CN111370662A - Sodium titanate nanowire-foamed nickel composite material and preparation method and application thereof - Google Patents
Sodium titanate nanowire-foamed nickel composite material and preparation method and application thereof Download PDFInfo
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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Abstract
The invention belongs to the technical field of electrode materials, and particularly relates to a sodium titanate nanowire-foam nickel composite material as well as a preparation method and application thereof. The preparation method of the sodium titanate nanowire-foamed nickel composite material provided by the invention comprises the following steps: mixing titanium dioxide, sodium hydroxide, a surfactant and water to obtain a mixed solution; placing the foamed nickel in the mixed solution, and carrying out hydrothermal reaction to obtain a primary composite material; and cleaning, drying and calcining the primary composite material in sequence to obtain the sodium titanate nanowire-foam nickel composite material. The test results of the embodiment show that the sodium titanate nanowire-foamed nickel composite material obtained by the preparation method provided by the invention has good cycle performance, high coincidence degree of 2-4 circles of discharge curves, obvious charge and discharge platforms, small specific capacity loss and excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and particularly relates to a sodium titanate nanowire-foam nickel composite material as well as a preparation method and application thereof.
Background
The sodium ion energy storage device is an energy storage device taking sodium ions as active energy storage ions, such as a sodium ion battery and a sodium ion hybrid capacitor. A Sodium-ion battery (Sodium-ion battery), which is a secondary battery (rechargeable battery), mainly depends on the movement of Sodium ions between a positive electrode and a negative electrode to work, and is similar to the working principle of a lithium ion battery. The sodium ion hybrid capacitor is characterized in that a sodium ion secondary battery and a super capacitor are crossed in the interior, and the sodium ion hybrid capacitor has the characteristics of high energy density, high power density, long service life and the like. Since the radius of sodium ions is 70% larger than that of lithium ions, many mature materials applied to the lithium ion energy storage device are not applicable to the sodium ion energy storage device, and therefore, the electrode material suitable for the sodium ion energy storage device is widely concerned by the technical personnel in the field.
In a sodium ion energy storage device taking sodium titanate as an electrode material, the sodium titanate has natural abundance, and has the advantages of low toxicity and low potential, but the sodium titanate has poor conductivity, and the structure of the electrode material is gradually destroyed along with the increase of cycle times due to the absence of a binder in the charging and discharging processes, so that the electrochemical performance of a pure sodium titanate electrode is poor, and the increasing electrical performance requirements of the sodium ion energy storage device cannot be met.
Disclosure of Invention
In view of the above, the present invention aims to provide a sodium titanate nanowire-nickel foam composite material and a preparation method thereof, and the sodium titanate nanowire-nickel foam composite material provided by the present invention has excellent electrochemical properties and self-supporting properties; the invention also provides application of the sodium titanate nanowire-foamed nickel composite material.
In order to achieve the purpose of the invention, the invention provides the following technical scheme:
the invention provides a preparation method of a sodium titanate nanowire-foamed nickel composite material, which comprises the following steps:
mixing titanium dioxide, sodium hydroxide, a surfactant and water to obtain a mixed solution;
placing the foamed nickel in the mixed solution, and carrying out hydrothermal reaction to obtain a primary composite material;
and cleaning, drying and calcining the primary composite material in sequence to obtain the sodium titanate nanowire-foam nickel composite material.
Preferably, the mass concentration of the titanium dioxide in the mixed solution is 1.7-33.3 g/L.
Preferably, the concentration of the sodium hydroxide in the mixed solution is 3-20 mol/L.
Preferably, the mass concentration of the surfactant in the mixed solution is 3.3-66.7 g/L.
Preferably, the surfactant comprises cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
Preferably, the temperature of the hydrothermal reaction is 180-230 ℃, the time is 12-48 h, and the pressure is 0.6-2.8 MPa.
Preferably, the drying temperature is 50-100 ℃, and the drying time is 10-36 h.
Preferably, the calcining temperature is 400-600 ℃, and the time is 2-5 h; the calcining temperature is obtained by heating at room temperature, and the heating rate is 0.5-3 ℃/min; the calcination is carried out in an inert gas atmosphere.
The invention also provides the sodium titanate nanowire-foamed nickel composite material prepared by the preparation method in the technical scheme, which comprises foamed nickel and sodium titanate nanowires loaded on the surface and in pore channels of the foamed nickel.
The invention also provides application of the sodium titanate nanowire-foamed nickel composite material in the technical scheme as an electrode material of a sodium ion energy storage device.
The invention provides a preparation method of a sodium titanate nanowire-foamed nickel composite material, which comprises the following steps: mixing titanium dioxide, sodium hydroxide, a surfactant and water to obtain a mixed solution; placing the foamed nickel in the mixed solution, and carrying out hydrothermal reaction to obtain a primary composite material; and cleaning, drying and calcining the primary composite material in sequence to obtain the sodium titanate nanowire-foam nickel composite material. According to the invention, the sodium titanate is directly attached to the foamed nickel by adopting hydrothermal reaction and calcination treatment, so that the slurry mixing and coating processes in the battery assembly process are reduced, the sodium titanate nanowires are well contacted with the foamed nickel, the electronic transmission is conveniently enhanced, the embedding/separating of sodium ions in materials is facilitated, the problem that the appearance of a sample is damaged in charging and discharging is greatly reduced, and the circulation stability is favorably enhanced; and by adding the surfactant, more nano sodium titanate is promoted to be attached to the foamed nickel, so that more nano wires are generated by the sodium titanate, the diffusion distance of sodium ions is shortened, the dynamic performance of the sodium titanate as a negative electrode material is improved, and the requirement of quick charge and discharge is favorably met; meanwhile, hydrothermal reaction is favorable for obtaining a nano sodium titanate material, the surface active area of the sodium titanate is increased, and the sodium titanate nanowire-foam nickel composite material is favorable for serving as an electrode to be in good contact with electrolyte to improve the capacity of the electrode material. Therefore, the sodium titanate nanowire-foam nickel composite material obtained by the invention has excellent electrochemical performance.
The test results of the embodiment show that the sodium titanate nanowire-foamed nickel composite material obtained by the preparation method provided by the invention has good cycle performance, high coincidence degree of 2-4 circles of discharge curves, obvious charge and discharge platforms, small specific capacity loss and excellent electrochemical performance.
Drawings
FIG. 1 is a photograph of a sodium titanate nanowire-nickel foam composite and nickel foam obtained in example 2;
FIG. 2 is an SEM image at 60 times magnification of the sodium titanate nanowire-nickel foam composite obtained in example 2;
FIG. 3 is an SEM image at 700 magnification of the sodium titanate nanowire-nickel foam composite obtained in example 2;
FIG. 4 is a cyclic voltammogram of the sodium titanate nanowire-nickel foam composite obtained in example 2 at 0.1 mV/s;
fig. 5 is a charge-discharge diagram of the sodium titanate nanowire-nickel foam composite obtained in comparative example 2.
Detailed Description
The invention provides a preparation method of a sodium titanate nanowire-foamed nickel composite material, which comprises the following steps:
mixing titanium dioxide, sodium hydroxide, a surfactant and water to obtain a mixed solution;
placing the foamed nickel in the mixed solution, and carrying out hydrothermal reaction to obtain a primary composite material;
and cleaning, drying and calcining the primary composite material in sequence to obtain the sodium titanate nanowire-foam nickel composite material.
In the present invention, the components are commercially available products well known to those skilled in the art unless otherwise specified.
The invention mixes titanium dioxide, sodium hydroxide, surfactant and water to obtain mixed solution.
In the present invention, the titanium dioxide is preferably titanium dioxide powder; the particle size of the titanium dioxide powder is preferably 20-30 nm, more preferably 22-28 nm, and most preferably 25 nm. In the invention, the mass concentration of the titanium dioxide in the mixed solution is preferably 1.7-33.3 g/L, more preferably 3-30 g/L, and still more preferably 5-25 g/L. In the invention, the concentration of the sodium hydroxide in the mixed solution is preferably 3-20 mol/L, more preferably 5-18 mol/L, and still more preferably 8-15 mol/L. In the present invention, the surfactant is preferably a cationic surfactant, more preferably cetyltrimethylammonium bromide or cetyltrimethylammonium chloride. In the invention, the mass concentration of the surfactant in the mixed solution is preferably 3.3-66.7 g/L, more preferably 5-64 g/L, and still more preferably 10-55 g/L.
According to the invention, titanium dioxide, sodium hydroxide and water are preferably mixed, and then the obtained reaction system is mixed with a surfactant, specifically, the sodium hydroxide and the water are mixed to obtain a sodium hydroxide solution, then the titanium dioxide is dissolved in the sodium hydroxide solution, and then the surfactant is added into the mixed system. In the present invention, the mixing of the titanium dioxide, sodium hydroxide and water is preferably performed under stirring, more preferably under ultrasonic stirring; the stirring rate and time are not limited in the present invention, and the titanium dioxide can be completely dissolved. In the present invention, the titanium dioxide is dissolved in sodium hydroxide and reacts to produce sodium titanate:
3TiO2+2NaOH→Na2Ti3O7+H2O。
after the mixed solution is obtained, the foam nickel is placed in the mixed solution for hydrothermal reaction to obtain the primary composite material.
The nickel foam used in the present invention is not particularly limited, and those known to those skilled in the art can be used. Before the foam nickel is placed in the mixed solution, the invention preferably removes impurities from the foam nickel and dries the foam nickel. In the invention, the impurity removal comprises acetone washing, hydrochloric acid washing and water washing which are sequentially carried out. In the present invention, the acetone washing is preferably performed under ultrasonic conditions; the frequency of the ultrasonic wave is preferably 40kHz, and the time is preferably 10-20 min. According to the invention, organic impurities in the foamed nickel are removed through the acetone washing. In the present invention, the concentration of the hydrochloric acid for washing with hydrochloric acid is preferably 3 mol/L. In the present invention, the hydrochloric acid washing is preferably performed under ultrasonic conditions; the frequency of the ultrasonic wave is preferably 40kHz, and the time is preferably 10-20 min. The present invention removes oxides from the nickel foam by pickling with the hydrochloric acid. In the present invention, the water for washing is preferably deionized water; the water washing in the present invention is not particularly limited, and may be water washing known to those skilled in the art. The invention removes floating dust, residual acetone and hydrochloric acid by water washing. In the invention, the drying temperature is preferably 60-80 ℃, and more preferably 65-75 ℃; the drying time is not particularly limited, and the condition that the foam nickel has no residual moisture is taken as the standard.
The present invention is not limited to the way of placing the nickel foam in the mixed solution, and the nickel foam may be placed by a method known to those skilled in the art, specifically, the nickel foam is completely immersed in the mixed solution with an angle of 45 °.
In the invention, the temperature of the hydrothermal reaction is preferably 180-230 ℃, more preferably 190-220 ℃, and further preferably 200-210 ℃; the time is preferably 12-48 h, more preferably 18-42 h, and further preferably 24-36 h; the pressure intensity is preferably 0.6-2.8 MPa, more preferably 0.8-2.6 MPa, and still more preferably 1-2.4 MPa. In the invention, the hydrothermal reaction equipment is preferably a high pressure resistant reaction kettle with a polytetrafluoroethylene lining. In the present invention, the total volume of the reaction system of the hydrothermal reaction is preferably less than 2/3 of the capacity of the reaction equipment, that is, the total volume of the reaction system of the hydrothermal reaction is preferably less than 2/3 of the capacity of the autoclave with polytetrafluoroethylene lining. In the invention, the dissolution-crystallization process of sodium titanate occurs in the hydrothermal reaction, the sodium titanate is dissolved, and the crystallization precipitation process occurs on the surface and in the pore canal of the foamed nickel, so as to generate the sodium titanate nanowire tightly combined with the foamed nickel.
After the primary composite material is obtained, the primary composite material is sequentially cleaned, dried and calcined to obtain the sodium titanate nanowire-foam nickel composite material.
The cleaning method of the present invention is not particularly limited, and a method known to those skilled in the art may be used. According to the invention, through the cleaning, the residual mixed liquid on the surface of the primary composite material and in the gaps is removed, the residual mixed liquid is prevented from changing the shape of the nanowire in the subsequent calcining process, and the shape of the sodium titanate nanowire generated by the hydrothermal reaction is ensured. In the invention, the drying temperature is preferably 50-100 ℃, more preferably 60-95 ℃, and further preferably 70-90 ℃; the time is preferably 10 to 36 hours, more preferably 13 to 33 hours, and still more preferably 16 to 30 hours.
In the invention, the calcination temperature is preferably 400-600 ℃, more preferably 420-580 ℃, and further preferably 450-550 ℃; the time is preferably 2 to 5 hours, more preferably 2.5 to 4.5 hours, and still more preferably 3 to 4 hours. In the invention, the calcining temperature is obtained by raising the temperature at room temperature, and the raising rate is preferably 0.5-3 ℃/min, more preferably 1-2.5 ℃/min, and still more preferably 1.5-2 ℃/min. In the present invention, the calcination is preferably performed in an inert gas atmosphere, more preferably argon. In the present invention, the calcination is advantageous to improve the crystallinity of the sodium titanate nanowire-foamed nickel composite.
The invention also provides the sodium titanate nanowire-foamed nickel composite material prepared by the preparation method in the technical scheme, which comprises foamed nickel and sodium titanate nanowires loaded on the surface and in pore channels of the foamed nickel.
In the invention, the diameter of the sodium titanate nanowire is preferably 45-55 nm, and more preferably 47-53 nm. In the invention, the loading amount of the sodium titanate nanowire on the foamed nickel is preferably 25-35%, and more preferably 28-32%.
The invention also provides application of the sodium titanate nanowire-foamed nickel composite material in the technical scheme as an electrode material of a sodium ion energy storage device. In the invention, the sodium titanate nanowire-foam nickel composite material is preferably a negative electrode material of a sodium ion energy storage device.
In order to further illustrate the present invention, the sodium titanate nanowire-nickel foam composite material provided by the present invention, the preparation method and the application thereof are described in detail below with reference to the examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 0.102g of titanium dioxide powder, 7.2g of sodium hydroxide and 60mL of water, stirring to completely dissolve the titanium dioxide powder, and then adding 0.198g of surfactant cetyl trimethyl ammonium bromide into a reaction system to obtain a mixed solution, wherein the mass concentration of the surfactant in the mixed solution is 3.3 g/L;
sequentially carrying out acetone washing for 10min, 3mol/L hydrochloric acid washing for 10min, water washing and drying at 60 ℃ on 5cm × 3cm × 0.15.15 cm foamed nickel, completely immersing in the obtained mixed solution, placing the obtained reaction system in a high-pressure-resistant reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction for 48h under the conditions of 0.6MPa pressure and 180 ℃ to obtain a primary composite material;
and (3) cleaning the obtained primary composite material, drying at 50 ℃ for 36h, raising the temperature to 400 ℃ at a heating rate of 0.5 ℃/min in an argon atmosphere, and carrying out heat preservation and calcination for 5h to obtain the sodium titanate nanowire-foamed nickel composite material.
Example 2
Mixing 1.05g of titanium dioxide powder, 24g of sodium hydroxide and 60mL of water, stirring to completely dissolve the titanium dioxide powder, and then adding 2.1g of surfactant cetyl trimethyl ammonium bromide into a reaction system to obtain a mixed solution, wherein the mass concentration of the surfactant in the mixed solution is 33.3 g/L;
sequentially washing 5cm × 3cm × 0.15.15 cm foamed nickel with acetone for 15min, washing with 3mol/L hydrochloric acid for 15min, washing with water and drying at 70 ℃, completely immersing in the obtained mixed solution, placing the obtained reaction system in a high-pressure-resistant reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction for 36h under the conditions of 2MPa pressure and 200 ℃ to obtain a primary composite material;
and (3) cleaning the obtained primary composite material, drying at the temperature of 80 ℃ for 24h, raising the temperature to 500 ℃ at the heating rate of 1.8 ℃/min in the argon atmosphere, and carrying out heat preservation and calcination for 3h to obtain the sodium titanate nanowire-foamed nickel composite material.
Macroscopic observation is carried out on the sodium titanate nanowire-foamed nickel composite material obtained in the example 2, and a physical photograph is shown in a figure 1. The left side of the figure 1 shows the foamed nickel subjected to pretreatment only, and the right side shows the sodium titanate nanowire-foamed nickel composite material obtained in example 2. As can be seen from fig. 1, the sodium titanate nanowire-foamed nickel composite material provided by the present invention is formed by attaching white sodium titanate to foamed nickel.
Scanning electron microscope tests are carried out on the sodium titanate nanowire-nickel foam composite material obtained in the example 2, and the obtained SEM images are shown in fig. 2 and fig. 3, wherein the figure 2 is an SEM image of the sodium titanate nanowire-nickel foam composite material obtained in the example 2 at 60 times magnification, and the figure 3 is an SEM image of the sodium titanate nanowire-nickel foam composite material obtained in the example 2 at 700 times magnification. As can be seen from fig. 2 and 3, in the sodium titanate nanowire-foamed nickel composite material provided by the present invention, the sodium titanate attached to the foamed nickel is in a nanowire form, and the foamed nickel and the sodium titanate nanowire are well combined.
Example 3
Mixing 1.998g of titanium dioxide powder, 48g of sodium hydroxide and 60mL of water, stirring to completely dissolve the titanium dioxide powder, and then adding 4g of surfactant cetyl trimethyl ammonium bromide into a reaction system to obtain a mixed solution, wherein the mass concentration of the surfactant in the mixed solution is 66.7 g/L;
sequentially carrying out acetone washing for 20min, 3mol/L hydrochloric acid washing for 20min, water washing and drying at 80 ℃ on 5cm × 3cm × 0.15.15 cm foamed nickel, completely immersing in the obtained mixed solution, placing the obtained reaction system in a high-pressure-resistant reaction kettle with a polytetrafluoroethylene lining, and carrying out hydrothermal reaction for 12h under the conditions of 2.8MPa pressure and 230 ℃ to obtain a primary composite material;
and (3) cleaning the obtained primary composite material, drying at the temperature of 100 ℃ for 12h, raising the temperature to 600 ℃ at the heating rate of 3 ℃/min in the argon atmosphere, and carrying out heat preservation and calcination for 5h to obtain the sodium titanate nanowire-foamed nickel composite material.
Application example 1
Beating the sodium titanate nanowire-foam nickel composite material obtained in the example 1 into a circular pole piece with the diameter of 10mm, and weighing the pole piece and putting the pole piece into a glove box for later use; at 1mol/L of NaClO4Ethylene Carbonate (EC) and diethyl carbonate (DEC) (1: 1 volume) solutions as electrolytes, sodium tablets as counter electrodes, were assembled into button sodium ion batteries in an argon filled glove box.
Application example 2
Beating the sodium titanate nanowire-foam nickel composite material obtained in the example 2 into a circular pole piece with the diameter of 10mm, and weighing the pole piece and putting the pole piece into a glove box for later use; at 1mol/L of NaClO4Ethylene Carbonate (EC) and diethyl carbonate (DEC) (1: 1 volume) solutions as electrolytes, sodium tablets as counter electrodes, were assembled into button sodium ion batteries in an argon filled glove box.
Test example 1
The sodium ion battery assembled in the application example 2 is subjected to charge and discharge tests under the current density of 50mAh/g and the voltage range of 0.01-2.5V, and the cyclic voltammetry curve of 0.1mV/s is shown in figure 4. As can be seen from FIG. 4, the EIS film is formed in the first circle (1st in the figure) so that the redox peak is not obvious, and the coincidence degree of the redox peaks in the two subsequent circles (2 nd and 3rd in the figure) is high, which indicates that the sodium titanate nanowire-foamed nickel composite material provided by the invention has better cycle performance.
The charge/discharge diagram obtained by the above charge/discharge test is shown in FIG. 5. As can be seen from FIG. 5, the specific capacity of the first charge and first discharge (1st) in the charge-discharge cycle is much higher than that of the cycles of the following circles, the contact ratio of the discharge curves of 2-4 circles (2 nd, 3rd and 4th in the figure) is high, and the sodium titanate nanowire-foamed nickel composite material has an obvious charge-discharge platform and small specific capacity loss, which indicates that the sodium titanate nanowire-foamed nickel composite material provided by the invention has excellent electrochemical performance.
Test example 2
The sodium ion battery assembled in the application example 1 and the application example 2 is subjected to a charge and discharge test under the current density of 50mAh/g and the voltage range of 0.01-2.5V, the discharge specific capacity is tested, and the obtained test result is shown in table 1.
TABLE 1 specific discharge capacity results (mAh. g) of sodium ion batteries obtained in application examples 1 to 2-1)
| 1st | 2nd | 3rd | 4th | |
| Application example 1 | 402 | 215 | 149 | 113 |
| Application example 2 | 485 | 249 | 185 | 134 |
As can be seen from table 1, the sodium ion battery prepared from the sodium titanate nanowire-nickel foam composite material provided by the invention has smaller specific capacity loss, which indicates that the sodium titanate nanowire-nickel foam composite material provided by the invention has excellent electrochemical performance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The preparation method of the sodium titanate nanowire-foamed nickel composite material is characterized by comprising the following steps of:
mixing titanium dioxide, sodium hydroxide, a surfactant and water to obtain a mixed solution;
placing the foamed nickel in the mixed solution, and carrying out hydrothermal reaction to obtain a primary composite material;
and cleaning, drying and calcining the primary composite material in sequence to obtain the sodium titanate nanowire-foam nickel composite material.
2. The method according to claim 1, wherein the mass concentration of titanium dioxide in the mixed solution is 1.7 to 33.3 g/L.
3. The method according to claim 1, wherein the concentration of sodium hydroxide in the mixed solution is 3 to 20 mol/L.
4. The method according to claim 1, wherein the mixed solution contains the surfactant at a mass concentration of 3.3 to 66.7 g/L.
5. The method of claim 1 or 4, wherein the surfactant comprises cetyltrimethylammonium bromide or cetyltrimethylammonium chloride.
6. The preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 180-230 ℃ for 12-48 h under a pressure of 0.6-2.8 MPa.
7. The preparation method according to claim 1, wherein the drying temperature is 50-100 ℃ and the drying time is 10-36 h.
8. The preparation method according to claim 1, wherein the calcining temperature is 400-600 ℃ and the calcining time is 2-5 h;
the calcining temperature is obtained by heating at room temperature, and the heating rate is 0.5-3 ℃/min;
the calcination is carried out in an inert gas atmosphere.
9. The sodium titanate nanowire-foam nickel composite material prepared by the preparation method of any one of claims 1 to 8, which is characterized by comprising foam nickel and sodium titanate nanowires loaded on the surface and in pore channels of the foam nickel.
10. Use of the sodium titanate nanowire-nickel foam composite material of claim 9 as an electrode material for a sodium ion energy storage device.
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Citations (5)
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