ZnSnO3Preparation method of nanorod material and energy storage application thereof
阅读说明：本技术 一种ZnSnO3纳米棒材料的制备方法及其储能应用 (ZnSnO3Preparation method of nanorod material and energy storage application thereof ) 是由 余佳阁 余链 操京峰 丁瑜 王�锋 杨雄 王丽 于 2021-08-05 设计创作，主要内容包括：本发明属于钠离子电池技术领域,具体公开了一种ZnSnO-(3)纳米棒材料的制备方法及其储能应用。本发明采用微波水热法制备得到了ZnSnO-(3)纳米棒材料,具体方法为：将氢氧化钠、锡源和锌源在冰浴条件下混合,然后在一定的微波水热条件下得到前驱体ZnSn(OH)-(6),再将所得前驱体ZnSn(OH)-(6)置于管式炉中,在惰性气氛保护下,升温至300-600℃,保温2-10h,得到ZnSnO-(3)纳米棒材料。该ZnSnO-(3)纳米棒材料应用于钠离子电池负极材料时,具有容量高、循环稳定性能好的特点,该材料在0.1 A·g～(-1)的电流密度下,电化学性能稳定,循环100周后,比容量仍保持在430 mAh·g～(-1),库伦效率接近100%。(The invention belongs to the technical field of sodium ion batteries, and particularly discloses ZnSnO 3 A preparation method of a nano rod material and an energy storage application thereof. The invention adopts a microwave hydrothermal method to prepare ZnSnO 3 The method for preparing the nano rod material comprises the following steps: mixing sodium hydroxide, a tin source and a zinc source under an ice-bath condition, and then obtaining a precursor ZnSn (OH) under a certain microwave hydrothermal condition 6 Then, the precursor ZnSn (OH) obtained was added 6 Arranged in a tube furnaceHeating to 600 ℃ under the protection of inert atmosphere, and preserving heat for 2-10h to obtain ZnSnO 3 A nanorod material. The ZnSnO 3 When the nano rod material is applied to the cathode material of the sodium ion battery, the material has the characteristics of high capacity and good cycle stability, and the material is 0.1 A.g ‑1 The electrochemical performance is stable under the current density of (2), and the specific capacity is still maintained at 430mAh g after the circulation for 100 weeks ‑1 Coulombic efficiency approaches 100%.)
1. ZnSnO3The preparation method of the nano rod material is characterized by comprising the following steps of:
s1, dissolving sodium hydroxide and a tin source in water, stirring for 0.5-1h under an ice bath condition, then slowly dropping a zinc source aqueous solution under a continuous stirring condition into a reactor, after dropping, continuously stirring the mixed solution under the ice bath condition for 12-24h, then transferring the mixed solution into a microwave reactor, setting the power at 100 and 1000W, heating to 110 and 300 ℃, preserving the temperature for 2-20h to obtain a turbid solution, washing the turbid solution by deionized water and absolute ethyl alcohol in a centrifugal mode, drying for 12-24h at 60-80 ℃ to obtain a precursor ZnSn (OH)6；
S2, preparing ZnSn (OH) as the precursor of S16Placing in a tube furnace under the protection of inert atmosphere at a temperature of 2-20 deg.C/minRaising the temperature to 600 ℃ at the temperature rising rate, and preserving the heat for 2-10h to obtain ZnSnO3A material;
s2 preparation of ZnSnO3The material is in a nano rod shape, and the diameter of the nano rod is 3-5 nm;
the tin source is at least one of tin dioxide, tin tetrachloride and sodium stannate;
the zinc source is at least one of zinc sulfate, zinc chloride, zinc carbonate, zinc nitrate and zinc oxalate.
2. The method of claim 1, wherein the temperature of S1 under ice bath conditions is 0-4 ℃; the zinc source is as follows: a tin source: the molar ratio of sodium hydroxide is 1: 1: (6.0-6.3); the concentration of the zinc source water solution is 0.1-0.5 mol/L; the dosage ratio of the tin source to the water in the S1 is 1 mmol: (15-25) mL.
3. The method according to claim 1, wherein the tin source is tin tetrachloride and the zinc source is zinc sulfate; the purities of the stannic chloride, the zinc sulfate and the sodium hydroxide are not lower than chemical purity.
4. The production method according to claim 2, wherein the concentration of the aqueous solution of the zinc source is 0.18 mol/L.
5. The preparation method according to claim 2, wherein the microwave hydrothermal conditions in S1 are as follows: setting the power at 200-500W, heating to 180-250 deg.C, and maintaining for 2-10 h.
6. The preparation method according to claim 2, wherein the microwave hydrothermal conditions in S1 are as follows: setting the power at 300W, heating to 180-250 ℃, and keeping the temperature for 2-10 h.
7. The preparation method according to claim 2, wherein the calcination process in S2 is as follows: under the protection of nitrogen, the temperature is raised to 500 ℃ at the temperature raising rate of 2-10 ℃/min, and the temperature is kept for 2-10 h.
8. The process of any of claims 1-7 to make ZnSnO3The nano-rod material is used as a negative electrode material to be applied to a sodium ion battery.
9. The application of claim 8, wherein in the specific application, the steps are as follows:
(1) conductive carbon black as conductive agent, polyvinylidene fluoride as binder and ZnSnO as active material3Mixing the nano-rods in an N, N-dimethyl pyrrolidone solvent according to the mass ratio of 20:20:60 to prepare slurry, then coating the slurry on a copper foil, drying and cutting the copper foil into electrode slices for later use;
(2) and (3) assembling the positive electrode shell, the electrode plate obtained in the step (1), the diaphragm, the sodium plate, the foamed nickel and the negative electrode shell, adding a proper amount of electrolyte, and packaging to obtain the sodium-ion half battery.
10. The use according to claim 9, wherein the membrane is a glass fiber membrane and the electrolyte is 1mol/L NaPF6/PC。
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to ZnSnO3A preparation method of a nano rod material and an energy storage application thereof.
Background
The zinc-tin oxide composite material has high theoretical capacity (1317mA · h/g) and high conductivity (2.5 multiplied by 10)2S/cm), low working potential, rich sources, low price and the like, and is a promising sodium-ion battery electrode material.
At present, the conventional method for preparing the zinc-tin-oxygen composite material is a hydrothermal method, and a sample obtained by the method has a cubic particle structure, is large in particle size, and is easy to agglomerate. When the material is applied to a sodium ion battery cathode material, the material has the problems of large volume expansion, poor combination with a binder and a conductive agent and the like, so that the circulation stability is poor and the reversible capacity is quickly attenuated.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide ZnSnO3A preparation method of a nano rod material and an energy storage application thereof. The invention adopts a microwave hydrothermal method to successfully obtain the rod-shaped ZnSnO3Nano material, ZnSnO of this morphology3The materials have not been reported. Rod-shaped ZnSnO3The material has the characteristics of uniform appearance and small size, and has excellent reversible capacity and cycling stability when being applied to a negative electrode material of a sodium-ion battery.
In order to achieve the purpose, the invention adopts the following technical scheme:
ZnSnO3The preparation method of the nano rod material comprises the following steps:
s1, dissolving sodium hydroxide and a tin source inStirring in water for 0.5-1h under ice bath condition, slowly droping the zinc source aqueous solution under continuous stirring condition, adding the zinc source aqueous solution into a reactor, after dripping, continuously stirring the mixed solution under ice bath condition for 12-24h, transferring the mixed solution into a microwave reactor, setting the power at 100-1000W, heating to 110-300 ℃, preserving the heat for 2-20h to obtain turbid solution, washing the turbid solution with deionized water and absolute ethyl alcohol in a centrifugal mode, drying at 60-80 ℃ for 12-24h to obtain a precursor ZnSn (OH)6；
S2, preparing ZnSn (OH) as the precursor of S16Placing in a tube furnace, heating to 300-600 ℃ at a heating rate of 2-20 ℃/min under the protection of inert atmosphere (such as nitrogen, and the like), and keeping the temperature for 2-10h to obtain ZnSnO3A material.
Further, ZnSnO obtained in S23The material is in a nano rod shape, and the diameter of the nano rod is 3-5 nm.
Further, the tin source is at least one of tin dioxide, tin tetrachloride and sodium stannate; preferably, the tin source is tin tetrachloride.
Further, the zinc source is at least one of zinc sulfate, zinc chloride, zinc carbonate, zinc nitrate and zinc oxalate; preferably, the zinc source is zinc sulfate.
Preferably, the tin source is tin tetrachloride (SnCl)4·5H2O), the zinc source is zinc sulfate (ZnSO)4·7H2O); the purities of the stannic chloride, the zinc sulfate and the sodium hydroxide are not lower than chemical purity.
Further, the tin source: the molar ratio of the zinc source is 1: 1.
further, the concentration of the zinc source water solution is 0.1-0.5 mol/L; preferably, the concentration of the zinc source aqueous solution is 0.18 mol/L.
Further, the zinc source: a tin source: the molar ratio of sodium hydroxide is 1: 1: (6.0-6.3).
Further, the ratio of the tin source to the water in the S1 is 1 mmol: (15-25) mL.
Preferably, the microwave water heating power in S1 is 200-500W; more preferably, the microwave hydrothermal power is 300W.
Preferably, the microwave hydrothermal temperature in S1 is 180-250 ℃, and the heat preservation time is 2-10 h.
Most preferably, the microwave hydrothermal conditions in S1 are: setting the power at 300W, heating to 180-250 ℃, and keeping the temperature for 2-10 h.
Further, the temperature in S1 under ice bath conditions was 0 to 4 ℃.
Preferably, the calcination process in S2: heating to 300-500 ℃ at the heating rate of 2-10 ℃/min, and preserving the heat for 2-10 h.
The above ZnSnO3The nano-rod material is used as a negative electrode material to be applied to a sodium ion battery. In the specific application, the steps are as follows:
(1) using N, N-dimethyl pyrrolidone as solvent, and mixing conductive carbon black (super-P) as conductive agent, polyvinylidene fluoride (PVDF) as binder, and active material (ZnSnO above)3Nano rod material) is mixed and dissolved in a solvent according to the mass ratio of 20:20:60 to prepare slurry, then the slurry is coated on a copper foil, and the copper foil is dried under the vacuum condition of 80 ℃ and cut into electrode slices for standby;
(2) sequentially stacking the positive electrode shell, the electrode plate obtained in the step (1), the diaphragm, the sodium plate, the foamed nickel and the negative electrode shell, adding a proper amount of electrolyte, and packaging to assemble the sodium ion half-cell, wherein the cell shell can be of a CR2032 type, the diaphragm can be a glass fiber diaphragm, and the electrolyte can be 1mol/LNaPF6/PC。
Compared with the prior art, the invention has the advantages and beneficial effects that:
1. the invention adopts a microwave hydrothermal method to prepare ZnSnO3The nano rod material provides a new way for preparing a series of metal oxide nano rod materials.
2. Compared with the traditional ZnSnO3Materials, ZnSnO prepared by the invention3When the nano rod material is applied to the cathode material of the sodium ion battery, the material has the characteristics of high capacity and good cycle stability, and the material is 0.1 A.g-1The electrochemical performance is stable under the current density of (2), and the specific capacity is still maintained at 430mAh g after the circulation for 100 weeks-1Coulombic efficiency approaches 100%.
Drawings
FIG. 1 is a bar prepared in example 1 of the present inventionZnSnO3An X-ray diffraction (XRD) pattern of the nanomaterial;
FIG. 2 is a rod-shaped ZnSnO prepared in example 1 of the present invention3A Transmission Electron Microscope (TEM) image of the nanomaterial;
FIG. 3 is a rod-shaped ZnSnO prepared in example 1 of the present invention3The nano material is in the range of 0.1 A.g-1A plot of cycling performance at current density;
FIG. 4 is a cubic ZnSnO prepared in comparative example 1 of the present invention3Transmission Electron Microscopy (TEM) images of nanomaterials.
Detailed Description
The technical solution of the present invention is further illustrated by the following examples in conjunction with the accompanying drawings.
In the following examples and comparative examples, the starting materials used were: SnCl4·5H2O、ZnSO4·7H2O and sodium hydroxide are analytically pure. The ice bath conditions used were: adding ice blocks into a constant-temperature heating magnetic stirrer (DF-101S, consolidated City instruments Co., Ltd.), and controlling the temperature to be 0 ℃; the microwave reactor used: is a Uwave-2000 multifunctional microwave synthesis extraction instrument from Shanghai New Instrument microwave chemical technology Co.
Example 1
1.264g of SnCl at room temperature4·5H2O (3.6mmol) and 0.896g NaOH (22.4mmol) were dissolved in 70mL of ultrapure water and stirred continuously at 0 ℃ for 0.5h under ice-bath conditions; then 20mL of 0.18 mol. L were added with continued stirring-1(3.6mmol) of ZnSO4·7H2Slowly dripping O aqueous solution into a reaction container, continuously stirring the mixed solution for 12h under an ice bath condition after dripping, transferring the mixed solution into a microwave reactor, setting the power to be 300W, heating to 180 ℃, preserving the temperature for 5h to obtain turbid solution, washing the turbid solution for three times by deionized water and absolute ethyl alcohol in sequence in a centrifugal mode, and drying at 80 ℃ for 12h to obtain a precursor ZnSn (OH)6The resulting precursor ZnSn (OH)6Moving the mixture to a tube furnace, heating the mixture to 500 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, and preserving the heat for 2h to obtain white powdered ZnSnO3And (3) nano materials.
FIG. 1 is ZnSnO prepared in example 13The X-ray diffraction (XRD) pattern of the nano material completely corresponds to ZnSnO3The PDF card number of (1) is 28-1486; FIG. 2 is the ZnSnO prepared3Transmission Electron Microscope (TEM) image of the nanomaterial showing ZnSnO3Is in the shape of a nanorod, and the diameter of the nanorod is 3-5 nm.
Example 2
1.264g of SnCl at room temperature4·5H2Dissolving O and 0.896g NaOH in 70mL of ultrapure water, and continuously stirring for 0.5h under the condition of ice bath at 0 ℃; then 20mL of 0.18 mol. L were added with continued stirring-1ZnSO of4·7H2Slowly dripping O aqueous solution into the reaction container, stirring the mixed solution for 12h under the ice bath condition after dripping, transferring the mixed solution into a microwave reactor, setting the power at 300W, heating to 110 ℃, preserving the temperature for 8h to obtain turbid solution, washing the turbid solution for three times by deionized water and absolute ethyl alcohol in sequence in a centrifugal mode, and drying at 80 ℃ for 12h to obtain a precursor ZnSn (OH)6The resulting precursor ZnSn (OH)6Moving the mixture to a tube furnace, heating the mixture to 600 ℃ at the heating rate of 5 ℃/min in the nitrogen atmosphere, and preserving the heat for 2h to obtain white powdered ZnSnO3And (3) nano materials.
Example 3
1.264g of SnCl at room temperature4·5H2Dissolving O and 0.896g NaOH in 70mL of ultrapure water, and continuously stirring for 0.5h under the condition of ice bath at 0 ℃; then 20mL of 0.18 mol. L were added with continued stirring-1ZnSO of4·7H2Slowly dripping O aqueous solution into a reaction container, continuously stirring the mixed solution for 12h under an ice bath condition after dripping, transferring the mixed solution into a microwave reactor, setting the power to be 300W, heating to 250 ℃, preserving the temperature for 6h to obtain turbid solution, washing the turbid solution for three times by deionized water and absolute ethyl alcohol in sequence in a centrifugal mode, and drying at 80 ℃ for 12h to obtain a precursor ZnSn (OH)6The resulting precursor ZnSn (OH)6Moving to a tube furnace, heating to 300 ℃ at a heating rate of 10 ℃/min in a nitrogen atmosphere, and preserving heat for 3h to obtain whitePowdered ZnSnO toner3And (3) nano materials.
Example 4
1.264g of SnCl at room temperature4·5H2Dissolving O and 0.896g NaOH in 70mL of ultrapure water, and continuously stirring for 0.5h under the condition of ice bath at 0 ℃; then 20mL of 0.18 mol. L were added with continued stirring-1ZnSO of4·7H2Slowly dripping O aqueous solution into a reaction container, continuously stirring the mixed solution for 12h under an ice bath condition after dripping, transferring the mixed solution into a microwave reactor, setting the power at 300W, heating to 300 ℃, preserving the temperature for 5h to obtain turbid solution, washing the turbid solution for three times by deionized water and absolute ethyl alcohol in sequence in a centrifugal mode, and drying at 80 ℃ for 12h to obtain a precursor ZnSn (OH)6The resulting precursor ZnSn (OH)6Moving the mixture to a tube furnace, heating the mixture to 500 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, and preserving the heat for 6h to obtain white powdered ZnSnO3And (3) nano materials.
Example 5
1.264g of SnCl at room temperature4·5H2Dissolving O and 0.896g NaOH in 70mL of ultrapure water, and continuously stirring for 0.5h under the condition of ice bath at 0 ℃; then 20mL of 0.18 mol. L were added with continued stirring-1ZnSO of4·7H2Slowly dripping O aqueous solution into a reaction container, stirring the mixed solution for 12h under an ice bath condition after dripping, transferring the mixed solution into a microwave reactor, setting the power to be 1000W, heating to 180 ℃, preserving the temperature for 10h to obtain turbid solution, washing the turbid solution for three times by deionized water and absolute ethyl alcohol in sequence in a centrifugal mode, and drying at 80 ℃ for 12h to obtain a precursor ZnSn (OH)6The resulting precursor ZnSn (OH)6Moving the mixture to a tube furnace, heating the mixture to 500 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, and preserving the heat for 10 hours to obtain white powdered ZnSnO3And (3) nano materials.
Example 6
1.264g of SnCl at room temperature4·5H2Dissolving O and 0.896g NaOH in 70mL of ultrapure water, and continuously stirring for 0.5h under the condition of ice bath at 0 ℃; then 20mL of 0 was added with continued stirring.18mol·L-1ZnSO of4·7H2Slowly dripping O aqueous solution into a reaction container, stirring the mixed solution for 12h under an ice bath condition after dripping, transferring the mixed solution into a microwave reactor, setting the power at 100W, heating to 180 ℃, preserving the temperature for 10h to obtain turbid solution, washing the turbid solution for three times by deionized water and absolute ethyl alcohol in sequence in a centrifugal mode, and drying at 80 ℃ for 12h to obtain a precursor ZnSn (OH)6The resulting precursor ZnSn (OH)6Moving the mixture to a tube furnace, heating the mixture to 500 ℃ at the heating rate of 2 ℃/min in the nitrogen atmosphere, and preserving the heat for 10 hours to obtain white powdered ZnSnO3And (3) nano materials.
Comparative example 1
1.264g of SnCl at room temperature4·5H2Dissolving O and 0.896g NaOH in 70mL of ultrapure water, and magnetically stirring for 30min at the temperature of 0 ℃ under the ice bath condition; then 20mL of 0.18 mol. L were added with continued stirring-1ZnSO of4·7H2And slowly dropwise adding the O aqueous solution into the solution, and continuously stirring the mixed solution for 12 hours under the ice bath condition after dropwise adding. And then transferring the solution to a hydrothermal kettle, preserving heat for 12 hours at 180 ℃ to obtain turbid solution, washing the turbid solution by deionized water and absolute ethyl alcohol respectively for three times in a centrifugal mode, and drying the turbid solution for 12 hours at 80 ℃ to obtain a precursor. Then the obtained precursor is moved into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and the temperature is kept for 2h to obtain white powder ZnSnO3And (3) nano materials.
FIG. 4 is ZnSnO prepared in comparative example 13Transmission Electron Microscope (TEM) image of the nanomaterial, and from FIG. 4, it can be found that ZnSnO obtained by this method3Is a cubic structured nano-particle with the particle diameter of 100-200 nm.
Comparative example 2
1.264g of SnCl at room temperature4·5H2Dissolving O and 0.896g NaOH in 70mL of ultrapure water, and magnetically stirring for 30min at the temperature of 0 ℃ under the ice bath condition; then 20mL of 0.18 mol. L were added with continued stirring-1ZnSO of4·7H2Slowly adding O aqueous solution dropwise into the above solution, and mixingThe solution was stirred for 12h under ice bath conditions. And then transferring the solution to a hydrothermal kettle, preserving heat for 12 hours at 120 ℃ to obtain turbid solution, washing the turbid solution by deionized water and absolute ethyl alcohol respectively for three times in a centrifugal mode, and drying the turbid solution for 12 hours at 80 ℃ to obtain a precursor. Finally, the obtained precursor is moved into a tube furnace, the temperature is raised to 500 ℃ at the heating rate of 5 ℃/min under the nitrogen atmosphere, and the temperature is kept for 2h to obtain white powder ZnSnO3And (3) nano materials.
Performance testing
A sodium ion half cell was assembled from the electrode material prepared in example 1 as follows.
N, N-dimethyl pyrrolidone is used as a solvent, conductive carbon black (super-P) serving as a conductive agent, polyvinylidene fluoride (PVDF) serving as a binder and an active material (the material prepared in the embodiment 1) are prepared into slurry according to the mass ratio of 20:20:60, then the slurry is coated on a copper foil, and the copper foil is dried under the vacuum condition at the temperature of 80 ℃ and cut into an electrode slice for later use. And then assembling the electrode plates into a sodium ion half-cell in a glove box. Firstly, stacking the positive electrode shell, the electrode plate, the diaphragm, the sodium sheet, the foamed nickel and the negative electrode shell in sequence, adding a proper amount of electrolyte, and then packaging. Wherein the battery case is CR2032 type, the diaphragm is a glass fiber diaphragm, and the electrolyte is 1mol/LNaPF6(general LiPF)6Dissolved in propylene carbonate).
The battery was charged at 0.1A · g-1The current density was cycled for 100 cycles to obtain a cycle performance chart, as shown in FIG. 3, and from FIG. 3, it can be seen that the material was at 0.1A · g-1The electrochemical performance is stable under the current density of (2), and the specific capacity is still maintained at 430mAh g after the circulation for 100 weeks-1Coulombic efficiency was close to 100%, representing excellent electrochemical stability.
ZnSnO according to example 13The ZnSnO prepared in examples 2-6 and comparative examples 1-23The nano-materials are also made into electrodes and sodium ion half-cells, and ZnSnO prepared in examples 1-6 and comparative examples 1-23The electrochemical properties of the sodium-ion half-cell composed of the nano-materials are shown in the following table 1:
TABLE 1
As can be seen from table 1, the nano materials prepared in examples 1 to 6 by microwave hydrothermal method have excellent electrochemical properties, high charge-discharge specific capacity, coulombic efficiency close to 100%, and great advantages compared with materials prepared by conventional methods.
Examples 1-6 ZnSnO prepared by microwave hydrothermal method3Is in a nano rod-shaped structure with the diameter of 3-5nm, and ZnSnO prepared by the traditional hydrothermal method3Is cubic structure with particle size of 100-200 nm. The particle size of the former is smaller and the distribution is more uniform, which is beneficial to the process of the intercalation/deintercalation of sodium ions, so the circulation performance of the former is better.
In addition, from the electrochemical performance data of examples 1-4, it can be found that the sample obtained at the microwave hydrothermal temperature in the range of 180-250 ℃ is excellent in performance, which indicates that the hydrothermal temperature is too low to facilitate rapid crystallization, and the temperature is too high to cause the pressure in the reaction kettle to be too high, thereby causing particle agglomeration and being not conducive to obtaining the nano material with uniform particle size. From examples 1, 5 and 6, it was found that the material properties obtained at a temperature raising power of about 300W were the best.