CN113223869B - Three-dimensional porous nanoflower-like NiS 2 Preparation and application of/carbon cloth composite material - Google Patents
Three-dimensional porous nanoflower-like NiS 2 Preparation and application of/carbon cloth composite material Download PDFInfo
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H—ELECTRICITY
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
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Abstract
The invention belongs to the field of inorganic nano material synthesis technology and energy storage materials, and particularly relates to three-dimensional porous nanoflower-shaped NiS 2 Preparation and application of the/carbon cloth composite material. By adding urea and ammonia-containing solution into the experimental system, three-dimensional flower-shaped Ni (OH) can be reduced 2 The reaction temperature can also be increased, and the three-dimensional flower-shaped Ni (OH) can be improved 2 Purity, in order to further improve the three-dimensional flower-like Ni (OH) 2 The invention also discloses a method for etching three-dimensional flower-shaped Ni (OH) 2 Preparation of three-dimensional porous nanoflower-shaped NiS by pore-forming on lamellar structure 2 The material can improve the electrochemical performance, and can avoid the problems of agglomeration and poor electrochemical circulation capability caused by simply introducing functional groups, and untight bonding and uneven distribution caused by introducing a second phase.
Description
Technical Field
The invention belongs to the field of inorganic nano material synthesis technology and energy storage materials, and particularly relates to three-dimensional porous nanoflower-shaped NiS 2 Preparation and application of the/carbon cloth composite 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.
Nano materials and their technologies are one of the hot spots of scientific research at present, and are considered as another industrial revolution of the century. With the further demand for nanomaterial applications in different fields, an important trend in the research of nanomaterial fabrication technology is currently the intensive control engineering research, which includes the control of particle size, surface shape and microstructure. Therefore, the synthesis of high-purity nano materials with controllable morphology and structure by adopting a proper method is an important research direction for researching advanced materials and high-performance materials.
The transition metal oxide has abundant redox activity in the energy storage process, and has wide research on the aspect of energy storage materials. Ni (OH) 2 As a typical transition metal oxide, the transition metal oxide has the advantages of low cost, easy synthesis, good stability, high electrochemical activity and the like, and has good application in the aspects of manufacturing batteries, capacitors, electrochemical catalysis and the like. However, as with other pseudocapacitive materials, this promising electrode material also has the problems of low intrinsic conductivity and severe volume expansion during cycling.
The inventors have found that some of the prior art combines Ni (OH) 2 Prepared into three-dimensional flower shape, but has high reaction temperature and long reaction time, or Ni (OH) 2 Irregular crystal form and low purity. And the three-dimensional flower-like structure has limited improvement effect on the electrochemical performance, if the performance is further improved, a functional group or a functional structure is required to be loaded, the preparation process is complex, and the prepared electrode element has poor electrochemical stability.
Disclosure of Invention
In order to solve the problem of three-dimensional flower-shaped Ni (OH) existing in the prior art 2 The invention provides a three-dimensional porous nano flower-shaped NiS, which has the problems of high reaction temperature, long reaction time, low purity and limited effect on improving electrochemical performance 2 Preparation and application of/carbon cloth composite material, urea and ammoniated solution are added into an experimental system, so that three-dimensional flower-shaped Ni (OH) can be reduced 2 The reaction temperature can be increased, and the three-dimensional flower-shaped Ni (OH) can be increased 2 Purity, in order to further improve the three-dimensional flower-like Ni (OH) 2 The invention also relates to a three-dimensional flower formed by the etching methodNi (OH) 2 Preparation of three-dimensional porous nanoflower NiS by pore-forming on lamellar structure 2 The material can improve the electrochemical performance, and can avoid the problems of agglomeration, poor electrochemical circulation capability, untight combination and uneven distribution caused by the introduction of a second phase, which are caused by the simple introduction of functional groups.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, a three-dimensional flower-like Ni (OH) is provided 2 A method of preparing a material comprising: dissolving nickel salt, an alkaline reagent and an acidic reagent in a solvent, mixing, and carrying out hydrothermal reaction to obtain the nickel-zinc-manganese-zinc composite catalyst.
In a second aspect of the invention, there is provided a three-dimensional flower-like Ni (OH) 2 Preparation method of material, and three-dimensional flower-shaped Ni (OH) prepared by using preparation method 2 A material.
In a third aspect of the invention, there is provided a three-dimensional flower-like Ni (OH) 2 Carbon cloth composite, three-dimensional flower-like Ni (OH) 2 The material is positioned on the surface of the carbon cloth.
In a fourth aspect of the invention, there is provided a three-dimensional flower-like Ni (OH) 2 The preparation method of the/carbon cloth composite material comprises the following steps: and (3) putting the carbon cloth into a solution containing nickel salt, an alkaline reagent and an acidic reagent, mixing, and carrying out hydrothermal reaction to obtain the carbon cloth.
In the fifth aspect of the invention, a three-dimensional porous nanoflower-shaped NiS is provided 2 Material, the three-dimensional porous nanoflower-like NiS 2 The material is in a nanometer flower shape consisting of a lamellar structure, and the lamellar structure is provided with through holes.
In a sixth aspect of the invention, a three-dimensional porous nanoflower-shaped NiS is provided 2 A method of preparing a material comprising: three-dimensional flower-shaped Ni (OH) 2 And (3) reacting the material with sulfur powder to obtain the material.
The seventh aspect of the invention provides a three-dimensional porous nanoflower NiS 2 Carbon cloth composite material, three-dimensional porous nanoflower-like NiS 2 The material is positioned on the surface of the carbon cloth.
In the eighth aspect of the invention, the invention provides three-dimensional porous nanoflower-shaped NiS 2 The preparation method of the/carbon cloth composite material comprises the following steps: putting carbon cloth intoMixing nickel salt, an alkaline reagent and an acidic reagent in a solution, carrying out hydrothermal reaction, and mixing the obtained product with sulfur powder for reaction to obtain the catalyst.
The ninth aspect of the invention provides a three-dimensional flower-shaped Ni (OH) 2 Material and/or three-dimensional flower-like Ni (OH) 2 Carbon cloth composite material and/or three-dimensional porous nanoflower-shaped NiS 2 Material and/or three-dimensional porous nanoflower-like NiS 2 The carbon cloth composite material is applied to the fields of batteries, vehicles and electric appliances.
In a tenth aspect of the present invention, there is provided a battery comprising three-dimensional flower-like Ni (OH) 2 Material and/or three-dimensional flower-like Ni (OH) 2 Carbon cloth composite material and/or three-dimensional porous nanoflower-shaped NiS 2 Material and/or three-dimensional porous nanoflower-like NiS 2 A/carbon cloth composite material.
One or more embodiments of the present invention have the following advantageous effects:
1) By adding urea and ammonia-containing solution into the experimental system, three-dimensional flower-shaped Ni (OH) can be reduced 2 The reaction temperature can be increased, and the three-dimensional flower-shaped Ni (OH) can be increased 2 And (4) purity.
2) Ni (OH) of carbon cloth 2 The load provides an ideal matrix, and the carbon material with double-layer capacitance and the metal oxide with pseudo-capacitance are organically combined, so that the electrochemical performance of the single-component material is improved. Simultaneously, ni (OH) is made by a one-step hydrothermal method 2 The carbon cloth grows in situ, does not need any conductive additive or adhesive, improves the utilization rate of the electrode material, and the obtained material has a three-dimensional flower-shaped structure, exposes more active sites, provides an effective channel for the interpenetration of electrolyte ions, and leads Ni (OH) 2 The carbon cloth composite material has good electrochemical performance.
3) If directly on the three-dimensional flower shape Ni (OH) 2 The functional groups are grafted on the surface of the material, and the problem of agglomeration or poor stability is easy to occur due to the interaction between the functional groups if Ni (OH) is in a three-dimensional flower shape 2 Adding a second phase into the material, wherein the second phase and three-dimensional flower-shaped Ni (OH) 2 The uniformity and adhesion of the material are poor. Therefore, the invention is inventiveEtching three-dimensional flower-shaped Ni (OH) 2 Preparation of three-dimensional porous nanoflower-shaped NiS by pore-forming on lamellar structure 2 The material increases the specific surface area of the material, provides more active sites for electrochemical reaction, and improves the electrochemical performance.
4) The electrochemical performance of the NiS is evaluated by adopting a cyclic voltammetry method and an electrode cyclic performance method, and the three-dimensional porous floriform NiS prepared by the method can be known 2 The/carbon cloth composite material has excellent electrochemical performance, so NiS 2 Has the potential to be used as a high-performance energy storage material.
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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 included to illustrate an exemplary embodiment of 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 shows three-dimensional flower-like Ni (OH) obtained in example 1 of the present invention 2 Scanning electron micrographs of the material;
FIG. 2 shows three-dimensional flower-like Ni (OH) obtained in example 1 of the present invention 2 An XRD pattern of the material;
FIG. 3 shows three-dimensional flower-like Ni (OH) obtained in example 2 of the present invention 2 Scanning electron microscope photos of the/carbon cloth composite material;
FIG. 4 shows three-dimensional flower-like Ni (OH) obtained in example 2 of the present invention 2 The cyclic voltammetry curves of the carbon cloth composite material at different scanning rates;
FIG. 5 shows three-dimensional flower-like Ni (OH) obtained in example 2 of the present invention 2 Electrochemical impedance curve of the/carbon cloth composite material;
FIG. 6 shows three-dimensional porous flower-like NiS obtained in example 11 of the present invention 2 Scanning electron micrographs of the material;
FIG. 7 shows the three-dimensional porous flower-like NiS obtained in example 11 of the present invention 2 An XRD pattern of the material;
FIG. 8 shows the three-dimensional porous flower-like NiS obtained in example 12 of the present invention 2 Scanning electron microscope photos of the/carbon cloth composite material;
FIG. 9 shows the three-dimensional poly-crystal obtained in example 12 of the present inventionKong Huazhuang NiS 2 The cyclic voltammetry curves of the carbon cloth composite electrode at different scanning rates;
FIG. 10 shows the three-dimensional porous flower-like NiS obtained in example 12 of the present invention 2 The/carbon cloth composite electrode has a cycle curve of 8000 charge-discharge cycles under the current density of 5A/g.
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.
In order to solve the three-dimensional flower-shaped Ni (OH) existing in the prior art 2 The invention provides a three-dimensional porous nano flower-shaped NiS, which has the problems of high reaction temperature, long reaction time, low purity and limited effect on improving electrochemical performance 2 Preparation and application of/carbon cloth composite material, urea and ammoniated solution are added into an experimental system, so that three-dimensional flower-shaped Ni (OH) can be reduced 2 The reaction temperature can also be increased, and the three-dimensional flower-shaped Ni (OH) can be improved 2 Purity, in order to further improve the three-dimensional flower-like Ni (OH) 2 The invention also discloses a method for etching three-dimensional flower-shaped Ni (OH) 2 Preparation of three-dimensional porous nanoflower-shaped NiS by pore-forming on lamellar structure 2 The material can improve the electrochemical performance, and can avoid the problems of agglomeration and poor electrochemical circulation capability caused by simply introducing functional groups, and untight bonding and uneven distribution caused by introducing a second phase.
Specifically, the invention is realized by the following technical scheme:
in a first aspect of the invention, a three-dimensional flower-like Ni (OH) is provided 2 A method of preparing a material comprising: dissolving nickel salt, an alkaline reagent and an acidic reagent in a solvent, mixing, and carrying out hydrothermal reaction to obtain the nickel-zinc-manganese-zinc composite catalyst.
If only the acidic solution is added, the hydrogen ions in the solution increase, the hydroxide ions decrease, and hydroxide cannot be generated. If only the alkaline solution is added, the alkalinity is too strong, so that the crystallization kinetic behavior of each crystal face is influenced, and the appearance is damaged. The pH value of the mixed solution can be accurately measured by instruments such as a pH meter and the like when the acidic solution and the alkaline solution are added simultaneously, so that the pH value required by the reaction is effectively controlled.
In the invention, only an acidic reagent and an alkaline reagent are needed to be used for adjusting the system to a pH value in a proper range, and the acidic reagent and the alkaline reagent are not needed to be continuously added in the reaction process.
Preferably, the nickel salt is selected from NiCl 2 ·6H 2 O，NiSO 4 ·6H 2 O，Ni(NO 3 ) 2 ·6H 2 O， Ni(CH 3 COO) 2 ·4H 2 One or more of O;
preferably, the alkaline agent is selected from urea, sodium carbonate, sodium bicarbonate, and the like;
preferably, the acidic reagent is selected from ammonia-containing reagents selected from ammonium fluoride, ammonium chloride, ammonium nitrate and ammonium sulfate;
preferably, the concentration of the nickel salt is 0.2-0.5mol/L;
preferably, the acidic reagent and the alkaline reagent are added in such amounts that the reaction system has a pH of from 8 to 11, preferably from 9 to 11.
The urea is decomposed into carbon dioxide and ammonium hydroxide under heating, and the ammonium hydroxide and nickel salt react under hydrothermal conditions to generate nickel hydroxide. In the case of ammonium fluoride, fluorine ions may be selectively adsorbed on each crystal face, so that the crystallization kinetic behavior of each crystal face is changed, and finally, the difference in crystal morphology is caused. And NH 4 + Adsorption is relatively difficult, but changes the polarity of the solution, affecting mass transfer. Flower shaped knotThe formation of structure is that ammonium hydroxide reacts with nickel salt to form a certain amount of crystal nucleus, and then under the action of fluoride ion and anisotropy, crystal orientation grows to finally form flower-like material.
Because urea is dissolved in water and then decomposed into carbon dioxide and ammonium hydroxide at a relatively low temperature, the ammonium hydroxide reacts with the nickel salt to form nickel hydroxide. The violent decomposition temperature of the urea is about 160 ℃, and the urea is rapidly decomposed to form ammonia gas, so that the decomposition rate of the urea is too high, the nucleation rate of crystals is far higher than the growth rate of the crystals, and the uniform flower-shaped structure is difficult to form.
Preferably, the temperature of the hydrothermal reaction is 60-180 ℃ and the time is 5-24h, preferably 110 ℃ and 10h.
The hydrothermal reaction temperature not only affects the three-dimensional flower-shaped Ni (OH) 2 The morphology of the material, and also its crystal type and purity. It is found that the hydrothermal reaction temperature is too high, which leads to a too high urea decomposition rate, so that the crystal nucleation rate is much higher than the crystal growth rate, and the uniform flower-like structure is difficult to form. Too low a hydrothermal reaction temperature may result in incomplete urea decomposition by XXX, and formation of nuclei is greatly restricted, resulting in Ni (OH) 2 The yield is reduced and the morphology cannot be controlled.
The preparation method further comprises the following steps: after the hydrothermal reaction is finished, the green precipitate generated in the solution is respectively washed by deionized water and absolute ethyl alcohol and then is placed in a vacuum drying oven for drying, and the three-dimensional flower-shaped Ni (OH) is obtained 2 A material.
In a second aspect of the invention, there is provided a three-dimensional flower-like Ni (OH) 2 Preparation method of material, and three-dimensional flower-shaped Ni (OH) prepared by using preparation method 2 A material.
In a third aspect of the invention, there is provided a three-dimensional flower-like Ni (OH) 2 Carbon cloth composite, three-dimensional flower-like Ni (OH) 2 The material is positioned on the surface of the carbon cloth.
The carbon cloth is Ni (OH) 2 The load provides an ideal matrix, and the carbon material with double-layer capacitance and the metal oxide with pseudo-capacitance are organically combined, so that the electrochemical performance of the single-component material is improved.
In a fourth aspect of the invention, there is provided a three-dimensional flower-like Ni (OH) 2 The preparation method of the/carbon cloth composite material comprises the following steps: and (3) putting the carbon cloth into a solution containing nickel salt, an alkaline reagent and an acidic reagent, mixing, and carrying out hydrothermal reaction to obtain the carbon cloth.
The type, proportion, concentration, pH value, reaction temperature and time of nickel salt, alkaline reagent and acidic reagent, and the three-dimensional flower-shaped Ni (OH) 2 The preparation method of the material is the same.
Benefit from Ni (OH) prepared by the invention 2 The three-dimensional flower-shaped structure of the carbon cloth composite material can expose more active sites, reduce the diffusion path of ions, effectively relieve the influence caused by volume expansion and effectively improve the electrochemical performance of the electrode.
To further promote the three-dimensional flower shape Ni (OH) 2 Electrochemical performance of/carbon cloth composite, said three-dimensional flower-like Ni (OH) 2 The preparation method of the/carbon cloth composite material also comprises a carbon cloth pretreatment step, wherein the pretreatment step comprises the following steps: cutting, washing, soaking in mixed acid, washing to neutrality, and drying.
The washing comprises washing with acetone, ethanol and deionized water;
the mixed acid is selected from two or three of nitric acid, hydrochloric acid and sulfuric acid, so that the mixed acid can fully absorb acid radical ions, the pH value of the mixed acid is tested every 1h, and the mixed acid is washed with distilled water for several times to be neutral after the acidity of the mixed acid reaches the maximum value.
The carbon cloth is composed of carbon fibers, and various auxiliary agents need to be sized and infiltrated in order to facilitate bundling and weaving in the spinning and weaving processes, and are attached to the commercially available carbon cloth. The invention further grows active materials by taking the carbon cloth as a matrix. The presence of these impurities can affect the structural and electrochemical performance of the final carbon cloth composite. The mixed acid is used as a strong oxidant, so that the impurities can be removed, and the growth of the active material is facilitated. In addition, the oxidation and the etching of the mixed acid enable the smooth surface of the carbon fiber to be rough, and the adsorption of metal ions and the growth of subsequent metal compounds are facilitated.
The three-dimensional flower shape Ni (OH) 2 Composite of/carbon clothThe preparation method of the material also comprises the steps of taking out the reacted carbon cloth, washing the carbon cloth by deionized water for a plurality of times, soaking the carbon cloth in ethanol solution for ultrasonic treatment, preferably, the ultrasonic treatment time is 1-10min, and repeating the process for three times to obtain the three-dimensional flower-shaped Ni (OH) 2 A/carbon cloth composite material.
In the fifth aspect of the invention, a three-dimensional porous nanoflower-shaped NiS is provided 2 Material, said three-dimensional porous nanoflower-like NiS 2 The material is in a nanometer flower shape consisting of a lamellar structure, and the lamellar structure is provided with through holes.
To further promote the three-dimensional flower shape Ni (OH) 2 The electrochemical stability of the material is generally improved by introducing functional groups or second phase particles in the prior art, but due to the interaction between the functional groups, the problems of agglomeration or poor stability are easily caused if Ni (OH) is in a three-dimensional flower shape 2 Adding a second phase into the material, wherein the second phase and three-dimensional flower-shaped Ni (OH) 2 The uniformity and adhesion of the material are poor. Therefore, the invention creatively adopts the etching method to etch three-dimensional flower-shaped Ni (OH) 2 Preparation of three-dimensional porous nanoflower-shaped NiS by pore-forming on lamellar structure 2 The material increases the specific surface area of the material, can expose more redox active sites, is beneficial to the rapid and effective diffusion of ions from electrolyte to the surface of the electrode material and the rapid transfer of electrons, better adapts to the volume change of the material in the charge-discharge process, and further improves the electrochemical performance of the electrode.
The invention provides a sixth aspect of the three-dimensional porous nanoflower-shaped NiS 2 A method of preparing a material comprising: three-dimensional flower-shaped Ni (OH) 2 And (3) reacting the material with sulfur powder to obtain the material.
Sulfur powder and Ni (OH) 2 The reaction principle and the process are as follows:
according to the sulfur powder and Ni (OH) 2 As can be seen from the reaction equation, SO is generated during the reaction 2 Is a direct cause of the occurrence of holes, so that some larger holes appearAnd (4) the aperture. Some small and dense holes need further magnification to be seen, and NiS can be seen from the scans in FIG. 6 and FIG. 8 2 NiS grown on nanosheets and carbon cloth 2 The nanoplate surface was not smooth, indicating that NiS was present after vulcanization 2 The surface also distributes the dense holes.
Preferably, the three-dimensional flower shape Ni (OH) 2 The mass ratio of the material to the sulfur powder is 1:1-1, preferably 1:5;
preferably, the reaction temperature is 200-500 ℃, the reaction time is 1-5h, preferably 300 ℃,3h;
preferably, the reaction is carried out under an inert atmosphere selected from nitrogen, argon, helium.
Research shows that the original three-dimensional flower-like structure is destroyed by using excessive sulfur powder, and Ni (OH) is damaged by using too little sulfur powder 2 Is not fully vulcanized and is insufficient to form NiS 2 The three-dimensional flower-like structure can be damaged even NiO can be directly generated due to overhigh temperature of the hydrothermal reaction, the subsequent vulcanization is not facilitated, and the nano sheet-like structure can not be polymerized into the flower-like structure or even can not be synthesized into Ni (OH) due to overlow temperature of the hydrothermal reaction 2 。
The prepared three-dimensional porous nanometer flower-shaped NiS 2 The material has a porous structure and a large specific surface area, when the material reacts with electrolyte, ions can be diffused through the pores, the charge transfer rate is accelerated, the electrochemical performance is increased, a large number of exposed active sites are provided, the specific capacitance performance is good, and the cycle performance and the rate performance are improved.
The seventh aspect of the invention provides a three-dimensional porous nanoflower NiS 2 Carbon cloth composite material, three-dimensional porous nanoflower-like NiS 2 The material is positioned on the surface of the carbon cloth.
The carbon material with double electric layer capacitance and the transition metal sulfide with pseudo capacitance are organically combined, and the defect of poor capacitance performance of a single carbon material or a transition metal oxide is overcome.
In the eighth aspect of the invention, the invention provides three-dimensional porous nanoflower-shaped NiS 2 The preparation method of the/carbon cloth composite material comprises the following steps: putting the carbon cloth into an alkaline test containing nickel saltMixing the solution of the agent and the acid reagent, carrying out hydrothermal reaction, and mixing the obtained product with sulfur powder for reaction to obtain the sulfur-containing catalyst.
The type, proportion, concentration, pH value, reaction temperature and time of nickel salt, alkaline reagent and acidic reagent, and the three-dimensional flower-shaped Ni (OH) 2 The preparation method of the material is the same.
In order to further promote the three-dimensional porous nano flower-shaped NiS 2 Electrochemical performance of/carbon cloth composite, said three-dimensional flower-like Ni (OH) 2 The preparation method of the/carbon cloth composite material also comprises a carbon cloth pretreatment step, wherein the pretreatment step comprises the following steps: cutting, washing, soaking in mixed acid, washing to neutrality, and drying.
The washing comprises washing with acetone, ethanol and deionized water;
the mixed acid is selected from two or three of nitric acid, hydrochloric acid and sulfuric acid, so that the mixed acid can fully absorb acid radical ions, the pH value of the mixed acid is tested every 1h, and the mixed acid is washed with distilled water for several times to be neutral after the acidity of the mixed acid reaches the maximum value.
The three-dimensional porous nano flower-shaped NiS 2 The preparation method of the/carbon cloth composite material also comprises the steps of taking out the reacted carbon cloth, washing the carbon cloth by deionized water for a plurality of times, soaking the carbon cloth in ethanol solution for ultrasonic treatment, preferably, the ultrasonic treatment time is 1-10min, and repeating the process for three times to obtain the three-dimensional porous nano flower-shaped NiS 2 A/carbon cloth composite material.
NiS is prepared by adopting in-situ growth technology 2 The carbon cloth composite material avoids the use of adhesives, increases the contact area of the electrode and the electrolyte and promotes the transmission of charges. In addition, the three-dimensional flower-like morphology is beneficial to rapid and effective diffusion of ions from the electrolyte to the surface of the electrode material, rapid transfer of electrons and better adaptation to volume change of the material in the charge-discharge process, and the porous structure has higher specific surface area and can provide more active sites for electrochemical reaction, so that NiS (nickel sulfide) can be obtained 2 Has the potential to be used as a high-performance energy storage material.
In a ninth aspect of the invention, there is provided a three-dimensional flower-like Ni (OH) 2 Material and/or three-dimensional flower-like Ni (OH) 2 /carbon cloth compositeMaterial and/or three-dimensional porous nanoflower-like NiS 2 Material and/or three-dimensional porous nanoflower-like NiS 2 The carbon cloth composite material is applied to the fields of batteries, vehicles and electric appliances.
In a tenth aspect of the present invention, there is provided a battery comprising three-dimensional flower-like Ni (OH) 2 Material and/or three-dimensional flower-like Ni (OH) 2 Carbon cloth composite material and/or three-dimensional porous nanoflower-shaped NiS 2 Material and/or three-dimensional porous nanoflower-like NiS 2 A/carbon cloth composite 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 Ni (OH) 2 Method for producing a material
Preparation of metal salt solution: weigh 1.2g of Ni (CH) on an electronic balance 3 COO) 2 ·4H 2 O g, dissolved in 20mL deionized water, stirred well, sonicated for 30 minutes, and then transferred to teflon liners.
Preparing a precipitator solution with the pH value of 10, weighing 3g of urea, dissolving in 30mL of deionized water, and stirring for 30 minutes. 0.7g of ammonium fluoride was weighed, dissolved in 20mL of deionized water, and stirred for 30 minutes. The ammonium fluoride solution was then added to the urea solution with a syringe to give a precipitant solution with a pH of about 10.
And slowly injecting the prepared precipitator solution into the tetrafluoroethylene lining by using an injector, sealing the tetrafluoroethylene lining in a stainless steel high-pressure reaction kettle, and reacting for 10 hours at 110 ℃ by adopting a hydrothermal self-assembly method. Washing the powder sample with water and anhydrous ethanol respectively, and drying in a vacuum tube furnace to obtain three-dimensional flower-shaped Ni (OH) 2 。
FIG. 1 shows the three-dimensional flower-like Ni (OH) obtained 2 The flower-like structure of the flower-like structure can be obviously seen from the scanning electron microscope picture.
FIG. 2 shows the three-dimensional flower-like Ni (OH) obtained 2 Wherein the spectrum has six obvious diffraction peaks at 19.2, 33.1, 38.6, 52.1, 59.1 and 62.7 degrees, which are respectively assigned to Ni (OH) 2 (001) and (1)00 Crystal faces (JCPDS No. 14-0117) of (101), (102), (110) and (111), and the method can be used for successfully synthesizing the target material three-dimensional flower-shaped Ni (OH) 2 。
EXAMPLE 2 three-dimensional flower-like Ni (OH) 2 Carbon cloth composite material
Pretreatment of the carbon cloth: firstly, 1 x 2cm is cut 2 The carbon cloth of (2); and (3) sequentially dripping dozens of drops of acetone and ethanol, washing with deionized water, and drying the obtained carbon cloth in a drying oven for one night. The carbon cloth after complete drying was treated with nitric acid and hydrochloric acid at a ratio of 1: soaking in 1 proportion of mixed acid solution until the acidity reaches the maximum, washing with distilled water for several times until the solution is neutral, drying in a vacuum drying oven for one night, and placing in a polytetrafluoroethylene lining.
Preparation of metal salt solution: weigh 1.2g of Ni (CH) on an electronic balance 3 COO) 2 ·4H 2 O g dissolved in 20mL deionized water, stirred well and sonicated for 30 minutes before transferring to a teflon liner with carbon cloth.
Preparing a precipitator solution with the pH value of 10, weighing 3g of urea, dissolving in 30mL of deionized water, and stirring for 30 minutes. 0.7g of ammonium fluoride was weighed, dissolved in 20mL of deionized water, and stirred for 30 minutes. The ammonium fluoride solution was then added to the urea solution with a syringe to give a precipitant solution with a pH of about 10.
The prepared precipitant solution was slowly injected into the above tetrafluoroethylene inner liner using a syringe. Then sealing the mixture in a stainless steel high-pressure reaction kettle, and reacting for 10 hours at 110 ℃ by adopting a hydrothermal self-assembly method.
And taking out the carbon cloth sample, washing the carbon cloth sample with water for a plurality of times, placing the carbon cloth sample in ethanol for 2 minutes by ultrasonic treatment, repeating the process for three times, and placing the carbon cloth sample in a drying oven for drying. Obtaining three-dimensional flower-shaped Ni (OH) 2 A/carbon cloth composite material. With the obtained three-dimensional flower-shaped Ni (OH) 2 The/carbon cloth composite material is used as a working electrode, the calomel electrode is used as a reference electrode, the platinum sheet electrode is used as a counter electrode, and KOH solution is used as electrolyte to assemble a three-electrode system for electrochemical test.
FIG. 3 shows the three-dimensional flower-like Ni (OH) obtained 2 A scanning electron microscope picture of the carbon cloth composite material,three-dimensional flower-like Ni (OH) can be seen 2 Uniformly loaded on the carbon cloth substrate.
FIG. 4 shows the three-dimensional flower-like Ni (OH) obtained 2 The/carbon cloth composite material is a cyclic voltammetry curve of a working electrode tested in a three-battery system. According to the calculation formula of the specific capacitance, the specific capacitance of the electrode at the scanning rate of 2mV/s is about 625F/g, and when the scanning rate is as high as 100mV/s, the specific capacitance is about 248F/g, which indicates that the assembled super capacitor has good capacitance and rate performance.
FIG. 5 shows the assembled three-dimensional flower-like Ni (OH) 2 The/carbon cloth composite material is an electrochemical impedance diagram of an electrode material tested under a three-battery system, and the impedance diagram shows that the slope is small, namely the electrolyte ion transmission resistance is small, and the charge transmission is facilitated.
Example 3
The only difference was that the precipitant solution had a pH of 9, as in example 2.
Example 4
The only difference is that the precipitant solution has a pH of 11, as in example 2.
Example 5
The same as in example 2, except that the hydrothermal reaction was carried out at a reaction temperature of 90 ℃.
Example 6
The same as in example 2, except that the hydrothermal reaction was carried out at a reaction temperature of 130 ℃.
Example 7
The difference from example 2 is only that the reaction time is 5 hours in the hydrothermal reaction.
Example 8
The same as in example 2, except that the hydrothermal reaction was carried out, the reaction time was 20 hours.
Example 9
Same as example 2, except that 1.5g of Ni (NO) was used as the metal salt 3 ) 2 ·6H 2 O。
Example 10
Same as example 2, except that 1.2g of the metal salt was usedNiCl 2 ﹒6H 2 O。
Three-dimensional flower-like Ni (OH) obtained in examples 2 to 10 2 The electrochemical properties of the/carbon cloth composite are shown in table 1.
TABLE 1 three-dimensional flower-like Ni (OH) obtained in examples 2 to 10 2 Electrochemical performance of/carbon cloth composite material
As can be seen from table 1, the pH of the precipitant, the hydrothermal reaction temperature, the hydrothermal reaction time, and the type of the metal salt all affected the electrochemical properties of the composite material, and only the composite material prepared under the conditions described in example 2 had the best electrochemical properties.
Example 11 three-dimensional porous Nanohua-like NiS 2 Material
Preparation of metal salt solution: weigh 1.5g Ni (NO) with an electronic balance 3 ) 2 ·6H 2 And O, dissolving in 20mL of deionized water, stirring uniformly, performing ultrasonic treatment for 30 minutes, and then transferring into a polytetrafluoroethylene lining filled with carbon cloth.
Preparing a precipitator solution with the pH value of 10, weighing 3g of urea, dissolving in 30mL of deionized water, and stirring for 30 minutes. 0.7g of ammonium fluoride was weighed, dissolved in 20mL of deionized water, and stirred for 30 minutes. The ammonium fluoride solution was then added to the urea solution with a syringe to give a precipitant solution with a pH of about 10.
Slowly injecting the prepared precipitant solution into the tetrafluoroethylene lining by using an injector, sealing the tetrafluoroethylene lining in a stainless steel high-pressure reaction kettle, reacting for 12 hours at 120 ℃ by adopting a hydrothermal in-situ growth technology, cooling to room temperature, respectively cleaning a powder sample by using distilled water and absolute ethyl alcohol, and then drying in a vacuum tube furnace to obtain three-dimensional flower-shaped Ni (OH) 2 。
And (3) vulcanization treatment: weighing three-dimensional flower-shaped Ni (OH) according to the mass of 1:5 2 And sulfur powder, the two are respectively placed in the porcelain boat, the sulfur powder is placed in the upper air inlet, and Ni (OH) 2 Placing in a lower air port, vulcanizing at 300 deg.C for 3h under nitrogen atmosphere, and cooling to room temperatureThen taking out to obtain the three-dimensional porous flower-shaped NiS 2 And (3) nano materials.
According to the flow direction of argon, sulfur elemental gas is generated after sulfur powder is decomposed at high temperature, the gas reacts with nickel hydroxide along with the flow direction of argon to carry out vulcanization, the vulcanization process is stable, and the original flower-shaped structure can be kept as far as possible.
FIG. 6 shows the resulting three-dimensional porous flower-like NiS 2 The scanning electron micrograph of (a) shows that the three-dimensional flower-like structure is evident from FIG. 6 a; by further magnification observation, FIG. 6b shows NiS 2 The porous structure of the nano material has pore size distribution with different sizes on almost every nano sheet.
FIG. 7 shows the resulting three-dimensional porous flower-like NiS 2 Wherein seven distinct diffraction peaks at 27.3, 31.6, 35.3, 38.8, 45.3, 53.6 and 61.2 degrees in the spectrum are respectively assigned to NiS 2 The (111), (200), (210), (211), (220), (311) and (321) crystal faces (JCPDS No. 11-0099) of the method can conclude that the method successfully synthesizes the three-dimensional porous flower-shaped NiS of the target material 2 。
Example 12 three-dimensional porous Nanohua NiS 2 Carbon cloth composite material
Pretreatment of the carbon cloth: firstly, 1 x 2cm is cut 2 The carbon cloth of (2); and sequentially carrying out ultrasonic cleaning in acetone solution, absolute ethyl alcohol and deionized water, and drying the obtained carbon cloth in a drying box for one night. Soaking the completely dried carbon cloth in an acid solution mixed by nitric acid and sulfuric acid in a ratio of 1:1 for ultrasonic treatment until the acidity reaches the maximum, washing the carbon cloth with distilled water for several times until the carbon cloth is neutral, and drying the carbon cloth in a vacuum drying oven for one night.
Ni(OH) 2 Synthesizing a/carbon cloth composite material: weigh 1.5g Ni (NO) with an electronic balance 3 ) 2 ·6H 2 And O, dissolving in 20mL of deionized water, uniformly stirring, and then carrying out ultrasonic treatment for 30 minutes. And then transferred to a teflon liner with carbon cloth. Preparing a precipitant solution with the pH value of 10, weighing 3g of urea, dissolving the urea in 30mL of deionized water, and stirring for 30 minutes. 0.7g of ammonium fluoride was weighed, dissolved in 20mL of deionized water, and stirred for 30 minutes. Then, the ammonium fluoride was dissolved in a syringeThe solution was added to a urea solution to give a precipitant solution with a pH of about 10.
And slowly injecting the prepared precipitator solution into the tetrafluoroethylene lining by using an injector, sealing the tetrafluoroethylene lining in a stainless steel high-pressure reaction kettle containing the treated carbon cloth, reacting for 12 hours at 120 ℃ by adopting a hydrothermal in-situ growth technology, cooling to room temperature, taking out a carbon cloth sample, washing with water for several times, placing in ethanol for 2 minutes by ultrasonic treatment, repeating the process for three times, and placing in a drying box for drying. Obtaining three-dimensional flower-shaped Ni (OH) 2 A/carbon cloth composite material.
And (3) vulcanization treatment: weighing sulfur powder which is 5 times of the mass of the active material after the pure carbon cloth is removed, placing the sulfur powder in a magnetic boat under the upper carbon cloth, vulcanizing at 300 ℃ for 3h under the nitrogen protective atmosphere, cooling to room temperature, and taking out to obtain the three-dimensional porous flower-shaped NiS 2 A/carbon cloth composite material. The obtained three-dimensional porous flower-shaped NiS 2 The/carbon cloth composite material is used as a working electrode, ag/AgCl 2 The electrode is a reference electrode, the platinum sheet electrode is a counter electrode, and KOH solution is used as electrolyte to assemble a three-electrode system for electrochemical test.
The sulfur powder is under the upper carbon cloth, and the sulfur powder and the active material on the carbon cloth can directly react at high temperature, so that the vulcanization is more complete.
FIG. 8 is the resulting three-dimensional porous flower-like NiS 2 Scanning electron micrograph of the/carbon cloth composite material, and from FIG. 8a, it can be seen that the three-dimensional porous flower-like NiS 2 Uniformly loading on the carbon cloth substrate; it is further seen from FIG. 8b that the carbon cloth is first loaded with a layer of NiS 2 Nanosheets as a substrate followed by three-dimensional porous flowered NiS 2 Can grow better onto the carbon cloth.
FIG. 9 shows the three-dimensional porous flower-like NiS obtained by the above method 2 The/carbon cloth composite material is a cyclic voltammetry curve of a working electrode tested in a three-battery system. According to a calculation formula of specific capacitance, the specific capacitance of the electrode at a scanning rate of 2mV/s is 806.5F/g, and when the scanning rate is as high as 50mV/s, the specific capacitance is 478.3F/g, which shows that the assembled super capacitor has good capacitance and rate performance.
FIG. 10 shows the three-dimensional porous flower-like NiS 2 The/carbon cloth composite material is a cycle performance diagram of 8000 times of tests of charge-discharge cycles of a working electrode under a three-battery system at a current density of 5A/g, and NiS can be seen from the diagram 2 The electrode can still keep 93.8 percent of the original capacitance value after 8000 times of charge-discharge cycles, and the electrode is proved to have good cycle performance and potential for preparing high-performance energy storage materials.
Example 13
The same as in example 12, except that the nickel salt used was 1.2g of Ni (CH) 3 COO) 2 ·4H 2 O。
Example 14
The same as in example 12, except that the nickel salt used was 1.2g NiCl 2 ﹒6H 2 O。
Example 15
The same as in example 12, except that the hydrothermal reaction was carried out at a reaction temperature of 60 ℃.
Example 16
The same as in example 12, except that the hydrothermal reaction was carried out at a reaction temperature of 180 ℃.
Example 17
The same as in example 12, except that the hydrothermal reaction was carried out, the reaction time was 6 hours.
Example 18
The reaction time was 18 hours in the hydrothermal reaction, which is the same as in example 12.
Example 19
The same as example 12, except that the ratio of the sample to the sulfur powder at the time of vulcanization reaction was 1:10.
example 20
The same as example 12, except that the ratio of the sample to the sulfur powder at the time of vulcanization reaction was 1:3.
three-dimensional porous Nanoflorid-like NiS obtained in examples 12 to 20 2 The electrochemical properties of the/carbon cloth composite material are shown in table 2.
TABLE 2 three-dimensional porous nanoflower NiS obtained in examples 12-20 2 Carbon clothElectrochemical performance of the 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 modifications may be made to the embodiments described above, or equivalents may be substituted for elements thereof. 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 (6)
1. Three-dimensional porous nanometer flower-like NiS 2 The carbon cloth composite material is characterized in that the three-dimensional porous nanometer flower-shaped NiS 2 The material is positioned on the surface of the carbon cloth;
the three-dimensional porous nanometer flower-shaped NiS 2 The material is in a nanometer flower shape consisting of a lamellar structure, and the lamellar structure is provided with a through hole;
the three-dimensional porous nano flower-shaped NiS 2 The preparation method of the/carbon cloth composite material comprises the following steps: putting carbon cloth into a solution containing nickel salt, an alkaline reagent and an acidic reagent, mixing, and carrying out hydrothermal reaction to obtain three-dimensional flower-shaped Ni (OH) 2 Mixing with sulfur powder for reaction to obtain the product;
the temperature of the hydrothermal reaction is 60-150 ℃ and the time is 5-24h;
the three-dimensional flower shape Ni (OH) 2 The mass ratio of the material to the sulfur powder is 1:5;
the reaction temperature is 300 ℃, and the reaction time is 3 hours;
the reaction is carried out under an inert atmosphere selected from nitrogen, argon, helium.
2. The three-dimensional porous nanoflower NiS of claim 1 2 The/carbon cloth composite material is characterized in that the nickel salt is selected from NiCl 2 ∙6H 2 O，NiSO 4 ∙6H 2 O，Ni(NO 3 ) 2 ∙6H 2 O，Ni(CH 3 COO) 2 ∙4H 2 One or more of O;
the alkaline reagent is selected from urea, sodium carbonate and sodium bicarbonate;
the acidic reagent is selected from ammonia-containing reagents selected from ammonium fluoride, ammonium chloride, ammonium nitrate and ammonium sulfate;
the concentration of the nickel salt is 0.2-0.5mol/L;
the adding amount of the acidic reagent and the alkaline reagent is to ensure that the pH value of the reaction system is 8-11.
3. The three-dimensional porous nanoflower NiS of claim 2 2 The carbon cloth composite material is characterized in that the adding amount of the acid reagent and the alkaline reagent is such that the pH value of a reaction system is 9-11.
4. The three-dimensional porous nanoflower NiS of claim 1 2 The carbon/cloth composite material is characterized in that the temperature of the hydrothermal reaction is 110 ℃ and the time is 10 hours.
5. The three-dimensional porous nanoflower NiS of any one of claims 1-4 2 The carbon cloth composite material is applied to the fields of batteries, vehicles and electric appliances.
6. A battery comprising the three-dimensional porous nanoflower-like NiS 2/carbon cloth composite of any one of claims 1-4.
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