and low price. The positive electrode material is one of the major bottlenecks in the scale application. Vanadium sodium phosphate (Na) 3 V 2 (PO 4 ) 3 ) The three-dimensional open framework and the larger channel can be used for the rapid transmission of sodium ions, so that the three-dimensional open framework and the larger channel are one of the main choices of the positive electrode of the sodium-ion battery. However, na 3 V 2 (PO 4 ) 3 The voltage plateau of (A) is only-3.4V and the vanadium resource is expensive, resulting in Na 3 V 2 (PO 4 ) 3 The cost is high. In recent years, a compound with Na 3 V 2 (PO 4 ) 3 Cathode material manganese titanium sodium phosphate (Na) with similar structure 3 MnTi(PO 4 ) 3 ) Are of great interest to researchers. The composite material has two voltage platforms of 3.5V and 4.1V, and the manganese and the titanium are cheap, so that the composite material has the potential of large-scale use. However, na 3 MnTi(PO 4 ) 3 The cycle performance, rate capability and coulombic efficiency are not ideal. Na is mixed with 3 V 2 (PO 4 ) 3 With Na 3 MnTi(PO 4 ) 3 The ternary phosphate anode material is combined to construct, so that respective advantages are expected to be exerted, and respective disadvantages are overcome.
Disclosure of Invention
Aiming at the existing problems, the invention provides a sodium ion battery anode material ternary phosphate/carbon and a synthesis method thereof. By co-doping of manganese and titanium with Na 3 V 2 (PO 4 ) 3 To construct ternary phosphate Na 3 V x Mn 1-0.5x Ti 1-0.5x (PO 4 ) 3 The/carbon (x is more than or equal to 0.5 and less than or equal to 1.0) anode material not only effectively reduces the cost, but also improves the average working voltage of the material. Use of organic phosphonic acid and sodium organic acid as Na 3 V x Mn 1-0.5x Ti 1-0.5x (PO 4 ) 3 Phosphate radical, carbon source and all or part of sodium source required by carbon synthesis, and the synthesis process is simple and efficient. In addition, the electrode material obtained by the method has good rate capability and long cycle life. The invention effectively solves the problem of Na serving as the positive electrode material of the sodium-ion battery 3 V 2 (PO 4 ) 3 The problems of high price, poor performance and the like exist.
The invention also provides a positive electrode material Na containing the sodium-ion battery 3 V x Mn 1-0.5x Ti 1-0.5x (PO 4 ) 3 A sodium ion battery of carbon.
The invention is realized by the following technical scheme:
a method for synthesizing ternary phosphate/carbon serving as a positive electrode material of a sodium-ion battery comprises the following steps:
(1) Firstly, adding deionized water into organic sodium and organic phosphonic acid, stirring and dissolving to obtain a clear solution; then adding a vanadium source, heating and stirring to obtain blue gel; continuously adding a titanium source and a manganese source, heating and stirring until the mixture is dry, and drying the obtained gel-like solid;
(2) Grinding the solid obtained after drying in the step (1), presintering under the protection of nitrogen, naturally cooling, taking out and grinding again, sintering under the protection of nitrogen, and naturally cooling to obtain the product of ternary phosphate/carbon (Na) serving as the positive electrode material of the sodium-ion battery 3 V x Mn 1-0.5x Ti 1-0.5x (PO 4 ) 3 Carbon, x is more than or equal to 0.5 and less than or equal to 1.0.
In the scheme, in the step (1), the ratio of the raw materials is required to satisfy that the molar ratio of sodium to vanadium to manganese to titanium to phosphonic acid groups is 3.
In the above scheme, in the step (1), the organic sodium salt is trisodium citrate or sodium gluconate.
In the above scheme, in the step (1), the vanadium source is ammonium metavanadate or sodium metavanadate.
In the above scheme, in the step (1), the organic phosphonic acid is aminotrimethylene phosphonic acid or hydroxyethylidene diphosphonic acid.
In the above scheme, in the step (1), the manganese source is manganese acetate, manganese carbonate or manganese oxalate.
In the above scheme, in the step (1), the titanium source is titanium dioxide or tetrabutyl titanate.
In the scheme, in the step (1), the heating temperature is 80-100 ℃.
In the above scheme, in the step (1), the drying conditions 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, in the step (2), the pre-sintering conditions are as follows: pre-sintering for 2-6 h at 300-400 ℃ under the protection of nitrogen.
In the above scheme, in the step (2), the sintering conditions are as follows: sintering for 8-12 h under the protection of nitrogen at 500-800 ℃.
The ternary phosphate/carbon is obtained according to the synthesis method of the sodium-ion battery positive electrode material.
A sodium ion battery comprises the sodium ion battery anode material ternary phosphate/carbon.
Compared with the prior art, the invention has the beneficial effects that:
the sodium-ion battery anode material of the invention is ternary phosphate Na 3 V x Mn 1-0.5x Ti 1-0.5x (PO 4 ) 3 Carbon compared with Na 3 V 2 (PO 4 ) 3 Not only the cost is greatly reduced, but also the voltage platform is improved; the organic phosphonic acid selected contains phosphonic acid groups and carbon-containing groups and therefore has a multifunctional character, i.e. provides Na as well 3 V x Mn 1-0.5x Ti 1-0.5x (PO 4 ) 3 Phosphate radical required by carbon synthesis and amorphous carbon for coating are formed; the sodium organic acid selected contains sodium and carbon-containing groups and also has a reducing agent per se, and thus has a multifunctional property, i.e. both Na and Na are supplied 3 V x Mn 1-0.5x Ti 1-0.5x (PO 4 ) 3 All or part of sodium required by synthesis in carbon forms amorphous carbon for coating, and can also 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 does not generate any toxic waste gas and waste water, and the synthesis process is simple and efficient; the cathode material obtained by the method has good rate performance and long cycle life.
Drawings
Fig. 1 is an XRD pattern of a sample prepared in 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 charge and discharge curve at a 1C rate of a sample prepared in example 1 of the present invention; and (b) is a cycle performance chart of the compound at a multiplying power of 1C.
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 image of a sample prepared in example 2 of the present invention.
Fig. 7 (a) is a charge and discharge curve at 1C rate of a sample prepared in example 2 of the present invention; and (b) is a cycle performance graph of the material at a multiplying power of 1C.
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 charge and discharge curve at a rate of 1C for a sample prepared in example 3 of the present invention; and (b) is a cycle performance chart of the compound at a multiplying power of 1C.
FIG. 12 is a graph of rate capability for samples prepared in example 3 of the present invention.
Fig. 13 is an XRD pattern of a sample prepared in example 4 of the present invention.
FIG. 14 is an SEM image of a sample prepared in example 4 of the present invention.
Fig. 15 (a) is a first charge and discharge curve at a rate of 1C for a sample prepared in example 4 of the present invention; and (b) is a cycle performance chart of the compound at a multiplying power of 1C.
FIG. 16 is a graph of rate capability for samples prepared in example 4 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.
The invention relates to a sodium ion battery anode material ternary phosphate/carbon and a synthesis method thereof, which comprises the following steps:
(1) Weighing organic acid sodium, a vanadium source, a manganese source, a titanium source and organic phosphonic acid according to the molar ratio of sodium to vanadium to titanium to phosphonic acid groups of 3 x (1-0.5 x) to 3, wherein x is more than or equal to 0.5 and less than or equal to 1.0. Firstly, adding deionized water into organic sodium and organic phosphonic acid, stirring and dissolving to obtain a clear solution. Then, a vanadium source was added, and the mixture was heated and stirred to obtain a blue gel. Continuously adding a titanium source and a manganese source, heating and stirring the blue-green solution at 80-100 ℃ until the water is evaporated to dryness, and drying the obtained gel-like solid in an oven at 80-100 ℃ for 5-12 h;
(2) Grinding the solid obtained in the step (1), presintering for 2-6 h under the protection of nitrogen at 300-400 ℃, naturally cooling to room temperature, taking out and grinding again, sintering for 8-12 h under the protection of nitrogen at 500-800 ℃, and naturally cooling to obtain the product.
Preferably, the organic acid sodium is trisodium citrate and sodium gluconate.
Preferably, the vanadium source is ammonium metavanadate or sodium metavanadate.
Preferably, the organic phosphonic acid is aminotrimethylene phosphonic acid, hydroxyethylidene diphosphonic acid.
Preferably, the manganese source is manganese acetate, manganese carbonate or manganese oxalate.
Preferably, the titanium source is titanium dioxide, tetrabutyl titanate.
The ternary phosphate/carbon as the positive electrode material of the sodium-ion battery is obtained according to the synthesis method.
A sodium ion battery comprises the sodium ion battery anode material ternary phosphate/carbon.
Example 1
According to organic acid sodium and vanadiumThe molar ratio of the source to the manganese source to the titanium source to the organic phosphonic acid is 6. Adding an appropriate amount of deionized water into aminotrimethylene phosphonic acid and sodium gluconate, stirring and dissolving to obtain a clear solution, then adding sodium metavanadate, stirring and dissolving to obtain a blue solution. And continuously adding tetrabutyl titanate and manganese carbonate to obtain a light blue solution. Heating and stirring the light blue solution at 80 ℃, putting the light blue solution into an oven when the water is evaporated to dryness and the sample is gelatinous, and drying the light blue solution at 80 ℃ for 12 hours. The obtained solid is ground and presintered for 6 hours at 300 ℃ under the protection of nitrogen. Naturally cooling to room temperature, taking out, grinding again, sintering for 8h at 650 ℃ under the protection of nitrogen, and naturally cooling to obtain the product Na serving as the positive electrode material of the sodium-ion battery 3 V 1.0 Mn 0.5 Ti 0.5 (PO 4 ) 3 (iii) carbon.
FIG. 1 is an XRD pattern of the product obtained in this example, showing that the product is a single ordered sodium super ionic conductor (NASICON) structure belonging to hexagonal rhombohedral phase without any impurity phase. According to the SEM image shown in fig. 2, the resulting material exhibited a small particle morphology. The obtained product was assembled into an experimental button-type half cell to measure its charge-discharge specific capacity and cycle performance, and the results are shown in fig. 3. When the charge and discharge were carried out at a rate of 1C, the charge and discharge curve had two typical plateaus as shown in FIG. 3 (a), and the voltage curves were located around-3.45 and-3.85V, respectively. The results of the cycle performance test are shown in FIG. 3 (b), and the specific capacity after 500 cycles is 78.62mAh g -1 The capacity retention rate was 87.8%. 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.
Example 2
The method is characterized by comprising the following steps of 1, weighing trisodium citrate, sodium metavanadate, manganese acetate, titanium dioxide and hydroxy ethylidene diphosphonic acid according to the molar ratio of organic acid sodium to vanadium to manganese to titanium to organic phosphonic acid being 6. Adding a proper amount of deionized water into hydroxyethylidene diphosphonic acid and trisodium citrate, stirring and dissolving to obtain a clear solution, then adding sodium metavanadate, stirring and dissolving to obtain a blue solution. Titanium dioxide and manganese acetate are continuously added to obtain a light blue solution. Will be shallowAnd heating and stirring the blue solution at 85 ℃, putting the blue solution into an oven when the water is evaporated to dryness and the sample is gelatinous, and drying the blue solution at 85 ℃ for 10 hours. The obtained solid is ground and presintered for 4 hours at 315 ℃ under the protection of nitrogen. Naturally cooling to room temperature, taking out, grinding again, sintering for 12h at 500 ℃ under the protection of nitrogen, and naturally cooling to obtain the product Na serving as the positive electrode material of the sodium-ion battery 3 V 1.0 Mn 0.5 Ti 0.5 (PO 4 ) 3 Carbon/carbon.
FIG. 5 is an XRD pattern of the product obtained in this example, which shows that the product has a single ordered sodium super ionic conductor (NASICON) structure, belongs to hexagonal rhombohedral phase, and has no any impurity phase. According to the SEM image shown in FIG. 6, the resulting material exhibited a particulate morphology. The obtained product was assembled into an experimental button-type half cell to measure its charge-discharge specific capacity and cycle performance, and the results are shown in fig. 7. The charge-discharge curve is shown in FIG. 7 (a), and the voltage curve has two typical plateaus, which are respectively located at about 3.45V and 3.85V. The results of the cycle performance test are shown in FIG. 7 (b), and the specific capacity after 500 cycles is 70.58mAh g -1 The capacity retention rate was 88.2%. 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.
Example 3
Weighing trisodium citrate, ammonium metavanadate, manganese oxalate, titanium dioxide and amino trimethylene phosphonic acid according to the molar ratio of organic sodium, vanadium source, manganese source, titanium source and organic phosphonic acid being 9. Adding a proper amount of deionized water into aminotrimethylene phosphonic acid and trisodium citrate, stirring and dissolving to obtain a clear solution, then adding ammonium metavanadate, stirring and dissolving to obtain a light blue solution, and continuously adding titanium dioxide and manganese oxalate to obtain a blue-green solution. Heating and stirring the blue-green 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 ℃. Grinding the obtained solid, and presintering for 2h at 400 ℃ under the protection of nitrogen. Naturally cooling to room temperature, taking out, grinding again, sintering for 8h at 800 ℃ under the protection of nitrogen, and naturally cooling to obtain the product Na serving as the positive electrode material of the sodium-ion battery 3 V 0.667 Mn 0.667 Ti 0.667 (PO 4 ) 3 Carbon/carbon。
FIG. 9 is an XRD pattern of the product obtained in this example, showing that the product is a single ordered sodium super ionic conductor (NASICON) structure belonging to hexagonal rhombohedral phase without any impurity phase. According to the SEM image shown in fig. 10, the resulting material exhibited cross-linked sponge-like aggregates and successfully incorporated a continuous intact carbon skeleton. The obtained product was assembled into an experimental button-type half cell to measure its charge-discharge specific capacity and cycle performance, and the results are shown in fig. 11. The charge-discharge curve is shown in FIG. 11 (a), and the voltage curve has two typical plateaus, which are respectively located at about 3.45V and 3.85V. The results of the cycle performance test are shown in FIG. 11 (b), and the specific capacity after 1000 cycles is 51.58mAh g -1 The capacity retention rate was 98.4%. 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.
Example 4
Weighing sodium gluconate, sodium metavanadate, manganese acetate, tetrabutyl titanate and hydroxy ethylidene diphosphonic acid according to the molar ratio of organic acid sodium, vanadium source, manganese source, titanium source and organic phosphonic acid of 12. Adding a proper amount of deionized water into hydroxyethylidene diphosphonic acid and sodium gluconate, stirring and dissolving to obtain a clear solution, then adding sodium metavanadate, stirring and dissolving to obtain a light blue solution, and continuously adding tetrabutyl titanate and manganese acetate to obtain a dark green solution. Heating and stirring the dark green solution at 90 ℃, putting the dark green solution into an oven when the water is evaporated to dryness and the sample is gelatinous, and drying the dark green solution at 90 ℃ for 10 hours. Grinding the obtained solid, and presintering for 2h at 400 ℃ under the protection of nitrogen. Naturally cooling to room temperature, taking out, grinding again, sintering for 8h at 700 ℃ under the protection of nitrogen, and naturally cooling to obtain the product Na serving as the positive electrode material of the sodium-ion battery 3 V 0.5 Mn 0.75 Ti 0.75 (PO 4 ) 3 Carbon/carbon.
FIG. 13 is an XRD pattern of the product obtained in this example, showing that the product is a single ordered sodium super ionic conductor (NASICON) structure belonging to hexagonal rhombohedral phase. According to the SEM image shown in fig. 14, the resulting material exhibited a large number of carbon skeleton-supported granular shapes. The obtained product is assembled into an experimental button type half cell to measure the charge-discharge specific capacity andthe cycle performance, results are shown in figure 15. The charging and discharging curves are shown in fig. 15 (a), and the voltage curve has two typical plateaus, which are respectively positioned near-3.45V and-3.85V. The results of the cycle performance test are shown in FIG. 15 (b), and the specific capacity after 1000 cycles is 53.58mAh g -1 The capacity retention rate was 81.6%. The rate performance test is carried out under different rates, and the result is shown in figure 16, and the material shows good rate performance.
As can be seen from the above examples, the method for synthesizing ternary phosphate/carbon as a positive electrode material of a sodium-ion battery is a preparation method for synthesizing ternary phosphate/carbon as a positive electrode material of a sodium-ion battery based on organic phosphonic acid and organic sodium, and the selected organic phosphonic acid contains phosphonic acid groups and carbon-containing groups, so that the method has the multifunctional characteristic of providing Na 3 V x Mn 1- 0.5x Ti 1-0.5x (PO 4 ) 3 Phosphate radical required by carbon synthesis and amorphous carbon for coating are formed; the sodium organic acid selected contains sodium and carbon-containing groups and has a reducing agent per se, thus having a multifunctional property, i.e. providing both Na and Na 3 V x Mn 1-0.5x Ti 1-0.5x (PO 4 ) 3 All or part of sodium required by synthesis in carbon forms amorphous carbon for coating, and simultaneously can also 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 does not generate any toxic waste gas and waste water, and the synthesis process is simple and efficient; the cathode material obtained by the method has good rate capability and long cycle life.
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 (9)

1. A method for synthesizing ternary phosphate/carbon serving as a positive electrode material of a sodium-ion battery is characterized by comprising the following steps of:
(1) Firstly, adding deionized water into organic sodium and organic phosphonic acid, stirring and dissolving to obtain a clear solution; then, adding a vanadium source, heating and stirring to obtain blue gel; continuously adding a titanium source and a manganese source, heating and stirring until the mixture is dry, and drying the obtained gel-like solid;
(2) Grinding the solid obtained after drying in the step (1), presintering under the protection of nitrogen, naturally cooling, taking out and grinding again, sintering under the protection of nitrogen, and naturally cooling to obtain the product of ternary phosphate/carbon (Na) serving as the positive electrode material of the sodium-ion battery 3 V x Mn 1-0.5x Ti 1-0.5x (PO 4 ) 3 Carbon, wherein x is more than or equal to 0.5 and less than or equal to 1.0.
2. The method for synthesizing ternary phosphate/carbon as the positive electrode material of the sodium-ion battery as claimed in claim 1, wherein in the step (1), the ratio of the raw materials is that the molar ratio of sodium to vanadium to manganese to titanium to phosphonic acid is 3 (x) (1-0.5 x) to 3,0.5 x is less than or equal to 1.0.
3. The method for synthesizing ternary phosphate/carbon as the positive electrode material of the sodium-ion battery as claimed in claim 1, wherein in the step (1), the organic sodium is trisodium citrate or sodium gluconate; the organic phosphonic acid is amino trimethylene phosphonic acid or hydroxy ethylidene diphosphonic acid; the vanadium source is ammonium metavanadate or sodium metavanadate; the manganese source is manganese acetate, manganese carbonate or manganese oxalate; the titanium source is titanium dioxide or tetrabutyl titanate.
4. The method for synthesizing ternary phosphate/carbon as a positive electrode material of a sodium-ion battery according to claim 1, wherein the heating temperature in the step (1) is 80 ℃ to 100 ℃.
5. The method for synthesizing ternary phosphate/carbon as a positive electrode material of a sodium-ion battery according to claim 1, wherein in the step (1), the drying treatment conditions are as follows: drying the mixture in an oven at the temperature of between 80 and 100 ℃ for 5 to 12 hours.
6. The method for synthesizing ternary phosphate/carbon as the positive electrode material of the sodium-ion battery according to claim 1, wherein in the step (2), the presintering conditions are as follows: pre-sintering for 2-6 h under the protection of argon at 300-400 ℃.
7. The method for synthesizing ternary phosphate/carbon as the positive electrode material of the sodium-ion battery according to claim 1, wherein in the step (2), the sintering condition is as follows: sintering for 8-12 h under the protection of argon at 500-800 ℃.
8. A sodium ion battery positive electrode material ternary phosphate/carbon, characterized in that it is obtained by the synthesis method according to any one of claims 1 to 7.
9. A sodium-ion battery comprising the positive electrode material Na for a sodium-ion battery according to claim 8 3 V x Mn 1- 0.5x Ti 1-0.5x (PO 4 ) 3 (iii) carbon.
CN202211011040.7A 2022-08-23 2022-08-23 Ternary phosphate/carbon as positive electrode material of sodium-ion battery, synthetic method of ternary phosphate/carbon and sodium-ion battery Withdrawn CN115483372A (en)

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CN115849328A (en) * 2022-12-26 2023-03-28 中国科学技术大学 Sodium vanadium titanium phosphate, preparation method and application thereof

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115849328A (en) * 2022-12-26 2023-03-28 中国科学技术大学 Sodium vanadium titanium phosphate, preparation method and application thereof

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