CN114242972A - Nickel-rich high-voltage sodium ion battery positive electrode material and preparation method and application thereof - Google Patents

Nickel-rich high-voltage sodium ion battery positive electrode material and preparation method and application thereof Download PDF

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CN114242972A
CN114242972A CN202111424144.6A CN202111424144A CN114242972A CN 114242972 A CN114242972 A CN 114242972A CN 202111424144 A CN202111424144 A CN 202111424144A CN 114242972 A CN114242972 A CN 114242972A
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sodium
nickel
sulfate
sodium ion
positive electrode
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余海军
张学梅
谢英豪
李爱霞
钟应声
李长东
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Priority to GB2313956.1A priority patent/GB2619230A/en
Priority to PCT/CN2022/115953 priority patent/WO2023093180A1/en
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    • H—ELECTRICITY
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Abstract

The invention belongs to the technical field of sodium ion batteries, and discloses a nickel-rich high-voltage sodium ion positive electrode material, and a preparation method and application thereof, wherein the general formula of the sodium ion positive electrode material is NasNit(PO4)(SO4) (ii) s is more than or equal to 2 and less than or equal to 4, and t is more than or equal to 0.5 and less than or equal to 1.5; m is at least one oxide of zinc, nickel, aluminum, manganese, chromium, molybdenum, manganese, copper and calcium. The stabilizer is added into the sodium ion anode material, so that the structural stability of the anode material is enhanced, and the cyclic discharge performance of the material is improved; the coating layer (formed by tightly combining the metal oxide and the anode material) in the sodium ion anode material can stabilize the ion and electron transmission dynamic performance of the material, improve the cycle performance of the anode material, prevent the material from continuously agglomerating and control the particle size.

Description

Nickel-rich high-voltage sodium ion battery positive electrode material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a nickel-rich high-voltage sodium ion battery positive electrode material, and a preparation method and application thereof.
Background
Lithium ion batteries have satisfactory properties such as high energy density and excellent cycle life, and are successfully applied to mobile electronic devices, electric and energy storage power for transportation, and the like. Currently, thanks to the vigorous development of new energy, lithium battery energy storage devices in the fields of Hybrid Electric Vehicles (HEV), Electric Vehicles (EV), smart grids, and the like are in more demand. The current problem is that lithium and the material costs associated with lithium battery manufacturing are rising dramatically, leading to an increase in the price of lithium ion batteries, and thus insufficient resource prospects and maldistribution of lithium have prompted research into more sustainable and less costly and more profitable options.
A sodium ion battery would be a suitable alternative. Sodium is more abundant in the crust; the standard redox potential of sodium is only 0.326V higher than that of lithium metal, and its electronegativity is only 0.05V lower than that of lithium, but the theoretical specific mass capacity of lithium is (3860mAh g)-1) Theoretical specific volumetric capacity (2060mAh cm)-3) Are all far higher than the theoretical specific capacity (1160 mAh.g) of sodium-1) Theoretical volumetric specific capacity (1130mAh cm)-3) It can be seen that the performance of the sodium ion battery is inferior to that of the lithium ion battery, therefore, since 2001, researchers have conducted a great deal of research on improving the electrochemical performance of sodium, such as developing high-performance electrode materials, providing superior working voltage, ascertaining the decomposition reaction and formation products of the electrode in the electrolyte, and enhancing the electrochemistryThe cycling stability and other aspects are beneficial to solving the problems of energy density and service life of the sodium ion battery.
In recent years, with the continuous rise of the price of lithium ion batteries, especially the consumption of lithium resources and the shortage of lithium in the world, the difficulty of lithium shortage has to be faced in the future, and researches have found that sodium with similar chemical properties to lithium is very expected to become a next-generation secondary battery following the lithium ion batteries, but as the radius of sodium ions is larger, the atomic weight is heavier, and the standard potential of sodium is higher, which generally results in poorer reversible capacity and lower energy density, the performance of the sodium ion batteries is generally inferior to that of the lithium ion batteries, and the electrochemical performances of various aspects such as the capacity, voltage, cycling capacity and the like of iron-sodium phosphate positive electrode materials are lower than that of the iron-lithium phosphate positive electrode materials.
At present, Na4MP2O7(M＝Fe、Co、Mn、Cu、PO4、SO4、CO3) Polyanion anode material can be more than 3.5V (vs Na)+Na) and exhibits excellent cycle stability, and is a very potential positive electrode material. For example, Na4Co3(PO4)2P2O7It is in the range of 3.0-4.4V (vs Na)+Na) voltage window at 0.2C rate to provide 95mAh g-1And capacity retention rate in 100 cycles>95％；Na4Fe3(PO4)2(P2O7) The product releases 129mAh g as the positive electrode material of sodium ion battery-1And the average operating voltage exceeds 3.2V (vs Na)+Na) electrode, but for Na4MPO4For the sodium ion battery, the energy density is low, the cycle performance is poor and still is the maximum short plate, and the energy density of the battery depends on the specific capacity and the working voltage of the material, so the research and development of a positive electrode material with high specific capacity and high first working voltage is urgently needed.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art described above. Therefore, the invention provides a nickel-rich high-voltage sodium ion positive electrode material, and a preparation method and application thereof, wherein the sodium ion positive electrode material has excellent cycle performance, high specific capacity and a first working voltage of 3.8V.
In order to achieve the purpose, the invention adopts the following technical scheme:
a sodium ion anode material with a general formula of NasNit(PO4)(SO4) (ii) s is more than or equal to 2 and less than or equal to 4, and t is more than or equal to 0.5 and less than or equal to 1.5; and M is at least one oxide of zinc, nickel, aluminum, manganese, chromium, molybdenum, manganese, copper and calcium.
Preferably, s is greater than or equal to 2.5 and less than or equal to 3.5, and t is greater than or equal to 0.5 and less than or equal to 1.2.
Preferably, the sodium ion cathode material has the formula of Na2.6Ni1.2(PO4)(SO4)/F@Al2O3-C、Na3.4Ni0.8(PO4)(SO4)/F@CuO-C、Na3Ni(PO4)(SO4) At least one of/F @ ZnO-C.
A preparation method of a sodium ion cathode material comprises the following steps:
mixing a nickel source solution, a sulfuric acid source, a phosphoric acid source and a fluorine source, carrying out microwave hydrothermal reaction, and concentrating to obtain a triphosphate precursor;
mixing the tri-acid salt precursor with a sodium source and a stabilizer, and heating for reaction to obtain NasNit(PO4)(SO4)/F；
To the NasNit(PO4)(SO4) and/F, adding a sodium washing agent for infiltration, and sintering to obtain the sodium ion anode material.
Preferably, the nickel source solution is obtained by mixing a nickel source with an organic acid.
Further preferably, the organic acid is at least one of tartaric acid, oxalic acid, citric acid, formic acid or acetic acid.
Further preferably, the concentration of the organic acid is 0.01 to 12 wt%.
Further preferably, the nickel source is at least one of nickel sulfate, nickel hydroxide, nickel nitrate, nickel chloride or nickel carbonate.
Preferably, the sulfuric acid source is at least one of sulfuric acid, sodium sulfate, ammonium bisulfate, sodium bisulfate, or nickel sulfate.
Preferably, the phosphoric acid source is at least one of phosphoric acid, sodium phosphate, ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate, sodium hydrogen phosphate, or nickel phosphate.
Preferably, the fluorine source is at least one of ammonium fluoride, potassium fluoride, sodium fluoride or hydrogen fluoride.
Preferably, the temperature of the microwave hydrothermal reaction is 100-300 ℃, and the time of the microwave hydrothermal reaction is 1-60 min; the temperature is preferably 120 ℃ to 240 ℃ and the time is preferably 5 to 300 min.
Preferably, the concentration further comprises wetting and drying the triacid precursor.
Preferably, the mixing further comprises ball milling the triacid precursor for 0.5-12h, wherein the size of the particles after ball milling is less than 50 μm.
Preferably, the sodium source is at least one of sodium hydroxide, sodium citrate, sodium oxalate, sodium acetate, sodium phosphate, sodium sulfate, sodium carbonate or sodium chloride.
Preferably, the stabilizer is 1, 4-phthalic acid, 2, 5-dipropyloxy-1, 4-dihydrazide, N ' -tetrakis (4-methoxyphenyl) -9H-carbazole-3, 6-diamine, 4', 4-trimethyl-2, 2 ': at least one of 6', 2-terpyridine.
Preferably, the stabilizer is 0.01-5 wt% of the total mass of the triacid precursor and the sodium source.
Preferably, the soaking is followed by drying, wherein the drying temperature is 60-150 ℃.
Preferably, the temperature of the heating reaction is 300-800 ℃, and the time of the heating reaction is 0.5-24 h.
Preferably, the NasNit(PO4)(SO4) The solid-liquid ratio of the/F to the sodium washing agent is (0.1-3): (1-5) g/ml.
Preferably, the sodium washing agent is at least one of zinc sulfate, nickel sulfate, aluminum sulfate, manganese sulfate, chromium sulfate, molybdenum sulfate, copper sulfate or calcium sulfate.
On one hand, the sodium washing agent can wash away residual sodium hydroxide on the surface of the anode material, reduce residual sodium in the anode material and reduce side reactions on the surface of the anode material. On the other hand, sodium ions in sodium hydroxide on the surface of the positive electrode material are exchanged by acid salt, part of metal ions are added to be hydrolyzed and deposited on the surface of the positive electrode material, and after drying, dehydration is carried out to change into metal oxide to be deposited on the surface of the positive electrode material.
Preferably, the sintering temperature is 400-800 ℃, and the sintering atmosphere is inert gas.
A battery comprises the sodium ion positive electrode material.
Preferably, the voltage of a working platform of a battery prepared from the sodium ion cathode material during initial discharge is greater than 3.8V.
Compared with the prior art, the invention has the following beneficial effects:
1. the stabilizer is added into the sodium ion anode material, so that the structural stability of the anode material is enhanced, and the cyclic discharge performance of the material is improved; the coating layer in the sodium ion anode material (after the treatment of sodium washing agent, metal ions are hydrolyzed and deposited on the surface of the anode material, and after dehydration, the metal ions become metal oxide, and the metal oxide is tightly combined with the anode material), can improve the ion and electron transmission dynamic performance of the material, improve the cycle performance of the anode material, prevent the nickel-rich high-pressure sodium ion anode material from continuously agglomerating and growing up, and control the particle size.
2. According to the preparation method, the distribution of internal particles of the trisalt precursor synthesized by a microwave method is more uniform, so that the consistency of electron transmission rate and heat transfer efficiency of each position in the prepared nickel-rich high-voltage anode material is high, and the stability of the internal structure of the material is facilitated; and the stable structure and good heat dissipation characteristic of the stabilizer are utilized, and the stabilizer is added into the anode material, so that the structural stability of the anode material is enhanced, and the cyclic discharge performance of the material is improved.
3. When the nickel-rich high-pressure sodium ion positive electrode material precursor is prepared, the temperature of the tris-salt precursor is quickly raised by utilizing microwave synthesis, and the reaction can be completed within 3-20min generally, so that the reaction process is quick, and the reaction time is shortened by more than 90%; moreover, the synthesis temperature is controlled at 300 ℃ of 100-; under the controllable electromagnetic environment, the crystal nucleus and the growth of the tri-acid salt precursor are accelerated, the crystal grain appearance is controllable, and meanwhile, the uniformity of the tri-acid salt precursor is better, so that the synthesis of the material with high crystallinity and uniform and complete particles is facilitated.
Drawings
FIG. 1 is a process flow diagram for preparing a sodium ion positive electrode material according to example 1 of the present invention;
FIG. 2 is a schematic diagram of a sodium ion positive electrode material prepared in example 1 of the present invention;
FIG. 3 is an SEM image of a sodium ion cathode material prepared in example 1 of the present invention;
fig. 4 is a TEM image of the sodium ion positive electrode material prepared in example 1 of the present invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
Example 1
The positive electrode material of the present example was Na2.6Ni1.2(PO4)(SO4)/F@Al2O3-C。
A process flow diagram of the sodium ion cathode material prepared in this embodiment is shown in fig. 1, nickel hydroxide and citric acid are mixed to obtain a solution a, ammonium sulfate, phosphoric acid and ammonium fluoride are mixed to obtain a solution B, the solution B is stirred, the solution B is added to the solution a to obtain a solution C, the solution C is placed in a ceramic crucible, and the ceramic crucible is sent to a microwave reactor, heated and cooled to obtain a trisalt precursor. Ball milling the precursor of the triacid, mixing with sodium hydroxide, N, N, N',evenly mixing the N' -tetra (4-methoxyphenyl) -9H-carbazole-3, 6-diamine slurry, and heating to obtain Na2.6Ni1.2(PO4)(SO4) and/F. Aluminum sulfate and Na2.6Ni1.2(PO4)(SO4) Soaking in/F, heating, and cooling to obtain Na2.6Ni1.2(PO4)(SO4)/F@Al2O3-C。
The specific steps for preparing the sodium ion cathode material of the embodiment are as follows:
(1) microwave hydrothermal synthesis of a trisalt precursor: mixing 1.12g of nickel hydroxide and 150 mL5.5w% of citric acid to obtain a solution A, mixing 19mL0.53mol/L of ammonium sulfate, 14.9mL0.67mol/L of phosphoric acid and 9mL0.17mol/L of ammonium fluoride to obtain a solution B, stirring, gradually dropwise adding the solution B into the solution A to obtain a solution C, taking 20mL of the solution C, placing the solution C in a ceramic crucible, conveying to a microwave reactor, filling argon into the microwave reactor, and setting under 350W: and (3) heating for the first time to 110 ℃, stably evaporating for 6min, heating for the second time to 275 ℃, stably evaporating for 25min, and cooling to obtain a triacid precursor, wherein the temperature rise time between the two sections is 180 s.
(2) Synthesis of Na2.6Ni1.2(PO4)(SO4) F: ball-milling the triacid precursor for 7.5H, then stirring and uniformly mixing with 17.5mL of 1.5mol/L sodium hydroxide and 18 mL1.66wt% of N, N, N ', N' -tetra (4-methoxyphenyl) -9H-carbazole-3, 6-diamine slurry, heating for 8H at 300 ℃ in a heating furnace under the argon environment to obtain a sodium ion anode material Na2.6Ni1.2(PO4)(SO4)/F。
(3) Sodium washing treatment: 4.5mL of 0.019mol/L aluminum sulfate was divided equally into three parts, and 1.5g of Na ion positive electrode material2.6Ni1.2(PO4)(SO4) Mixing and infiltrating for three times, drying in an oven at 110 ℃ for 10h overnight, sintering in a heating furnace under argon environment at 470 ℃ for 8h, and cooling to obtain a sodium ion anode material-Na2.6Ni1.2(PO4)(SO4)/F@Al2O3-C。
Example 2
The positive electrode material of sodium ion of the present example has the formulaIs Na3.4Ni0.8(PO4)(SO4)/F@CuO-C。
The preparation method of the sodium ion cathode material of the embodiment comprises the following specific steps:
(1) microwave hydrothermal synthesis of a trisalt precursor: dissolving 1.24g of nickel sulfate in 150 mL7.1w% of oxalic acid to obtain a solution A, mixing 19mL0.53mol/L of ammonium sulfate, 1.33g of diammonium phosphate and 12mL0.18mol/L of ammonium fluoride to obtain a solution B, stirring, gradually dropwise adding the solution B into the solution A to obtain a solution C, taking 20mL of the solution C, placing the solution C in a ceramic crucible, conveying the ceramic crucible to a microwave reactor, filling argon into the microwave reactor, and setting the following conditions under the condition of 500W: and (3) heating for the first time to 115 ℃, stabilizing for 3min, heating for the second time to 240 ℃, stabilizing for 20min, and cooling to obtain a triacid precursor, wherein the temperature rise time between the two sections is 180 s.
(2) Synthesis of Na3.4Ni0.8(PO4)(SO4) F: ball-milling the tri-acid salt precursor to particle size<50 mu m, 22.7mL of 1.5mol/L sodium hydroxide, 18 mL1.5wt% 1, 4-phthalic acid and 2, 5-dipropyloxy-1, 4-dihydrazide slurry are stirred and mixed uniformly, and the mixture is heated for 6.5h at 540 ℃ under the argon atmosphere of a heating furnace to obtain a sodium ion cathode material-Na3.4Ni0.8(PO4)(SO4)/F。
(3) Sodium washing treatment: 4.5mL of 0.032mol/L copper sulfate were divided equally into three portions, and 1.5g of Na ion positive electrode material3.4Ni0.8(PO4)(SO4) Mixing and soaking for three times, drying in an oven at 150 ℃ for 4h, sintering in a heating furnace at 590 ℃ for 6.5h in an argon environment, and cooling to obtain a sodium ion anode material-Na3.4Ni0.8(PO4)(SO4)/F@CuO-C。
Example 3
The positive electrode material of the present example was Na3Ni(PO4)(SO4)/F@ZnO-C。
The preparation method of the sodium ion cathode material of the embodiment comprises the following specific steps:
(1) microwave hydrothermal synthesis of a trisalt precursor: dissolving 1.3g of nickel chloride in 500 mL0.317mol/Lw% citric acid to obtain a solution A, mixing 19mL0.53mol/L ammonium sulfate, 1.33g of diammonium phosphate and 17mL0.18mol/L ammonium fluoride to obtain a solution B, stirring, gradually dropwise adding the solution B into the solution A to obtain a solution C, taking 200mL of the solution C, placing the solution C in a ceramic crucible, conveying to a microwave reactor, filling argon into the microwave reactor, and setting under 350W: and (3) carrying out primary heating at 115 ℃, carrying out stable evaporation for 3min, carrying out secondary heating at 275 ℃, carrying out stable evaporation for 20min, and carrying out temperature rise for 180s between the two sections, and cooling to obtain a triphosphate precursor.
(2) Synthesis of Na3Ni(PO4)(SO4) F: ball milling the tri-acid salt precursor to particle size<50 μm, with 20mL of 1.5mol/L sodium hydroxide, 22mL of 1.5 wt% 4,4', 4-trimethyl-2, 2': stirring and uniformly mixing the 6', 2-terpyridine slurry, and heating for 8 hours at the set temperature of 620 ℃ in a heating furnace under the argon environment to obtain a sodium ion anode material Na3Ni(PO4)(SO4)/F。
(3) Sodium washing treatment: 6mL of 0.063mol/L zinc sulfate was divided equally into three portions, and 2.0g of Na ion as a positive electrode material3Ni(PO4)(SO4) Mixing and infiltrating for three times, drying for 3h at 125 ℃ in an oven, sintering for 6.5h at 470 ℃ in a heating furnace under the argon environment, and cooling to obtain a sodium ion anode material-Na3Ni(PO4)(SO4)/F@ZnO-C。
Comparative example 1
The positive electrode material of this comparative example, which has the formula Na3.4Ni0.8(PO4)(SO4)/F@Al2O3。
The preparation method of the sodium ion cathode material of the comparative example comprises the following specific steps:
(1) microwave hydrothermal synthesis of a trisalt precursor: dissolving 1.24g of nickel sulfate in 50 mL5.5w% of citric acid to obtain a solution A, mixing 19mL0.53mol/L of ammonium sulfate, 16mL0.67mol/L of phosphoric acid and 12mL0.18mol/L of ammonium fluoride to obtain a solution B, stirring, gradually dropwise adding the solution B into the solution A to obtain a solution C, taking 200mL of the solution C, placing the solution C in a ceramic crucible, heating for 8 hours at the temperature of 540 ℃ in an argon environment, and cooling to obtain a triacid precursor.
(2) Synthesis of Na3.4Ni0.8(PO4)(SO4) F: ball milling the tri-acid salt precursor to particle size<50 μm, with 22.7mL of 1.5mol/L sodium hydroxide, 18mL1.5 wt% of 4,4', 4-trimethyl-2, 2': stirring and mixing the 6', 2-terpyridine slurry uniformly, mixing uniformly, heating for 6.5h at 540 ℃ in a heating furnace under the argon environment to obtain a sodium ion anode material-Na3.4Ni0.8(PO4)(SO4)/F-C。
Comparative example 2
The positive electrode material of this comparative example, which has the formula Na3.4Ni0.8(PO4)(SO4)/F@Al2O3。
The preparation method of the sodium ion cathode material of the comparative example comprises the following specific steps:
(1) microwave hydrothermal synthesis of a trisalt precursor: dissolving 1.24g of nickel sulfate in 50 mL5.5w% of citric acid to obtain a solution A, mixing 19mL0.53mol/L of ammonium sulfate, 1.42g of diammonium hydrogen phosphate and 12mL0.18mol/L of ammonium fluoride to obtain a solution B, stirring, gradually dropwise adding the solution B into the solution A to obtain a solution C, taking 200mL of the solution C, placing the solution C in a ceramic crucible, heating for 8 hours at the temperature of 540 ℃ in an argon environment, and cooling to obtain a triacid precursor.
(2) Synthesis of Na3.4Ni0.8(PO4)(SO4) F: ball milling the tri-acid salt precursor to particle size<50 mu m, and is uniformly mixed with 22.7mL of 1.5mol/L sodium hydroxide, and the mixture is heated for 6.5h at 540 ℃ in a heating furnace under the argon environment to obtain a sodium ion cathode material Na3.4Ni0.8(PO4)(SO4)/F。
(3) Sodium washing treatment: 6mL of 0.022mol/L aluminum sulfate was divided equally into three portions, and 2.0g of Na ion as a positive electrode material3.4Ni0.8(PO4)(SO4) Mixing and infiltrating the mixture with/F for three times, drying the mixture in an oven at 95 ℃ to constant weight, sintering the mixture for 6.5 hours at 540 ℃ in a heating furnace under the argon environment, and cooling to obtain a sodium ion anode material-Na3.4Ni0.8(PO4)(SO4)/F@Al2O3。
Comparative example 3
The sodium ion positive electrode material of this comparative example has the formulaNa3Ni(PO4)(SO4)/F。
The preparation method of the sodium ion cathode material of the comparative example comprises the following specific steps:
(1) microwave hydrothermal synthesis of a trisalt precursor: dissolving 1.55g of nickel sulfate in 50 mL5.5w% of citric acid to obtain a solution A, mixing 19mL0.53mol/L of ammonium sulfate, 1.53g of diammonium hydrogen phosphate and 12mL0.18mol/L of ammonium fluoride to obtain a solution B, stirring, gradually dropwise adding the solution B into the solution A to obtain a solution C, taking 200mL of the solution C, placing the solution C in a ceramic crucible, conveying the ceramic crucible to a microwave reactor, filling argon into the microwave reactor, and setting under 350W: and (3) heating for the first time to 90 ℃, stably evaporating for 6min, heating for the second time to 275 ℃, stably evaporating for 25min, and cooling to obtain a triacid precursor, wherein the temperature rise time between the two sections is 180 s.
(2) Synthesis of Na3Ni(PO4)(SO4) F: ball milling the tri-acid salt precursor to particle size<50 mu m, and 20mL of 1.5mol/L sodium hydroxide, drying in an oven at 125 ℃ for 3h, heating in a heating furnace under argon atmosphere at 540 ℃ for 8h to obtain a sodium ion anode material-Na3Ni(PO4)(SO4)/F。
Examples 1-3 and comparative examples 1-3 were analyzed:
the sodium ion positive electrode material prepared in the examples 1-3 and the comparative examples 1-3, the carbon black conductive agent and the polytetrafluoroethylene are mixed according to the mass ratio of 80: 10: 10 mixing and dissolving in deionized water to prepare slurry, then coating the slurry on an aluminum foil to form a pole piece, drying the pole piece in a drying box at 80 ℃ for 12 hours, and stamping a die to prepare a wafer; cutting the wafer into a counter electrode pole piece with the diameter of 10 mm; adding 1.0mol/L NaClO into carbonate4For the electrolyte, Celgard2400 was a separator, and the cell assembly was performed in a vacuum glove box under an argon atmosphere. Performing AC impedance and cyclic voltammetry tests on the button cell by using an electrochemical workstation, performing charge and discharge tests on the button cell by using a LAND cell test system, wherein the tested current density is 30 mA.g-1。
Table 1 battery test data obtained for positive electrode materials prepared in examples 1 to 3 and comparative examples 1 to 3
Figure BDA0003377557520000081
In Table 1, the first discharge capacity of examples 1 to 3 was 128.3 to 132.6mAh g-1The platform voltage is 3.8V during the first discharge, and the first discharge capacity of comparative examples 1 to 3 is 115.6 to 117.7 mAh.g-1The platform voltage is 3.6-3.7V during the first discharge, and when the 100 th discharge occurs; the discharge capacity of examples 1 to 3 was still 107.5 to 108.7mAh g-1Comparative examples 1 to 3 had initial discharge capacities of 89.8 to 93.2 mAh.g-1(ii) a The first, 10 th and 100 th discharge efficiencies of the batteries obtained from the positive electrode materials prepared in examples 1 to 3 were also higher than those of the batteries obtained from the positive electrode materials prepared in comparative examples 1 to 3. Shows that the electrochemical performance of the nickel-rich high-pressure sodium ion positive electrode material is improved after the soaking treatment by microwave hydrothermal, adding a stabilizer and a sodium washing agent
In fig. 2 and 4, a layer of alumina is adhered to the surface of the sodium ion positive electrode material prepared in example 1 and is tightly combined with the sodium ion positive electrode material, and the surface of the nickel-rich high-pressure sodium ion positive electrode material in fig. 3 is rough and has a particle size of about 12 μm.
The embodiments of the present invention have been described in detail with reference to the accompanying drawings, but the present invention is not limited to the above embodiments, and various changes can be made within the knowledge of those skilled in the art without departing from the gist of the present invention. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.

Claims (10)

1. The sodium ion positive electrode material is characterized in that the general formula of the sodium ion positive electrode material is NasNit(PO4)(SO4) (ii)/F @ M-C; and M is at least one oxide of zinc, nickel, aluminum, manganese, chromium, molybdenum, manganese, copper and calcium, wherein s is more than or equal to 2 and less than or equal to 4, and t is more than or equal to 0.5 and less than or equal to 1.5.
2. The sodium ion positive electrode material according to claim 1, wherein s is in a range of 2.5. ltoreq. s.ltoreq.3.5, and t is in a range of 0.5. ltoreq. t.ltoreq.1.2.
3. The method for producing a sodium ion positive electrode material according to any one of claims 1 to 2, characterized by comprising the steps of:
mixing a nickel source solution, a sulfuric acid source, a phosphoric acid source and a fluorine source, carrying out microwave hydrothermal reaction, and concentrating to obtain a triphosphate precursor;
mixing the tri-acid salt precursor with a sodium source and a stabilizer, and heating for reaction to obtain NasNit(PO4)(SO4)/F；
To the NasNit(PO4)(SO4) and/F, adding a sodium washing agent for infiltration, and sintering to obtain the sodium ion anode material.
4. The method according to claim 3, wherein the nickel source solution is obtained by dissolving a nickel source in an organic acid; the organic acid is at least one of tartaric acid, oxalic acid, citric acid, formic acid and acetic acid; the nickel source is at least one of nickel sulfate, nickel hydroxide, nickel nitrate, nickel chloride or nickel carbonate.
5. The production method according to claim 3, wherein the sulfuric acid source is at least one of sulfuric acid, sodium sulfate, ammonium bisulfate, sodium bisulfate, or nickel sulfate.
6. The method of claim 3, wherein the phosphoric acid source is at least one of phosphoric acid, sodium phosphate, ammonium phosphate, diammonium phosphate, ammonium dihydrogen phosphate, sodium hydrogen phosphate, or nickel phosphate.
7. The production method according to claim 3, wherein the fluorine source is at least one of ammonium fluoride, potassium fluoride, sodium fluoride, or hydrogen fluoride; the sodium source is at least one of sodium hydroxide, sodium citrate, sodium oxalate, sodium acetate, sodium phosphate, sodium sulfate, sodium carbonate or sodium chloride; the stabilizer is 1, 4-phthalic acid, 2, 5-dipropyloxy-1, 4-dihydrazide, N, N, N ', N' -tetra (4-methoxyphenyl) -9H-carbazole-3, 6-diamine, 4', 4-trimethyl-2, 2': at least one of 6', 2-terpyridine.
8. The preparation method according to claim 3, wherein the temperature of the microwave hydrothermal reaction is 100 ℃ and 300 ℃, and the time of the microwave hydrothermal reaction is 1-60 min; the Na issNit(PO4)(SO4) The solid-liquid ratio of the/F to the sodium washing agent is (0.1-3): (1-5) g/ml.
9. The method according to claim 3, wherein the sodium washing agent is at least one of zinc sulfate, nickel sulfate, aluminum sulfate, manganese sulfate, chromium sulfate, molybdenum sulfate, copper sulfate, or calcium sulfate.
10. A battery comprising the sodium ion positive electrode material according to any one of claims 1 to 2.
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