CN111056574B - Method for preparing pattern Co on foam nickel substrate3O4Method for preparing nano material - Google Patents

Method for preparing pattern Co on foam nickel substrate3O4Method for preparing nano material Download PDF

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CN111056574B
CN111056574B CN201911413751.5A CN201911413751A CN111056574B CN 111056574 B CN111056574 B CN 111056574B CN 201911413751 A CN201911413751 A CN 201911413751A CN 111056574 B CN111056574 B CN 111056574B
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hydrochloric acid
foamed nickel
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cobalt salt
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CN111056574A (en
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仝玉萍
张红松
史玉茸
王晗晗
张亚辉
张涌
郝用兴
倪增磊
李宁宁
李振洋
杨煜晨
李鑫宇
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North China University of Water Resources and Electric Power
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Abstract

The invention providesProvides a method for preparing pattern Co on a foamed nickel substrate3O4A method of nanomaterials comprising the steps of: s1: placing the foam nickel screen into a centrifugal tube, sequentially soaking the foam nickel screen in absolute ethyl alcohol and hydrochloric acid solution, washing and drying to obtain a processed nickel screen; s2: mixing urea and deionized water to obtain a solution A, heating cobalt salt, adding the cobalt salt into the solution A to obtain a solution B, carrying out vacuum treatment on the solution B, enabling water in the solution B to form gathered micro-bubbles in a vacuum environment, enabling the cobalt salt to be uniformly dissolved in the solution B to obtain a solution C, and finally adding a catalyst into the solution C to obtain a solution D; s3: adjusting the pH value of the solution D, transferring the solution D into a high-pressure reaction kettle, adding a treated nickel net, carrying out stepped constant-temperature reaction, washing and drying to obtain Co3O4And (3) nano materials.

Description

Method for preparing pattern Co on foam nickel substrate3O4Method for preparing nano material
Technical Field
The invention belongs to the technical field of material preparation, and particularly relates to a method for preparing pattern Co on a foam nickel substrate3O4A method of preparing a nanomaterial.
Background
Co currently on the market3O4The development of products mainly comprises two main categories, wherein the first category is the industrial production of Co3O4And (3) powder materials. The common characteristics of the industries are that the activity of the product can meet the low-end requirements of the current electrochemical industry and the production cost is low, but the types of the products are too few to meet the specific requirements of various fields of electrochemistry. With the improvement of living standard and the requirement of electrochemical materials, the industrially produced Co3O4The powder material can not meet the requirements of people. The second type is to prepare Co with high electrochemical activity by adopting different synthesis methods under laboratory conditions3O4And (3) nano materials. The product has the characteristics of high electrochemical activity, diversified types and controllable appearance, and can meet specific requirements of different electrochemical fields. However, the yield of the product is low, the production cost is too high, and the industrial large-scale production cannot be realized.
Co3O4The material is a good metal compound material of transition elements, can be used as a catalyst and is an environment-friendly capacitor. At present Co3O4The preparation method is multiple, and the invention adopts a hydrothermal method to grow Co on the foamed nickel3O4. The hydrothermal method has the advantages of low energy consumption and wide application range, and can synthesize large-size single crystals and small-particle-size nano particles; the experimental conditions and the appearance of the sample are easy to control, and the like. Another feature of the present invention is the advantage of direct growth on a foamed nickel substrate. Foamed nickel is widely used as an active material and a support substrate material of a battery because it has advantages of a large specific surface area, a high porosity, an excellent conductivity, etc., and has a good chemical stability in various liquid environments. The electrode material directly grown on the foamed nickel substrate can be directly used as an electrode material when being applied to a super capacitor, and the influence of a binder and a conductive agent on the conductivity of the electrode material is eliminated.
Patent application No. 200910060852.9Application discloses a Co3O4A method for preparing a nanotube array. Although the nanotube array synthesized by the method has high purity, high specific surface area and short synthesis period, the method meets the requirements of electronic grade powder materials. But the preparation process is too complicated, the economic benefit and the social benefit are low, and the large-scale production cannot be carried out.
Disclosure of Invention
Aiming at the problems, the invention provides a method for preparing pattern Co on a foamed nickel substrate3O4A method of preparing a nanomaterial.
The technical scheme of the invention is as follows: method for preparing pattern Co on foam nickel substrate3O4The method for preparing the nano material mainly comprises the following steps:
s1: cutting the foam nickel screen into square sheets of 3.0cm multiplied by 3.0cm, putting the square sheets into a centrifugal tube, adding absolute ethyl alcohol to submerge the foam nickel screen, sealing the foam nickel screen, centrifugally soaking the foam nickel screen on a centrifugal machine at 40-42 ℃ for 10-12 h, taking out the foam nickel screen, putting the soaked foam nickel screen into an overflow container, continuously adding 3mol/L hydrochloric acid solution from the bottom of the overflow container until the hydrochloric acid solution submerges the foamed nickel net and overflows, replacing the hydrochloric acid solution with deionized water after overflowing and cleaning for 1-2 h, continuously overflowing and cleaning for 1-2 h, aerating the hydrochloric acid solution and the deionized water by a micro aerator to ensure that the hydrochloric acid solution and the deionized water are filled with bubbles in the overflow cleaning process, cleaning the interior of the foam nickel screen through bubbles, centrifugally dewatering the cleaned foam nickel screen on a centrifugal machine, and drying the cleaned foam nickel screen for 6-8 hours at 50 ℃ in a drying box to obtain a processed nickel screen;
s2: weighing cobalt salt, a catalyst and urea, mixing and stirring the urea and deionized water in a molar ratio of 1: 10-12 to obtain a solution A, heating the cobalt salt to 50-60 ℃, adding the cobalt salt into the solution A to obtain a solution B, vacuumizing the solution B, enabling water in the solution B to form gathered micro bubbles in a vacuum environment to rise, vacuumizing until no obvious bubbles are generated in the solution B, uniformly dissolving the cobalt salt in the solution B to obtain a solution C, finally adding the catalyst into the solution C, sealing a preservative film, and stirring until the catalyst is completely dissolved to obtain a solution D;
s3: the pH of solution DAdjusting the value to 8-11, transferring the solution D into a high-pressure reaction kettle, vertically putting the nickel net treated in the S1 into the high-pressure reaction kettle for step-type constant-temperature reaction, taking out the nickel net after the high-pressure reaction kettle is cooled to room temperature, soaking the nickel net after reaction in absolute ethyl alcohol for 0.5-0.6 h, then washing with deionized water, drying, and calcining at 380-420 ℃ for 1-2 h to obtain Co3O4And (3) nano materials.
Furthermore, a collecting container is arranged outside the overflow container in the S1, the hydrochloric acid solution overflowing during cleaning is collected and then is circularly used for overflow cleaning through filtering and separation, and the cost can be reduced through recycling.
Further, the molar ratio of the cobalt salt, the catalyst and the urea in S2 is 1:3: 1.
Preferably, the cobalt salt described in S2 is Co (NO)3)2·6H2O、CoCl2·6H2O、Co(COOCH3)2·4H2And O is one of the compounds.
More preferably, the cobalt salt described in S2 is Co (NO)3)2·6H2O。
Preferably, the catalyst described in S2 is one of cetyltrimethylammonium bromide (CTAB), polyvinylpyrrolidone (PVP), Sodium Dodecyl Sulfate (SDS).
More preferably, the catalyst described in S2 is cetyltrimethylammonium bromide (CTAB).
Further, the vacuum degree of the solution B subjected to vacuum treatment in the step S2 is-0.03 to-0.07 MPa.
Preferably, the solution for adjusting the pH value in S3 is 1mol/L ammonia water.
Further, the step type constant temperature reaction in S3 specifically includes: heating to 120 ℃ at the heating rate of 2 ℃/min, reacting at the constant temperature of 120 ℃ for 30-40 min, then continuously heating to 150 ℃ at the heating rate of 1 ℃/min, reacting at the constant temperature of 150 ℃ for 10-20 min, heating to 180 ℃ at the heating rate of 5 ℃/min, and reacting at the constant temperature of 180 ℃ for 50-60 min.
The invention has the beneficial effects that:
1. the invention cleans the processed foam nickel screen by a microbubble overflow cleaning method, deeply cleans the interior of the foam nickel screen by utilizing the bubble rising principle in the solution, washes away impurities adhered to the pores in the foam nickel screen and ensures the stability of the reaction.
2. According to the invention, the mixed solution is vacuumized, and the negative pressure formed in a vacuum state is utilized to enable water in the solution to form gathered micro bubbles in a vacuum environment to rise, so that the binding force of each substance in the solution is enhanced, each substance is more uniformly dispersed in the solution, and the reaction efficiency of the solution and a nickel screen is enhanced.
3. The invention utilizes a hydrothermal method to grow Co on the foamed nickel3O4The preparation process has low energy consumption and wide applicability, can synthesize large-size single crystals and small-particle-size nano particles, easily control the conditions changed in experiments, and conveniently obtain materials with different shapes.
4. The hydrothermal method can simply and effectively control the reaction and the growth of crystals, and the experimental requirements are met by changing the hydrothermal time, the reaction temperature, the solution components and the additive in the synthesis process.
5. The material directly growing on the foamed nickel substrate can be directly used as an electrode material when being applied to a supercapacitor material in the later period, and the material growing on the substrate can eliminate the influence of a binder and a conductive agent on the conductivity of the electrode material.
Drawings
FIG. 1 is a graph showing the growth of Co on nickel foam3O4XRD analysis pattern of the nanomaterial.
FIG. 2 is a graph showing the growth of Co on nickel foam3O4EDS analysis of nanomaterials.
FIG. 3 shows the growth of Co using cobalt nitrate as cobalt source3O4SEM image of (d).
FIG. 4 shows the growth of Co using cobalt chloride as cobalt source3O4SEM image of (d).
FIG. 5 shows the growth of Co using cobalt acetate as cobalt source3O4SEM image of (d).
FIG. 6 shows the growth of PVP as surfactant on nickel foamCo3O4SEM images of different magnifications.
FIG. 7 shows the growth of Co on nickel foam with SDS as surfactant3O4SEM images of different magnifications.
FIG. 8 shows the growth of Co on nickel foam at pH 83O4SEM images of different magnifications.
FIG. 9 shows the growth of Co on nickel foam at pH 10, 113O4SEM images of different magnifications.
FIG. 10 shows the growth of Co on nickel foam with SDS as surfactant3O4Different magnification TEM images of (a).
FIG. 11 is a cyclic voltammetry test of Co grown on nickel foam3O4The electrochemical performance of (2).
FIG. 12 shows the self-growth of Co in a constant current charge/discharge test3O4And (3) charging and discharging curves of the electrode under different current densities.
FIG. 13 is self-growing Co in cycling stability test3O4The electrode was cycled 20 times at a current density of 7mA/cm2 for a charge-discharge curve.
FIG. 14 is a graph of self-grown Co in AC impedance testing3O4AC impedance curve of electrode at-0.1V potential.
Detailed Description
For the understanding of the technical solution of the present invention, the following description is further illustrated with reference to fig. 1 to 14 and specific examples, which are not intended to limit the scope of the present invention.
Example 1:
s1: cutting the foam nickel screen into square sheets of 3.0cm multiplied by 3.0cm, placing the square sheets into a centrifugal tube, adding absolute ethyl alcohol to submerge the foam nickel screen, sealing the foam nickel screen, centrifugally soaking the foam nickel screen on a centrifugal machine at 40 ℃ for 10 hours, taking out the foam nickel screen, placing the soaked foam nickel screen in an overflow container, continuously adding 3mol/L hydrochloric acid solution from the bottom of the overflow container until the hydrochloric acid solution submerges the foamed nickel net and overflows, after the overflow cleaning is carried out for 1h, replacing the hydrochloric acid solution with deionized water, continuously carrying out the overflow cleaning for 1h, wherein a collecting container is arranged outside the overflow container, the hydrochloric acid solution overflowing during the cleaning is collected and then is circularly used for the overflow cleaning through filtration and separation, the hydrochloric acid solution and the deionized water are aerated through a micro-aerator, so that the hydrochloric acid solution and the deionized water are filled with bubbles in the overflow cleaning process, cleaning the interior of the foam nickel screen through bubbles, centrifugally dewatering the cleaned foam nickel screen on a centrifugal machine, and drying the cleaned foam nickel screen for 6 hours at 50 ℃ in a drying box to obtain a processed nickel screen;
s2: according to Co (NO)3)2·6H2Weighing Co (NO) according to the molar ratio of O, hexadecyl trimethyl ammonium bromide to urea of 1:3:13)2·6H2O, cetyl trimethyl ammonium bromide and urea, mixing and stirring the urea and deionized water according to a molar ratio of 1:10 to obtain a solution A, and mixing Co (NO)3)2·6H2Heating O to 50 deg.C, adding into solution A to obtain solution B, vacuumizing the solution B to-0.03 Mpa, allowing water in the solution B to form gathered micro bubbles in vacuum environment, and vacuumizing until NO bubbles are generated in the solution B to make Co (NO) be dissolved in the solution B3)2·6H2Dissolving O in the solution B uniformly to obtain a solution C, adding cetyl trimethyl ammonium bromide into the solution C, sealing the preservative film, and stirring until the cetyl trimethyl ammonium bromide is completely dissolved to obtain a solution D;
s3: adjusting the pH value of the solution D to 8 by using 1mol/L ammonia water, transferring the solution D into a high-pressure reaction kettle, vertically putting the nickel net processed in S1 into the high-pressure reaction kettle, heating to 120 ℃ at the heating rate of 2 ℃/min, reacting at constant temperature of 120 ℃ for 30min, continuously heating to 150 ℃ at the heating rate of 1 ℃/min, reacting at constant temperature of 150 ℃ for 10min, heating to 180 ℃ at the heating rate of 5 ℃/min, reacting at constant temperature of 180 ℃ for 50min, cooling the high-pressure reaction kettle to room temperature, taking out the nickel net, soaking the nickel net after reaction in absolute ethyl alcohol for 0.5h, washing with deionized water, drying, calcining at 380 ℃ for 1h to obtain Co3O4And (3) nano materials.
Example 2:
s1: cutting the foam nickel screen into square sheets of 3.0cm multiplied by 3.0cm, placing the square sheets into a centrifugal tube, adding absolute ethyl alcohol to submerge the foam nickel screen, sealing the tube, centrifugally soaking the tube on a centrifugal machine at 41 ℃ for 11 hours, taking out the tube, placing the soaked foam nickel screen into an overflow container, continuously adding 3mol/L hydrochloric acid solution from the bottom of the overflow container until the hydrochloric acid solution submerges the foamed nickel net and overflows, after the overflow cleaning is carried out for 1.5h, replacing the hydrochloric acid solution with deionized water, continuously carrying out the overflow cleaning for 1.5h, arranging a collecting container outside the overflow container, collecting the overflowing hydrochloric acid solution in the cleaning process, then carrying out filtering separation circulation for the overflow cleaning, aerating the hydrochloric acid solution and the deionized water through a micro-aerator to ensure that the hydrochloric acid solution and the deionized water are filled with bubbles in the overflow cleaning process, cleaning the interior of the foam nickel screen through bubbles, centrifugally dewatering the cleaned foam nickel screen on a centrifugal machine, and drying the cleaned foam nickel screen in a drying box at 50 ℃ for 7 hours to obtain a processed nickel screen;
s2: according to CoCl2·6H2Weighing CoCl with the molar ratio of O, polyvinylpyrrolidone and urea of 1:3:12·6H2O, polyvinylpyrrolidone and urea, mixing and stirring the urea and deionized water according to the molar ratio of 1:11 to obtain a solution A, and adding CoCl2·6H2Heating O to 55 deg.C, adding into the solution A to obtain solution B, vacuumizing the solution B to-0.05 Mpa, and allowing water in the solution B to form gathering micro-bubbles in vacuum environment to rise to allow CoCl2·6H2Uniformly dissolving O in the solution B to obtain a solution C, finally adding polyvinylpyrrolidone into the solution C, sealing the preservative film, and stirring until the polyvinylpyrrolidone is completely dissolved to obtain a solution D;
s3: adjusting the pH value of the solution D to 10 by using 1mol/L ammonia water, transferring the solution D into a high-pressure reaction kettle, vertically putting the nickel net processed in S1 into the high-pressure reaction kettle, heating to 120 ℃ at the heating rate of 2 ℃/min, carrying out constant-temperature reaction at 120 ℃ for 35min, then continuously heating to 150 ℃ at the heating rate of 1 ℃/min, carrying out constant-temperature reaction at 150 ℃ for 15min, then heating to 180 ℃ at the heating rate of 5 ℃/min, carrying out constant-temperature reaction at 180 ℃ for 55min, cooling the high-pressure reaction kettle to room temperature, taking out the nickel net, soaking the nickel net after reaction in absolute ethyl alcohol for 0.55h, then washing with deionized water, drying, and calcining at 400 ℃ for 1.5h to obtain Co3O4And (3) nano materials.
Example 3:
s1: cutting the foam nickel screen into square sheets of 3.0cm multiplied by 3.0cm, placing the square sheets into a centrifugal tube, adding absolute ethyl alcohol to submerge the foam nickel screen, sealing the foam nickel screen, centrifugally soaking the foam nickel screen on the centrifugal machine at 42 ℃ for 12 hours, taking out the foam nickel screen, placing the soaked foam nickel screen in an overflow container, continuously adding 3mol/L hydrochloric acid solution from the bottom of the overflow container until the hydrochloric acid solution submerges the foamed nickel net and overflows, after 2h of overflow cleaning, replacing the hydrochloric acid solution with deionized water to continuously overflow and clean for 2h, wherein a collecting container is arranged outside the overflow container, the hydrochloric acid solution overflowing during cleaning is collected and then is circularly used for overflow cleaning through filtering and separation, the hydrochloric acid solution and the deionized water are aerated through a micro aerator, so that the hydrochloric acid solution and the deionized water are filled with bubbles in the overflow cleaning process, cleaning the interior of the foam nickel screen through bubbles, centrifugally dewatering the cleaned foam nickel screen on a centrifugal machine, and drying the cleaned foam nickel screen in a drying box at 50 ℃ for 8 hours to obtain a processed nickel screen;
s2: according to Co (COOCH)3)2·4H2Weighing Co (COOCH) at a molar ratio of O, sodium dodecyl sulfate and urea of 1:3:13)2·4H2O, sodium dodecyl sulfate and urea, mixing urea and deionized water in the molar ratio of 1 to 12 to obtain solution A, and adding Co (COOCH)3)2·4H2Heating O to 60 deg.C, adding into solution A to obtain solution B, vacuumizing the solution B to-0.07 Mpa, and allowing water in the solution B to form gathering micro-bubbles in vacuum environment to rise to make Co (COOCH)3)2·4H2Dissolving O in the solution B uniformly to obtain a solution C, adding sodium dodecyl sulfate into the solution C, sealing the preservative film, and stirring until the sodium dodecyl sulfate is completely dissolved to obtain a solution D;
s3: adjusting the pH value of the solution D to 11 by using 1mol/L ammonia water, transferring the solution D into a high-pressure reaction kettle, vertically putting the nickel screen processed in S1 into the high-pressure reaction kettle, heating to 120 ℃ at the heating rate of 2 ℃/min, reacting at constant temperature of 120 ℃ for 40min, then continuously heating to 150 ℃ at the heating rate of 1 ℃/min, reacting at constant temperature of 150 ℃ for 20min, then heating to 180 ℃ at the heating rate of 5 ℃/min,reacting at 180 ℃ for 60min at constant temperature, cooling the high-pressure reaction kettle to room temperature, taking out the nickel net, soaking the nickel net after reaction in absolute ethyl alcohol for 0.6h, washing with deionized water, drying, and calcining at 420 ℃ for 2h to obtain Co3O4And (3) nano materials.
XRD test
For Co growing on foamed nickel3O4The nanoarrays were subjected to XRD analysis as shown in figure 1. The results show that: XRD patterns of three growth samples with surface activity are obtained by XRD detection, and comparative Ni and Co are added3O4By comparing the standard contrast card of (1), we can see that the peak value of the sample completely coincides with that of Ni, and no grown Co appears3O4Peak value of the sample. This is because the amount of material grown on the nickel foam is too small, the material grown is not separated from the substrate when the sample is tested, and XRD shows the pattern of the substrate Ni because the substrate is a nickel mesh.
EDS analysis
Shown in FIG. 2 is a graph for Co grown on nickel foam3O4The nano-arrays were subjected to EDS analysis. The results show that: qualitative analysis of EDS images can show that only O, Co elements exist in the sample, which indicates that the sample has high purity and no other impurity elements, and quantitative analysis can obtain O, Co atomic percent ratio of the two elements to Co of 4:2.873O4The element ratio of 4:3 is very close, but the content of the O element is higher, and the O element mixed with a small amount of other sources in the detection sample can be detected. It can be confirmed that the substance grown is Co3O4The purity of the sample is high.
SEM test
FIG. 3 shows that cobalt nitrate is used as cobalt source to grow Co3O4SEM image of (d). In fig. 3, (a) and (b) are SEM images magnified 5000 and 20000 times, respectively, and uniform coating on the nickel mesh can be seen. FIG. (c) is an SEM image enlarged by 5000 times, and the rod-like structure can be clearly seen; FIG. d is an SEM photograph magnified 100000 times and measured to give a rod-like structure having a diameter of about 30 nm. Can presume the anion NO in the cobalt nitrate3 -The growth direction of the substance is promoted to be deviated to the rod-shaped structure.
FIG. 4 shows the growth of Co using cobalt chloride as cobalt source3O4SEM image of (d). In fig. 4, (a) (b) are SEM images magnified 10000 and 20000 times, respectively, and it can be seen that the nickel mesh is uniformly coated and has a good morphology. FIG. (c) is an SEM photograph magnified 50000 times and showing only a long bar-like shape; FIG. d is an SEM image magnified 100000 times and clearly shows that the cobalt chloride has an anion Cl of the cobalt chloride since it is formed into a long and thin shape of a candied haws by stacking a plurality of oblate spheroids-The material is beneficial to the growth of the material towards the shape of the candied haws, and the diameter of the candied haws is about 60nm through measurement.
FIG. 5 shows the growth of Co using cobalt acetate as cobalt source3O4SEM image of (d). In fig. 5, (a) and (b) are SEM images respectively magnified 10000 and 20000 times, and it can be seen that a large amount of substance is coated on the nickel mesh, and a certain morphology is presented. FIG. (c) is an SEM image at 50000 times magnification, and it can be seen that the substance is formed by stacking a large number of strips; the SEM image (d) is magnified 100000 times and the stacked strips are more evident, which can also be measured to have a strip-like structure width of about 70 nm. The anion CH in the cobalt acetate can be preliminarily deduced3COO-Promoting the growth of the substance into strips.
FIG. 6 shows that the surfactant PVP is PVP, Co grows on the nickel foam3O4SEM images of different magnifications. The diagram (a) is an SEM diagram magnified 2000 times, and it can be seen that a large amount of substance is covered on the foam nickel skeleton, the whole is still straight, the growth is good, the defect is caused, and we can see that a small fault appears, and the possible reason is that the growth continuity is not complete and needs to be improved later. The SEM images (b) and (c) are magnified 10000 and 20000 times, respectively, and it can be observed that the features are linear and are interlaced with each other.
FIG. 7 shows that the surfactant SDS grows Co on the foam nickel3O4SEM images of different magnifications. FIG. (a) is an SEM photograph magnified 1000 times, and shows well-grown pattern substances. The observation chart (b) is to observe the morphology of the composite material more clearlyThe SEM image magnified 2000 times shows a more distinct and floret-like morphology. FIG. c is an SEM image magnified 5000 times, and a pattern is observed alone, and the substances are orderly arranged and uniformly grown without agglomeration. The unique spatial structure of the micro-flower shape provides a plurality of electrochemically active sites which enhance the interaction between the electrode material and the foamed nickel substrate, and accelerate the transport of ions and electrons.
As shown in FIG. 8, cobalt nitrate for cobalt salt, CTAB as surfactant, urea as precipitant in aqueous solution, and ammonia water added to adjust pH to 8 are used to grow Co on foamed nickel3O4SEM images of different magnifications. The SEM image magnified 1000 times in the figure (a) shows that the growing substances obviously grow on the foamed nickel reticular skeleton, and the image magnified 2000 times on the basis of the SEM image is the figure (b), and the growing substances obviously show approximate appearance. The SEM image (c) is a 5000 times magnified SEM image showing a flower-heart shape, and the image (d) is an 20000 times magnified image, and it can be seen that the flower-heart shape is formed by stacking a plurality of small slices, and the unique morphology is for Co3O4Various properties of the material are advantageous.
FIG. 9 shows the growth of Co on nickel foam in a liquid environment with pH 10 and pH 113O4SEM image of (d). As can be seen from fig. 9, the mesh structure of the nickel mesh itself appears, and it is observed that very little substance exists on the nickel mesh skeleton, and the morphology of the substance is not seen. Therefore, it can be seen that in a strong alkaline environment, the solution is no longer stable and uniform, a large amount of precipitate is formed, and it is difficult to attach to the nickel foam, which is not favorable for Co3O4The material grows on the nickel foam.
TEM test
FIG. 10 shows that the surfactant SDS grows Co on the foam nickel3O4Different magnification TEM images of (a). From the TEM images, it can be seen that: FIG. (a) is the overall morphology of the sample, all in one-dimensional linear structures, FIG. (b) is an enlarged view of FIG. (a), FIG. (c) is a single enlarged TEM picture, and FIG. (d) is a diffraction pattern, illustrating that the sample is in a polycrystalline form. FIGS. (e), (f) are two high-resolution TEM pictures measured to have an interplanar spacing of 0.285nm, 0.285nm just corresponds to the {220} crystal plane, and the orientation of crystal growth can be judged according to the crystal plane spacing.
Electrochemical performance test analysis
Co directly grown on foamed nickel at normal temperature3O4The electrochemical performance test of (2) is completed by adopting a three-electrode electrochemical workstation. FIG. 11 shows cyclic voltammetry testing of Co grown on nickel foam3O4The electrochemical performance of (2). FIG. 11 (a) is a view of self-growing Co by cyclic voltammetry3O4CV curve diagram of electrode at scanning speed of 5 mV/s; (b) CV curves of different scanning rates of cyclic voltammetry; (c) the specific capacitance value of the cyclic voltammetry at different scanning rates is shown in the following table:
TABLE 1 cyclic voltammetry different scan rates to test Co grown on nickel foam3O4Specific capacitance value of electrochemical performance of
Figure BDA0002350631790000101
FIG. 12 shows the self-growth of Co in the constant current charge/discharge test3O4And (3) charging and discharging curves of the electrode under different current densities.
FIG. 13 shows the self-growth of Co in the cycling stability test3O4The electrode was at 7mA/cm2Charge and discharge curves at current density cycled 20 times.
FIG. 14 shows the self-growth of Co in the AC impedance test3O4AC impedance curve of electrode at-0.1V potential.
The results of the electrochemical performance tests show that: self-growing Co3O4The electrode material has good capacitance characteristic at low scanning speed within the working potential range (-0.1-0.6V), and the specific volume per unit mass is 275.78F/g when the scanning speed is 5 mV/s. And passing through the reactor for multiple times at a current density of 7mA/cm2And the cycling stability of the obtained electrode is good through cycling test. Next, we analyzed the impedance and found that the impedance of the electrolyte system was large, butThe resistance of the electrode material was good.

Claims (5)

1. Method for preparing pattern Co on foam nickel substrate3O4The method for preparing the nano material is characterized by mainly comprising the following steps of:
s1: cutting a foamed nickel net into square sheets of 3.0cm multiplied by 3.0cm, placing the square sheets into a centrifugal tube, adding absolute ethyl alcohol to immerse the foamed nickel net, sealing the square sheets, centrifugally soaking the sheets for 10 to 12 hours at 40 to 42 ℃ on a centrifugal machine, taking the sheets out, placing the soaked foamed nickel net into an overflow container, continuously adding 3mol/L hydrochloric acid solution from the bottom of the overflow container until the hydrochloric acid solution submerges and overflows the foamed nickel net, replacing the hydrochloric acid solution with deionized water after overflowing and cleaning for 1 to 2 hours, continuously overflowing and cleaning the hydrochloric acid solution and the deionized water for 1 to 2 hours, aerating the hydrochloric acid solution and the deionized water through a micro-aerator to fill bubbles in the overflowing and cleaning process, cleaning the interior of the foamed nickel net through the bubbles, centrifugally dewatering the cleaned foamed nickel net on the centrifugal machine, and drying the cleaned foamed nickel net in a drying box for 6 to 8 hours at 50 ℃ to obtain a treated nickel net;
s2: weighing cobalt salt, a catalyst and urea, mixing and stirring the urea and deionized water in a molar ratio of 1: 10-12 to obtain a solution A, heating the cobalt salt to 50-60 ℃, adding the cobalt salt into the solution A to obtain a solution B, vacuumizing the solution B, enabling water in the solution B to form gathered micro bubbles in a vacuum environment to rise, vacuumizing until no obvious bubbles are generated in the solution B, uniformly dissolving the cobalt salt in the solution B to obtain a solution C, finally adding the catalyst into the solution C, sealing a preservative film, and stirring until the catalyst is completely dissolved to obtain a solution D;
s3: adjusting the pH value of the solution D to 8-11, transferring the solution D into a high-pressure reaction kettle, vertically putting the nickel net processed in the step-type constant-temperature reaction in the high-pressure reaction kettle S1, cooling the high-pressure reaction kettle to room temperature, taking out the nickel net, soaking the nickel net after the reaction in absolute ethyl alcohol for 0.5-0.6 h, washing with deionized water, drying, and calcining at 380-420 ℃ for 1-2 h to obtain Co3O4A nanomaterial;
the molar ratio of the cobalt salt, the catalyst and the urea in S2 is 1:3: 1;
the catalyst in S2 is one of Cetyl Trimethyl Ammonium Bromide (CTAB), polyvinylpyrrolidone (PVP) and Sodium Dodecyl Sulfate (SDS);
the step type constant temperature reaction in the S3 comprises the following specific steps: heating to 120 ℃ at the heating rate of 2 ℃/min, reacting at the constant temperature of 120 ℃ for 30-40 min, then continuously heating to 150 ℃ at the heating rate of 1 ℃/min, reacting at the constant temperature of 150 ℃ for 10-20 min, heating to 180 ℃ at the heating rate of 5 ℃/min, and reacting at the constant temperature of 180 ℃ for 50-60 min.
2. The method of claim 1, wherein the pattern Co is formed on the foamed nickel substrate3O4The method for preparing the nano material is characterized in that a collecting container is arranged outside an overflow container in S1, and the hydrochloric acid solution overflowing during cleaning is collected and then is recycled for overflow cleaning through filtering separation.
3. The method of claim 1, wherein the pattern Co is formed on the foamed nickel substrate3O4A method of preparing a nanomaterial, wherein the cobalt salt described in S2 is Co (NO)3)2•6H2O、CoCl2•6H2O、Co(COOCH3)2•4H2And O is one of the compounds.
4. The method of claim 1, wherein the pattern Co is formed on the foamed nickel substrate3O4The method for preparing the nano material is characterized in that the vacuum degree of the solution B subjected to vacuum treatment in the S2 is-0.03 to-0.07 MPa.
5. The method of claim 1, wherein the pattern Co is formed on the foamed nickel substrate3O4The method for preparing the nano material is characterized in that the solution for adjusting the pH value in S3 is 1mol/L ammonia water.
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