CN113223866A - SnO (stannic oxide)2Preparation and application of @ PPy/carbon cloth composite electrode material - Google Patents

Abstract

The invention belongs to the field of nano material synthesis technology and energy storage materials, and particularly relates to SnO₂Preparation and application of the @ PPy/carbon cloth composite electrode material. The sodium citrate is added into an experimental system for the first time, and experiments show that when the sodium citrate is used as a ligand solution to react with tin salt, SnO with a flower-shaped structure and good dispersibility can be prepared without using a strong alkali reagent or a calcining step₂In the prior art, SnO with different shapes is prepared₂The problems of high-temperature calcination, high energy consumption, long time and high difficulty in strong acid and strong alkali treatment exist.

Description

SnO (stannic oxide)2Preparation and application of @ PPy/carbon cloth composite electrode material

Technical Field

The invention belongs to the field of nano material synthesis technology and energy storage materials, and particularly relates to SnO₂Preparation and application of the @ PPy/carbon cloth composite electrode material.

Background

The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.

In recent decades, with the continuous development and progress of science and technology, the demand of human society for energy is increasing, however, the traditional fossil energy is gradually exhausted, and also causes serious environmental pollution. In this context, the importance of efficient utilization and storage techniques for clean energy is self-evident. As a novel energy storage device, the super capacitor has the advantages of high power density, good cycle stability, cleanness, environmental protection and the like, and is widely researched. But the lower energy density limits their development relative to conventional ion batteries. The energy storage performance of the super capacitor is mainly determined by the electrode material, so the research on the electrode material is very important.

SnO₂As a typical transition metal oxide, the metal oxide has low cost, easy synthesis, environmental protection and high electrochemical activity, and can be widely applied to the aspects of sensors, batteries, capacitors, electrochemical catalysis, environment and the like. Although having many advantages, SnO₂Also has the disadvantages of poor conductivity, instability in the circulation process, and the like. In order to improve SnO₂Is an effective method for structural modification.

SnO by some researchers₂Prepared into granular or flower-like structures, but the inventor finds that SnO with different morphologies is prepared₂Meanwhile, some methods require high-temperature calcination to prepare flower-like structures, and some methods require strong acid and strong base to react, and the methods can prepare SnO with different shapes₂However, the high-temperature calcination consumes long time, the steps are complicated, and the treatment difficulty of the strong acid and strong alkali waste liquid is higher.

Disclosure of Invention

In order to solve the problem that SnO with different shapes is prepared in the prior art₂The problems of high-temperature calcination, high energy consumption, long time and high difficulty in strong acid and strong alkali treatment exist, and the invention provides SnO₂The preparation and application of the @ PPy/carbon cloth composite electrode material are characterized in that sodium citrate is added into an experimental system for the first time, and experiments show that when sodium citrate is used as a ligand solution to react with tin salt, a strong base reagent is not needed, and a calcining step is not needed to prepare the SnO with a flower-shaped structure with good dispersibility₂The problems in the prior art are solved. Furthermore, pure polypyrrole (PPy) acts as an electrodeWhen the material is used, the material is extremely unstable in the continuous charging and discharging process, and is easy to cause mechanical degradation, so that the electrochemical performance is poor. The carbon cloth is used as a support, the PPy and the transition metal oxide are compounded and supplement each other, so that the problem of poor capacitance performance of the PPy can be solved, and the overall electrochemical performance of the composite material can be improved.

Specifically, the invention is realized by the following technical scheme:

in a first aspect of the invention, there is provided a SnO with a three-dimensional flower-like structure₂A method of preparing a material comprising: mixing a tin salt solution and an alkaline ligand solution, and reacting to obtain SnO with a three-dimensional flower-like structure₂A material.

In a second aspect of the invention, there is provided a SnO₂@ PPy/carbon cloth composite electrode material, SnO₂Loaded on carbon cloth, SnO₂The surface is coated with PPy.

In a third aspect of the invention, there is provided a SnO₂The preparation method of the @ PPy/carbon cloth composite electrode material comprises the following steps: preparing a tin salt solution and an alkaline ligand solution into a mixed solution, adding carbon cloth for reaction to obtain SnO₂A/carbon cloth composite prepared by mixing SnO₂The/carbon cloth composite material is dipped into pyrrole solution for polymerization reaction to obtain SnO₂@ PPy/carbon cloth composite material.

In a fourth aspect of the invention, there is provided a SnO with a three-dimensional flower-like structure₂Preparation method of material, prepared SnO with three-dimensional flower-like structure₂Materials and/or SnO₂The application of the @ PPy/carbon cloth composite electrode material in the electrochemical field.

In a fifth aspect of the invention, there is provided an electrode material comprising SnO having a three-dimensional flower-like structure₂Preparation method of material, prepared SnO with three-dimensional flower-like structure₂Materials and/or SnO₂@ PPy/carbon cloth composite electrode material.

One or more embodiments of the present invention have the following advantageous effects:

1) the sodium citrate is added into an experimental system for the first time, and experiments show that when the sodium citrate is used as a ligand solution to react with tin salt, a strong alkali reagent is not needed to be used, and calcination is not neededThe step can prepare the SnO with the flower-shaped structure with good dispersibility₂Solves the problem that the prior art prepares SnO with different shapes₂The problems of high-temperature calcination, high energy consumption, long time and high difficulty in strong acid and strong alkali treatment exist.

2) The invention can grow SnO with three-dimensional flower-like structure on carbon cloth in situ₂The material does not need to use a binder, simplifies the operation steps and simultaneously strengthens the carbon cloth substrate and SnO₂Thereby improving the capacitive performance.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention. Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:

FIG. 1 is a three-dimensional flower-like SnO obtained in example 1 of the present invention₂Scanning electron micrographs of the material;

FIG. 2 is a three-dimensional flower-like SnO obtained in example 1 of the present invention₂An X-ray diffraction pattern of the material;

FIG. 3 is a three-dimensional flower-like SnO obtained in example 2 of the present invention₂Scanning electron microscope photo of the/carbon cloth composite material;

FIG. 4 is a three-dimensional flower-like SnO obtained in example 2 of the present invention₂Scanning electron microscope photo of @ PPy/carbon cloth composite material;

FIG. 5 is a three-dimensional flower-like SnO obtained in example 2 of the present invention₂The cyclic voltammetry curve of the @ PPy/carbon cloth composite material at different scanning rates;

FIG. 6 is a three-dimensional flower-like SnO obtained in example 2 of the present invention₂@ PPy/carbon cloth composite electrochemical impedance curves.

Detailed Description

The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The experimental procedures, in which specific conditions are not noted in the following examples, are generally carried out according to conventional conditions or according to conditions recommended by the manufacturers.

It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present disclosure. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.

SnO by some researchers₂Prepared into granular or flower-like structures, but the inventor researches and discovers that SnO can be applied to vegetation with different shapes₂Meanwhile, some methods require high-temperature calcination to prepare flower-like structures, and some methods require strong acid and strong base to react, and the methods can prepare SnO with different shapes₂However, the high-temperature calcination consumes long time, the steps are complicated, and the treatment difficulty of the strong acid and strong alkali waste liquid is higher.

In order to solve the problems, the invention provides SnO₂The preparation and application of the @ PPy/carbon cloth composite electrode material are characterized in that sodium citrate is added into an experimental system for the first time, experiments show that when sodium citrate is used as a ligand solution to react with tin salt, a strong base reagent is not needed, a calcination step is not needed, and SnO with a flower-shaped structure and good dispersibility can be prepared by a one-step method₂The problems in the prior art are solved.

Specifically, the invention is realized by the following technical scheme:

in a first aspect of the invention, there is provided a SnO with a three-dimensional flower-like structure₂A method of preparing a material comprising: mixing a tin salt solution and an alkaline ligand solution, and reacting to obtain SnO with a three-dimensional flower-like structure₂A material.

The principle of the reaction of the alkaline ligand and the tin salt is as follows:

the sodium citrate plays the role of a stabilizer and a complexing agent in the step, can form an alkaline environment and promote Sn (OH)₄Formation of a precipitate, Sn (OH)₄The precipitate will remove two molecules of water under appropriate hydrothermal conditions to produce SnO₂。

The purpose of using strong alkali in the prior art is to form an alkaline environment and promote the generation of precipitate, and the effect of the strong alkali is similar to that of sodium citrate, but the alkalinity is stronger and is difficult to control. Furthermore, the prior art often employs a calcination step for the purpose of producing Sn (OH) by hydrothermal reaction₄Dehydration to form SnO₂. In the invention, the adopted one-step hydrothermal method can directly generate SnO in the hydrothermal process₂The calcination step is omitted.

In one or more embodiments of the present invention, the tin salt is selected from the group consisting of crystalline tin tetrachloride, stannous chloride dihydrate, stannous chloride, stannous oxalate, stannic sulfate, and stannic nitrate;

preferably, the basic ligand is selected from sodium citrate, NH₄F. Urea;

when the alkaline ligand is sodium citrate and the tin salt is stannous chloride dihydrate, the addition of the sodium citrate can realize the preparation of the SnO with the three-dimensional flower-shaped structure without calcination₂Compared with other alkaline ligands, the material has the advantages that the flower-like structure prepared from the sodium citrate is more uniform, the lamella growth is more complete, and the specific surface area is larger.

Preferably, the tin salt concentration is 0.005-0.05g/mL, preferably 0.0282 g/mL;

preferably, the concentration of the alkaline ligand solution is 0.01-0.1g/mL, preferably 0.07365 g/mL;

preferably, the molar ratio of tin salt to basic ligand is (0.05-5):1, preferably 0.564: 1.473.

Preferably, the dissolving temperature of the alkaline ligand is 30-60 ℃, the dissolving time is 10-40min, and preferably 40 ℃ and 30 min.

In the dissolving process of the alkaline ligand solution, the higher the temperature is, the more the alkaline ligand solution is helpful to dissolve the alkaline ligand solution, but the overhigh temperature can damage the structure of the alkaline ligand and reduce the SnO of preparing the three-dimensional flower-like structure under the conditions of no calcination and no strong alkaline reagent₂The effect of the material.

In one or more embodiments of the present invention, the solvent used for the tin salt solution and the basic ligand solution is a mixed solvent of ethanol and deionized water. The mixed solvent of ethanol and deionized water has better mixing and dissolving effects than a single ethanol reagent or a water solvent, and the key influence parameter of the method without calcination effect is the key influence parameter.

Preferably, the volume ratio of the ethanol to the deionized water is 1 (0.5-2), preferably 1: 1;

preferably, the reaction temperature is 160-240 ℃, the reaction time is 6-12 h, preferably 160-200 ℃, 9h, preferably 200 ℃.

Due to the use of alkaline ligand and specific solvent, the invention can prepare SnO with three-dimensional flower-like structure at the reaction temperature without calcining₂The material and the reaction temperature are too high, so that the structure of the alkaline ligand can be damaged, the alkaline ligand cannot play a role, and SnO can be influenced₂The material has a morphology structure and is easy to agglomerate. If the reaction temperature is too low and the reaction is incomplete, high-temperature calcination is required at this time, and the generation of a three-dimensional flower-like structure is further promoted.

In one or more embodiments of the invention, the method further comprises the steps of washing and drying after the reaction is finished;

preferably, the washing comprises washing with deionized water several times, followed by ethanol several times.

Preferably, the drying temperature is 50-80 ℃, preferably 60 ℃.

In a second aspect of the invention, there is provided a SnO₂@ PPy/carbon cloth composite electrode material, SnO₂Loaded on carbon cloth, SnO₂The surface is coated with PPy.

Polypyrrole (PPy) is a common high-molecular conductive polymer material, and has a conjugated structure in which carbon-carbon single bonds and double bonds are sequentially arranged, so that the polypyrrole has good conductivity. In addition, the synthesis process of PPy is simple, the monomer cost is low, and the PPy has good physical and chemical stability, redox activity and higher specific capacitance. Thus, PPy has a wide range of applications in supercapacitors, sensors, electromagnetic shielding, electroluminescence, and solar cells. However, pure PPy as an electrode material is extremely unstable during continuous charging and discharging, and is easily subjected to mechanical degradation, resulting in poor electrochemical properties.

The invention adopts carbon cloth as a substrate material which is SnO₂And PPy loading provides an ideal matrix. The metal oxide with pseudo capacitance and the conductive polymer are organically combined with the carbon material with double electric layer capacitance, so that the advantages are complemented, and the electrochemical performance of the material far exceeding a single component is obtained. SnO conversion using simple hydrothermal and chemical oxidation processes₂And PPy is loaded on the carbon cloth, and any binder and conductive additive are not needed to be added, so that the impedance of the electrode material is reduced, and the utilization rate of the active material is improved. The three-dimensional flower-like structure of the obtained material has a large specific surface area, so that more active sites are provided, the reaction activity of the electrode material is improved, and the material has good electrochemical performance.

In the present invention, PPy is tightly coated with SnO₂The surface has certain interaction, promotes charge transmission, is beneficial to reducing impedance and improving electrochemical performance. If SnO₂And PPy alone, or simply mechanical mixing, do not produce this synergy.

In a third aspect of the invention, there is provided a SnO₂The preparation method of the @ PPy/carbon cloth composite electrode material comprises the following steps: preparing a tin salt solution and an alkaline ligand solution into a mixed solution, adding carbon cloth for reaction to obtain SnO₂A/carbon cloth composite prepared by mixing SnO₂The/carbon cloth composite material is dipped into pyrrole solution for polymerization reaction to obtain SnO₂@ PPy/carbon cloth composite material.

In one or more embodiments of the present invention, the tin salt is selected from crystalline tin tetrachloride, stannous oxalate, tin sulfate, and tin nitrate;

preferably, the tin salt concentration is 0.005-0.05g/mL, preferably 0.0282 g/mL;

preferably, the basic ligand is selected from sodium citrate, NH₄F. Urea;

when the alkaline ligand is sodium citrate and the tin salt is stannous chloride dihydrate, the addition of the sodium citrate can realize the preparation of the SnO with the three-dimensional flower-shaped structure without calcination₂Materials, sodium citrate preparation compared to other basic ligandsThe flower-shaped structure is more uniform, the lamella growth is more complete, and the specific surface area is larger.

In addition, when the alkaline ligand, the carbon cloth and the tin salt react in the same system, the carbon cloth can be SnO₂The load of the material provides a foundation, which is beneficial to improving the contact area of the alkaline ligand and the tin salt, and further beneficial to improving the overall electrical property of the composite material.

Preferably, the concentration of the alkaline ligand solution is 0.01-0.1g/mL, preferably 0.07365 g/mL;

preferably, the molar ratio of tin salt to basic ligand is (0.05-5):1, preferably 0.564: 1.473;

synthesis of SnO₂The @ PPy/carbon cloth composite material can change the component proportion in the material and influence the electrochemical performance of the material.

Preferably, the dissolving temperature of the alkaline ligand is 30-60 ℃, the dissolving time is 10-40min, preferably 40 ℃, 30 min;

in the dissolving process of the alkaline ligand solution, the higher the temperature is, the more the alkaline ligand solution is helpful to dissolve the alkaline ligand solution, but the overhigh temperature can damage the structure of the alkaline ligand and reduce the SnO of preparing the three-dimensional flower-like structure under the conditions of no calcination and no strong alkaline reagent₂The effect of the material.

Preferably, the solvent used by the tin salt solution and the alkaline ligand solution is a mixed solvent of ethanol and deionized water;

preferably, the volume ratio of the ethanol to the deionized water is 1 (0.5-2), preferably 1: 1;

preferably, the temperature for adding the carbon cloth for reaction is 160-240 ℃, the reaction time is 6-12 h, preferably 200 ℃ and 9 h.

In one or more embodiments of the invention, the method further comprises a step of pretreating the carbon cloth before adding the carbon cloth for reaction;

preferably, the step of pretreating the carbon cloth comprises: cleaning, drying, soaking in acid solution, washing and drying;

preferably, the acid solution is selected from a mixed solution of hydrochloric acid and concentrated nitric acid;

preferably, the volume ratio of the hydrochloric acid to the nitric acid is 1 (0.5-2), preferably 1: 1;

preferably, the method also comprises the steps of washing and drying after the carbon cloth is added for reaction;

preferably, the washing comprises washing with deionized water for a plurality of times, and then washing with ethanol for a plurality of times;

preferably, the drying temperature is 50-80 ℃, preferably 60 ℃.

In one or more embodiments of the invention, the pyrrole solution is FeCl₃And pyrrole mixed solution, wherein the solvent is hydrochloric acid;

first, in an oxidizing agent (FeCl)₃) Under the action of (3), one charge-neutral pyrrole monomer molecule loses one electron and is oxidized into a cation free radical. Subsequently, the two cationic radicals combine to form the dication of the dimeric pyrrole, which undergoes disproportionation to form the electrically neutral dimeric pyrrole. The dipyrromethene is then oxidized again, binds to the cationic free radicals, and is then disproportionated to form a trimer. This reaction proceeds until chain-like PPy molecules having a polymerization degree of n are formed.

Preferably, the concentration of the dilute hydrochloric acid is 0.5-1.0M;

preferably, the FeCl₃And pyrrole concentration of 0.1-0.2M and 0.01-0.5M, respectively; preferably 0.1M FeCl₃Solution and 0.2M pyrrole solution.

Preferably, the polymerization reaction temperature is-10-80 ℃, and the time is 10-120min, preferably 30 min;

too high a polymerization temperature may affect the existing SnO₂The structure of the material does not meet the requirements of energy conservation and environmental protection; the polymerization temperature is too low to be in SnO₂The PPy layer is completely covered on the surface of the material, and the problem of single use of SnO₂Material or PPy layer.

Preferably, the SnO₂The mass ratio of the carbon cloth composite material to the pyrrole monomer is 8: 1;

preferably, the polymerization reaction further comprises the steps of washing and drying;

preferably, the washing comprises washing three times with a NaCl solution, dilute hydrochloric acid, and deionized water in sequence.

The invention combines the transition metal oxide with Faraday pseudo-capacitance, the conductive polymer and the carbon material with double electric layer capacitance, combines the advantages of the three, and overcomes the defect of single material performance.

The invention adopts a self-assembly solvothermal method and a chemical oxidation method for synthesis, the synthesis method is simple and easy to implement, and no adhesive or other additives are used in the synthesis process, so that the electrode impedance can be effectively reduced, and the utilization rate of the electrode material is improved.

The three-dimensional flower-like structure creates favorable conditions for the subsequent modification of other materials, has larger specific surface area and more active sites, and can enhance the reactivity of the material. Thus, three-dimensional flower-like structure SnO₂The material has good electrochemical performance.

Scanning electron microscope pair prepared three-dimensional flower-shaped SnO₂The @ PPy/carbon cloth composite material is subjected to morphology characterization, and the electrochemical performance of the material is evaluated by using a cyclic voltammetry method and an electrochemical impedance method. As can be seen from the characterization data, the three-dimensional flower-shaped SnO prepared by the invention₂The @ PPy/carbon cloth composite material has excellent electrochemical performance and is an energy storage material with very wide prospect.

In a fourth aspect of the invention, there is provided a SnO with a three-dimensional flower-like structure₂Preparation method of material, prepared SnO with three-dimensional flower-like structure₂Materials and/or SnO₂The application of the @ PPy/carbon cloth composite electrode material in the electrochemical field.

The electrochemical field comprises the fields of battery, electrode material of super capacitor and the like.

The battery is selected from lithium ion batteries, and the electrode is selected from a supercapacitor composite electrode.

In a fifth aspect of the invention, there is provided an electrode material comprising SnO having a three-dimensional flower-like structure₂Preparation method of material, prepared SnO with three-dimensional flower-like structure₂Materials and/or SnO₂@ PPy/carbon cloth composite electrode material.

The present invention is described in further detail below with reference to specific examples, which are intended to be illustrative of the invention and not limiting.

Example 1

Three-dimensional flower-like structure SnO₂Preparation of the Material

1. Preparation of metal salt solution: accurately weigh 0.564g of stannous chloride dihydrate (SnCl) using an electronic balance₂·2H₂O) is placed in a small beaker of 100mL, 10mL of ethanol and 10mL of deionized water are sequentially added, the mixture is stirred for 10min to be uniformly mixed, and then ultrasonic treatment is carried out for about 30min until white crystals are completely dissolved.

2. Preparation of a precipitating agent: accurately weigh 1.473g trisodium citrate (C) using an electronic balance₆H₅Na₃O₇) The mixture was placed in a 100mL small beaker, 10mL of ethanol and 10mL of deionized water were added in sequence, and the mixture was stirred in a water bath at 40 ℃ for 30min until the white crystals at the bottom of the beaker completely disappeared. Trisodium citrate belongs to strong base and weak acid salt, and generates hydroxide ions after being dissolved in water to form an alkaline environment. The hydroxide ions are then combined with the metal ions to obtain a precipitate.

3、SnO₂The preparation of (1): the nano material is prepared by adopting a solvothermal self-assembly method. The pretreated carbon is distributed at the bottom of the polytetrafluoroethylene lining, the metal salt solution and the precipitator solution are uniformly mixed, and the mixture is transferred into the lining and sealed in the shell of the stainless steel high-pressure reaction kettle. And (3) putting the reaction kettle into an oven at 200 ℃, and preserving heat for 9 hours. Taking out and naturally cooling to room temperature. Washing the reacted carbon cloth with ethanol and deionized water for three times, and drying at 60 ℃ for one night to obtain three-dimensional flower-shaped SnO₂Carbon cloth sample. Centrifuging the residual solution for three times, collecting precipitate, and drying in a 60 deg.C oven overnight to obtain three-dimensional flower-like SnO₂And (3) nano materials.

Example 2

SnO₂Preparation of @ PPy/carbon cloth composite electrode material

1. Pretreatment of the carbon cloth: the carbon cloth was cut into 1 × 2cm pieces and washed with acetone, ethanol and deionized water in sequence. The cleaned carbon cloth was placed in an oven at 60 ℃ and dried overnight. Preparing concentrated hydrochloric acid: concentrated nitric acid 1:1 (volume ratio), placing the carbon cloth in the mixed solution, soaking for 6 hours, washing for several times by using distilled water until the solution is neutral, finally drying in an oven at 60 ℃ for one night, and collecting the solution for later use.

2. Preparation of metal salt solution: accurately weigh 0.564g of stannous chloride dihydrate (SnCl) using an electronic balance₂·2H₂O) is placed in a small beaker of 100mL, 10mL of ethanol and 10mL of deionized water are sequentially added, the mixture is stirred for 10min to be uniformly mixed, and then ultrasonic treatment is carried out for 30min until white crystals are completely dissolved.

3. Preparation of a precipitating agent: accurately weigh 1.473g trisodium citrate (C) using an electronic balance₆H₅Na₃O₇) The mixture was placed in a 100mL small beaker, 10mL of ethanol and 10mL of deionized water were added in sequence, and the mixture was stirred in a water bath at 40 ℃ for 30min until the white crystals at the bottom of the beaker completely disappeared.

4、SnO₂Preparation of carbon cloth: the nano material is prepared by adopting a solvothermal self-assembly method. The pretreated carbon is distributed at the bottom of the polytetrafluoroethylene lining, the metal salt solution and the precipitator solution are uniformly mixed, and the mixture is transferred into the lining and sealed in the shell of the stainless steel high-pressure reaction kettle. And (3) putting the reaction kettle into an oven at 200 ℃, and preserving heat for 9 hours. Taking out and naturally cooling to room temperature. Washing the reacted carbon cloth with ethanol and deionized water for three times, and drying at 60 ℃ for one night to obtain three-dimensional flower-shaped SnO₂Carbon cloth sample. Centrifuging the residual solution for three times, collecting precipitate, and drying in a 60 deg.C oven overnight to obtain three-dimensional flower-like SnO₂And (3) nano materials.

5、SnO₂Preparation of @ PPy/carbon cloth: respectively using dilute hydrochloric acid solution as solvent to prepare 0.1M FeCl₃The solution and 0.2M pyrrole solution are stirred evenly, and then the two solutions are mixed under stirring and polymerized for 30 min. Washing the polymerized carbon cloth with NaCl solution, dilute hydrochloric acid and deionized water for three times in sequence, and drying to obtain the final product SnO₂@ PPy/carbon cloth composite material.

And (3) testing the performance of the sample:

so as to obtain three-dimensional flower-shaped SnO₂The @ PPy/carbon cloth composite material is used as a working electrode, the platinum sheet electrode is used as a counter electrode, and the saturated calomel electrode is used as a reference electrodeAnd a three-electrode system is assembled by taking a 1M KOH solution as an electrolyte to carry out electrochemical performance test.

FIG. 1 is a three-dimensional flower-like SnO of example 1₂The embroidered ball-shaped structure of the nano material can be obviously seen from the Scanning Electron Microscope (SEM) picture of the nano material.

FIG. 2 is a three-dimensional flower-like SnO of example 1₂The X-ray diffraction (XRD) pattern of the nano material has obvious diffraction peaks at 26.5, 33.1, 37.8, 51.3, 61.1 and 65.4 degrees, and respectively belongs to SnO₂The (110), (101), (200), (211), (310) and (301) crystal planes, so that the method can be concluded to successfully synthesize the three-dimensional flower-shaped SnO₂And (3) nano materials.

FIG. 3 is SnO prepared in example 2₂SEM pictures of the/carbon cloth composite material clearly show that three-dimensional flower-shaped SnO2 is loaded on the surface of the carbon fiber.

FIG. 4 is SnO prepared in example 2₂SEM photograph of @ PPy/carbon cloth composite material, SnO can be seen₂The surface is uniformly loaded with a layer of PPy.

FIG. 5 is a three-dimensional flower-like SnO obtained from example 2₂The @ PPy/carbon cloth composite material is a cyclic voltammetry curve tested by a working electrode under a three-battery system. According to the calculation formula of the specific capacitance, the specific capacitance of the electrode is about 1.61F/cm at the scanning rate of 2mV/s²When the scanning speed is as high as 100mV/s, the specific capacitance is about 0.194F/cm²The assembled super capacitor is shown to have good capacitance and rate performance.

FIG. 6 is a three-dimensional flower-like SnO prepared in example 2₂The @ PPy/carbon cloth composite material is used as an electrode material, and an electrochemical impedance graph is obtained by testing under a three-electrode system.

Example 3

The only difference was that the polymerization time instep 5 was 10min, as in example 2.

Example 4

The only difference was that the polymerization time instep 5 was 120min, as in example 2.

Example 5

The same as in example 2, except that in the hydrothermal reaction in step 4, the reaction temperature was 160 ℃.

Example 6

The same as in example 2, except that in the hydrothermal reaction in step 4, the reaction temperature was 180 ℃.

Example 7

The same as in example 2, except that in the hydrothermal reaction in step 4, the reaction time was 6 hours.

Example 8

The same as in example 2, except that in the hydrothermal reaction in step 4, the reaction time was 12 hours.

Example 9

As in example 2, except that the ratio of ethanol to water in the solvent in step 2 alone is 1: 2.

example 10

As in example 2, except that the ratio of ethanol to water in the solvent in step 2 only was 2: 1.

table 1 shows three-dimensional flower-like SnO prepared in examples 2-10₂The electrical properties of the @ PPy/carbon cloth composite material. As can be seen from the figure, the polymerization time, hydrothermal reaction temperature, time, and ratio of ethanol to water affect the cycle performance of the composite electrode, and only the three-dimensional flower-shaped SnO prepared under the conditions of example 2₂The @ PPy/carbon cloth composite material has the best electrical property.

TABLE 1 three-dimensional flower-like SnO prepared in examples 2-10₂Electric property of @ PPy/carbon cloth composite material

Although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that changes may be made in the embodiments and/or equivalents thereof without departing from the spirit and scope of the invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (10)

1. SnO with three-dimensional flower-shaped structure₂The preparation method of the material is characterized by comprising the following steps: mixing a tin salt solution and an alkaline ligand solution, and reacting to obtain SnO with a three-dimensional flower-like structure₂A material.

2. Three-dimensional flower-like structured SnO according to claim 1₂A method for preparing a material, characterized in that the tin salt is selected from crystalline tin tetrachloride, stannous chloride dihydrate, stannous chloride, stannous oxalate, stannic sulfate and stannic nitrate;

preferably, the tin salt concentration is 0.005-0.05g/mL, preferably 0.0282 g/mL;

preferably, the basic ligand is selected from sodium citrate, NH₄F. Urea;

preferably, the concentration of the alkaline ligand solution is 0.01-0.1g/mL, preferably 0.07365 g/mL;

preferably, the molar ratio of tin salt to basic ligand is 0.05-5:1, preferably 0.564: 1.473;

preferably, the dissolving temperature of the alkaline ligand is 30-60 ℃, the dissolving time is 10-40min, and preferably 40 ℃ and 30 min.

3. Three-dimensional flower-like structured SnO according to claim 1₂The preparation method of the material is characterized in that the solvent used by the tin salt solution and the alkaline ligand solution is a mixed solvent of ethanol and deionized water;

preferably, the volume ratio of the ethanol to the deionized water is 1:0.5-2, preferably 1: 1;

preferably, the reaction temperature is 160-240 ℃, the reaction time is 6-12 h, preferably 160-200 ℃, 9h, preferably 200 ℃.

4. The compound of claim 1SnO with flower-like structure₂The preparation method of the material is characterized by also comprising the steps of washing and drying after the reaction is finished;

preferably, the washing comprises washing with deionized water for a plurality of times, and then washing with ethanol for a plurality of times;

preferably, the drying temperature is 50-80 ℃, preferably 60 ℃.

5. SnO (stannic oxide)₂The @ PPy/carbon cloth composite electrode material is characterized in that SnO₂Loaded on carbon cloth, SnO₂The surface is coated with PPy.

6. A SnO according to claim 5₂A preparation method of the @ PPy/carbon cloth composite electrode material is characterized by comprising the following steps: preparing a tin salt solution and an alkaline ligand solution into a mixed solution, adding carbon cloth for reaction to obtain SnO₂A/carbon cloth composite prepared by mixing SnO₂The/carbon cloth composite material is dipped into pyrrole solution for polymerization reaction to obtain SnO₂@ PPy/carbon cloth composite;

preferably, the tin salt is selected from crystalline tin tetrachloride, stannous oxalate, tin sulfate and tin nitrate;

preferably, the tin salt concentration is 0.005-0.05g/mL, preferably 0.0282 g/mL;

preferably, the basic ligand is selected from sodium citrate, NH₄F. Urea;

preferably, the concentration of the alkaline ligand solution is 0.01-0.1g/mL, preferably 0.07365 g/mL;

preferably, the molar ratio of tin salt to basic ligand is 0.05-5:1, preferably 0.564: 1.473;

preferably, the dissolving temperature of the alkaline ligand is 30-60 ℃, the dissolving time is 10-40min, preferably 40 ℃, 30 min;

preferably, the solvent used by the tin salt solution and the alkaline ligand solution is a mixed solvent of ethanol and deionized water;

preferably, the volume ratio of the ethanol to the deionized water is 1:0.5-2, preferably 1: 1;

preferably, the temperature for adding the carbon cloth for reaction is 160-240 ℃, the reaction time is 6-12 h, preferably 200 ℃ and 9 h.

7. A SnO according to claim 5₂The preparation method of the @ PPy/carbon cloth composite electrode material is characterized by further comprising the step of pretreating the carbon cloth before adding the carbon cloth for reaction;

preferably, the step of pretreating the carbon cloth comprises: cleaning, drying, soaking in acid solution, washing and drying;

preferably, the acid solution is selected from a mixed solution of hydrochloric acid and concentrated nitric acid;

preferably, the volume ratio of the hydrochloric acid to the nitric acid is 1:0.5-2, preferably 1: 1;

preferably, the method also comprises the steps of washing and drying after the carbon cloth is added for reaction;

preferably, the washing comprises washing with deionized water for a plurality of times, and then washing with ethanol for a plurality of times;

preferably, the drying temperature is 50-80 ℃, preferably 60 ℃.

8. A SnO according to claim 6₂The preparation method of the @ PPy/carbon cloth composite electrode material is characterized in that the pyrrole solution is FeCl₃And pyrrole mixed solution, wherein the solvent is hydrochloric acid;

preferably, the concentration of the hydrochloric acid is 0.5-1.0M;

preferably, the FeCl₃And pyrrole concentration of 0.1-0.2M and 0.01-0.5M, respectively;

preferably, the polymerization reaction temperature is-10-80 ℃, and the time is 10-120min, preferably 30 min;

preferably, the SnO₂The mass ratio of the carbon cloth composite material to the pyrrole monomer is 8: 1;

preferably, the polymerization reaction further comprises the steps of washing and drying;

preferably, the washing comprises washing three times with a NaCl solution, dilute hydrochloric acid, and deionized water in sequence.

9. Three-dimensional flower-like structured SnO according to any of claims 1 to 4₂Preparation method of material, prepared SnO with three-dimensional flower-like structure₂Material and/or SnO according to claim 5₂The application of the @ PPy/carbon cloth composite electrode material in the electrochemical field.

10. An electrode material comprising the three-dimensional flower-like structure SnO according to any of claims 1 to 4₂Preparation method of material, prepared SnO with three-dimensional flower-like structure₂Material and/or SnO according to claim 5₂@ PPy/carbon cloth composite electrode material.

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