CN115947315A - Transition metal selenide for supercapacitor electrode material and preparation method thereof - Google Patents
Transition metal selenide for supercapacitor electrode material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a transition metal selenide for a super capacitor electrode material and a preparation method thereof, and relates to the technical field of electrode material preparation. Copper chloride dihydrate, nickel compound or ferrous chloride tetrahydrate, stannide and selenium powder are used as a reactant precursor, an organic solvent is added for solvothermal reaction, the reaction product is cooled to room temperature after the reaction is finished, and the reaction product is washed and dried to obtain the transition metal selenide. The transition metal selenide electrode material prepared by the invention has a great development prospect in the field of energy storage devices such as super capacitors, and the like, and the invention utilizes the mutual synergistic effect of binary substances to excite the electrochemical performance of the material, thereby providing a new idea for the development of super capacitors.
Description
Technical Field
The invention relates to the technical field of electrode material preparation, in particular to a transition metal selenide for a super capacitor electrode material and a preparation method thereof.
Background
With social development and era progress, traditional fossil energy sources expose more and more problems, including insufficient energy supply and environmental pollution caused by energy consumption.
Under the condition of continuously increasing global demand for fossil energy, the method mainly uses electric power, and better accords with the requirements of low-carbon economic concepts and environmental protection through the electric power and other clean energy sources obtained by transforming or processing natural resources such as wind energy, solar energy, tidal energy, ocean energy and the like. The power does not completely replace fossil energy due to problems of energy storage devices, cost and the like.
In order to promote further application of electric power in life, the existing energy storage device needs to be continuously improved. The currently used main energy storage devices are secondary batteries such as lithium ion batteries, nickel-metal hydride batteries, cadmium-nickel batteries and the like, but the secondary batteries have short cycle life, poor safety, higher maintenance cost and lower power density. The super capacitor is a green energy storage device and device with great development prospect, and has irreplaceable superiority compared with secondary batteries such as lithium ion batteries and the like. Such as: the high-power-density energy storage device has the advantages of high power density, long charge-discharge cycle life, short charge time, long storage life and high reliability, and solves the problems of high specific power and high specific energy output of the energy storage device.
In the prior electrode material, the transition metal oxide/hydroxide has the problems of low conductivity and poor stability, but the transition metal selenide has structural diversity and strong electrochemical activity, has higher electronic conductivity compared with the transition metal oxide/hydroxide and sulfide, can obtain high specific capacitance and energy density as the electrode material, and has the advantages of low cost, high theoretical specific capacitance, rich raw materials and the like, so the transition metal selenide is considered to be a good supercapacitor pseudo-capacitance electrode material.
The electrochemical performance of the electrode material depends on the composition and the morphological structure of the material, so that the configuration of each component is optimized, the synthetic route is reasonably designed, and the problems of disordered morphological structure, complex preparation process and the like of the pure inorganic electrode material can be solved.
Disclosure of Invention
The invention aims to provide a transition metal selenide for a supercapacitor electrode material and a preparation method thereof, so as to solve the problems in the prior art.
In order to achieve the purpose, the invention provides the following scheme:
the invention provides a preparation method of transition metal selenide, which is prepared by adopting a first method or a second method and comprises the following steps:
the method I comprises the following steps:
adding an organic solvent into copper chloride dihydrate, nickel compounds, tin compounds and selenium powder serving as reactant precursors, carrying out a solvothermal reaction, cooling to room temperature after the reaction is finished, and washing and drying reaction products to obtain the transition metal selenide;
the organic solvent is a mixed solution of N, N-dimethylformamide and triethylenetetramine.
The second method comprises the following steps:
copper chloride dihydrate, ferrous chloride tetrahydrate, stannide and selenium powder are used as reactant precursors, an organic solvent is added for solvothermal reaction, the reaction product is cooled to room temperature after the reaction is finished, and the transition metal selenide is obtained after the reaction product is washed and dried;
the organic solvent is a mixed solution of N, N-dimethylformamide and triethylenetetramine. Preferably, before the solvothermal reaction, the system is magnetically stirred at the rotating speed of 800-2000 r/min for 20-50 min.
Preferably, the washing process is specifically as follows: washing with deionized water and absolute ethyl alcohol alternately for 3 times, and separating washing liquid from reaction products in a centrifugal mode after each washing, wherein the centrifugal rotating speed is 3500-5000 r/min, and the centrifugal time is 15-30 min.
Preferably, the molar ratio of the copper chloride dihydrate to the nickel compound to the tin compound to the selenium powder is 1.8-2.5.
Preferably, the molar ratio of the copper chloride dihydrate, the ferrous chloride tetrahydrate, the stannide and the selenium powder is 1.8-2.5.
Preferably, the ratio of the sum of the molar amounts of the reactant precursors to the molar amount of the organic solvent is 9.4 to 14.
Preferably, the nickel compound is nickel chloride hexahydrate, nickel sulfate hexahydrate or nickel acetate tetrahydrate.
Preferably, the stannide is stannous chloride pentahydrate or stannous chloride dihydrate.
Preferably, the molar ratio of the N, N-dimethylformamide to the triethylenetetramine is 0-1.
Preferably, the temperature of the solvothermal reaction is 180-240 ℃ and the time is 12-30h.
Preferably, the drying is vacuum drying, the drying temperature is 60-70 ℃, the drying time is 10-15h, and the relative value of the vacuum degree is 0.07-0.09MPa.
The invention also provides the transition metal selenide prepared by the preparation method.
The invention further provides application of the transition metal selenide serving as an electrode material of a super capacitor.
The invention ensures the good particle size and shape of the synthesis by regulating and controlling the reaction conditions such as precursor proportion, system reaction temperature, time and the like.
The invention discloses the following technical effects:
(1) The precursor and the reagent used in the method are common chemicals, so the method has low cost, and is economic and effective;
(2) The invention utilizes a one-step solvothermal method, and has controllable preparation conditions, mild reaction conditions and simple process;
(3) The surface of the material synthesized by the method has a special micro-morphology, the specific surface area of the material is increased by the structure, abundant electrochemical active sites are provided for oxidation-reduction reaction, and the diffusion and transmission of electrolyte ions are accelerated;
(4) The transition metal selenide electrode material prepared by the invention has a great development prospect in the field of energy storage devices such as super capacitors and the like, and the invention utilizes the mutual synergistic effect of binary substances to excite the electrochemical performance of the material and provides a new idea for the development of super capacitors.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required in the embodiments will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art that other drawings can be obtained according to the drawings without creative efforts.
In fig. 1, (a) and (b) are Scanning Electron Micrographs (SEM) of the transition metal selenide material prepared in example 1;
FIG. 2 is an X-ray diffraction pattern (XRD) of the transition metal selenide material prepared in example 1;
fig. 3 is an elemental map of the transition metal selenide material prepared in example 1;
in fig. 4, (a) is a Cyclic Voltammogram (CV) of the transition metal selenide material prepared in example 1, and (b) is a constant current charge-discharge diagram (GCD) of the transition metal selenide material prepared in example 1;
fig. 5 is an electrochemical impedance diagram (EIS) of the transition metal selenide material prepared in example 1;
fig. 6 (a), (b) are SEM images of the transition metal selenide material obtained in example 5;
in fig. 7, (a) is an XRD pattern of the transition metal selenide material obtained in example 5, and (b) is an XRD pattern of the transition metal selenide material obtained in example 6;
fig. 8 is an electrochemical performance test chart of the transition metal selenide material obtained in example 5: (a) Cyclic Voltammogram (CV), (b) constant current charge-discharge diagram (GCD);
fig. 9 is an electrochemical impedance diagram (EIS) of the transition metal selenide material obtained in example 5;
fig. 10 is a constant current charge-discharge diagram of the transition metal selenide material obtained in example 5 at 2000 times.
Detailed Description
Reference will now be made in detail to various exemplary embodiments of the invention, the detailed description should not be construed as limiting the invention but rather as a more detailed description of certain aspects, features and embodiments of the invention.
It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. In addition, for numerical ranges in the present disclosure, it is understood that each intervening value, to the upper and lower limit of that range, is also specifically disclosed. Every smaller range between any stated value or intervening value in a stated range and any other stated or intervening value in a stated range is encompassed within the invention. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present invention. All documents mentioned in this specification are incorporated by reference herein for the purpose of disclosing and describing the methods and/or materials associated with the documents. In case of conflict with any incorporated document, the present specification will control.
It will be apparent to those skilled in the art that various modifications and variations can be made in the specific embodiments of the present disclosure without departing from the scope or spirit of the disclosure. Other embodiments will be apparent to those skilled in the art from consideration of the specification. The description and examples are intended to be illustrative only.
As used herein, the terms "comprising," "including," "having," "containing," and the like are open-ended terms that mean including, but not limited to.
The "parts" in the present invention are all parts by mass unless otherwise specified.
Example 1 preparation of transition metal selenide
(1) 2mmol of CuCl as a precursor of the reactant 2 ·2H 2 O、1mmol NiCl 2 ·6H 2 O、1mmol SnCl 4 ·4H 2 O and 4mmol Se powder are sequentially added into a polytetrafluoroethylene lining of a reaction kettle, then 1mol of N, N-dimethylformamide and 0.1mol of triethylenetetramine are added into the lining to prepare a precursor solution, and the precursor solution is magnetically stirred for 30min at the rotating speed of 1500r/min to be fully dissolved. Then, the polytetrafluoroethylene lining containing the uniformly mixed precursor solution is hermetically placed in a matched reaction kettle, and the reaction kettle is placed in a 200 ℃ oven for reaction for 20 hours;
(2) Taking out the reaction kettle after the materials in the reaction kettle are reacted, naturally cooling to room temperature, then discarding supernatant, and collecting a black target product at the bottom of the reaction kettle;
(3) Alternately washing the target product with deionized water and absolute ethyl alcohol for 3 times respectively, centrifuging the supernatant at a rotating speed of 3500r/min for 15min after washing each time, and drying the cleaned target product in a vacuum drying oven with a vacuum degree relative value of 0.07MPa at 60 ℃ for 15h to obtain the transition metal selenide material.
The prepared transition metal selenide material is analyzed by a Scanning Electron Microscope (SEM), an X-ray diffraction pattern (XRD) and an X-ray energy spectrum (EDS):
FIGS. 1 (a), (b) are SEM images of the transition metal selenide material obtained, from which it can be seen that the material is a hollow microsphere composed of a unique particulate agglomerated structure, and the surface is also distributed with a number of lamellar sheet structures. The active surface area provided by the hollow microsphere structures enables the transition metal selenide material to fully expose redox active sites, so that effective contact between the material and electrolyte is accelerated, and capacitance is improved, and the specific surface area of the material is increased by the sheet structure distributed on the surface, so that electrons are captured, and the charge and discharge rate is improved.
FIG. 2 is an XRD pattern, image, of the obtained transition metal selenide materialDiffraction peaks with higher intensities at 27.18 °, 30.53 °, 33.30 °, 36.54 °, 45.08 °, 50.29 °, 53.40 °, 65.53 °, 72.52 ° and 83.44 ° were shown, which can be indexed to Cu 2 NiSnS 4 (JCPDS NO. 26-0551) having (111), (220), (311), (331), (400) crystal plane and NiSe 2 (JCPDS NO. 41-1495) has (200), (210), (211), (311), (511) crystal planes. This demonstrates the successful synthesis of a composite transition metal selenide material.
Fig. 3 is an EDS diagram of the obtained transition metal selenide material, showing that the distribution of Cu, ni, sn, se elements in the product is relatively uniform.
In conclusion, the chemical environment of various elements analyzed was consistent with EDS, further confirming that the product is a transition metal selenide.
And (3) electrochemical performance testing:
the transition metal selenide material prepared in example 1 is used for testing the electrochemical performance of the three electrodes, and the specific operation is as follows:
(1) Weighing dry powder of 80mg of transition metal selenide, 10mg of polyvinylidene fluoride and 10mg of conductive carbon black in a fluorination bottle, dropwise adding about 0.02mol of N-methyl pyrrolidone, and magnetically stirring for about 3 hours to uniformly mix the materials;
(2) The stirred slurry was uniformly dipped on the washed nickel foam (dipping area about 1 cm) 2 ) Drying in a vacuum drying oven at 60 ℃ for 12h to prepare a working electrode;
(3) 3mol/L KOH is taken as electrolyte, and an aluminum foil electrode (1 cm) 2 ) For the counter electrode, a saturated calomel electrode was used as a reference electrode, and a three-electrode electrochemical test was performed at room temperature using an electrochemical workstation (CHI 660E).
FIG. 4 is a graph of electrochemical performance testing of transition metal selenide materials, and FIG. 4 (a) shows that each curve has a pair of distinct redox peaks at sweep rates of 5-50mV/s, which is related to the reversible oxidation reaction between the electrode and the electrolyte, and it is noted that as the sweep rate increases, the shape and redox characteristics of all CV curves remain unchanged, indicating that the electrode material has good capacitance performance and rate capability; the GCD curves of FIG. 4 (b) all show a voltage plateau with pseudocapacitance properties, and at current densities of 1.0-5.0A/g, all GCD curves exhibit a symmetrical appearance with no significant IR drop, indicating superior rate capability and co-product efficiency of the material. Due to the strong synergistic effect among Cu, ni, sn and Se and the contribution of a unique nano condensed structure to the utilization rate of active substances, the composite transition metal selenide electrode material shows a high specific capacitance of 534F/g at a current density of 1.0A/g, and the results fully illustrate the outstanding redox reaction kinetics and excellent electronic conductivity of the material.
Fig. 5 is an EIS plot of the transition metal selenide material, showing no significant curved semi-circle in the high frequency range, implying lower charge transfer resistance and faraday internal resistance of the material. The slope of the curve in the low frequency range changes slightly to an almost vertical line, indicating a faster absorption/desorption rate of the interfacial ions.
Example 2
(1) 1mmol of CuCl as a precursor of the reactant 2 ·2H 2 O、1mmol NiSO 4 ·6H 2 O、1mmol SnCl 4 ·4H 2 O and 4mmol Se powder are sequentially added into a polytetrafluoroethylene lining of a reaction kettle, then 1mol of N, N-dimethylformamide and 0.1mol of triethylenetetramine are added into the lining to prepare a precursor solution, and the precursor solution is magnetically stirred for 30min at the rotating speed of 1500r/min to be fully dissolved. Then, the polytetrafluoroethylene lining containing the uniformly mixed precursor solution is hermetically placed in a matched reaction kettle, and the reaction kettle is placed in a 200 ℃ oven for reaction for 20 hours;
(2) Taking out the reaction kettle after the materials in the reaction kettle are reacted, naturally cooling to room temperature, then discarding supernatant, and collecting a black target product at the bottom of the reaction kettle;
(3) Alternately washing the target product with deionized water and absolute ethyl alcohol for 3 times respectively, centrifuging the supernatant at a rotating speed of 3500r/min for 15min after washing each time, and drying the cleaned target product in a vacuum drying oven with a vacuum degree relative value of 0.07MPa at 60 ℃ for 12h to obtain the composite transition metal selenide material.
Example 3
(1) 2mmol of CuCl as a precursor of the reactant 2 ·2H 2 O、1mmol C 4 H 6 NiO 4 ·4H 2 O、1mmol SnCl 4 ·4H 2 O and 4mmol Se powder are sequentially added into a polytetrafluoroethylene lining of a reaction kettle, then 1mol of N, N-dimethylformamide and 0.1mol of triethylenetetramine are added into the lining to prepare a precursor solution, and the precursor solution is magnetically stirred for 30min at the rotating speed of 1500r/min to be fully dissolved. Then, the polytetrafluoroethylene lining containing the uniformly mixed precursor solution is hermetically placed in a matched reaction kettle, and the reaction kettle is placed in a 200 ℃ oven for reaction for 20 hours;
(2) Taking out the reaction kettle after the materials in the reaction kettle are reacted, naturally cooling to room temperature, then discarding supernatant, and collecting a black target product at the bottom of the reaction kettle;
(3) Alternately washing the target product with deionized water and absolute ethyl alcohol for 3 times respectively, centrifuging the supernatant at a rotating speed of 3500r/min for 15min after washing each time, and drying the cleaned target product in a vacuum drying oven with a vacuum degree relative value of 0.07MPa at 60 ℃ for 12h to obtain the composite transition metal selenide material.
Example 4
(1) 2mmol of CuCl as a precursor of the reactant 2 ·2H 2 O、1mmol NiCl 2 ·6H 2 O、1mmol SnCl 2 ·2H 2 O and 4mmol Se powder are sequentially added into a polytetrafluoroethylene lining of a reaction kettle, then 1mol of N, N-dimethylformamide and 0.1mol of triethylenetetramine are added into the lining to prepare a precursor solution, and the precursor solution is magnetically stirred for 30min at the rotating speed of 1500r/min to be fully dissolved. Then, the polytetrafluoroethylene lining containing the uniformly mixed precursor solution is hermetically placed in a matched reaction kettle, and the reaction kettle is placed in a 200 ℃ oven for reaction for 20 hours;
(2) Taking out the reaction kettle after the materials in the reaction kettle are reacted, naturally cooling to room temperature, then discarding supernatant, and collecting a black target product at the bottom of the reaction kettle;
(3) Alternately washing the target product with deionized water and absolute ethyl alcohol for 3 times respectively, centrifuging the supernatant at a rotating speed of 3500r/min for 15min after washing each time, and drying the cleaned target product in a vacuum drying oven with a vacuum degree relative value of 0.07MPa at 60 ℃ for 12h to obtain the composite transition metal selenide material.
Example 5
(1) 2mmol of CuCl of reactant precursor 2 ·2H 2 O、1mmol FeCl 2 ·4H 2 O、1mmol SnCl 4 ·4H 2 O and 4mmol Se powder are sequentially added into a polytetrafluoroethylene lining of a reaction kettle, 0.75mol of N, N-dimethylformamide and 0.075mol of triethylenetetramine are added into the polytetrafluoroethylene lining to prepare a precursor solution, and the precursor solution is magnetically stirred at the rotating speed of 1500r/min for 30min to be fully dissolved. Then, the polytetrafluoroethylene lining containing the uniformly mixed precursor solution is hermetically placed into a matched reaction kettle, and the reaction kettle is placed into a 220 ℃ oven for reaction for 20 hours;
(2) Taking out the reaction kettle after the materials in the reaction kettle are reacted, naturally cooling to room temperature, then discarding supernatant, and collecting a black target product at the bottom of the reaction kettle;
(3) Alternately washing the target product with deionized water and anhydrous ethanol for 3 times, centrifuging the supernatant at 3500r/min for 20min, and drying the cleaned target product in a vacuum drying oven with relative vacuum degree of 0.08MPa at 60 deg.C for 15h to obtain transition metal selenide material Cu 2 FeSnSe 4 。
Scanning Electron Microscope (SEM) and X-ray diffraction pattern (XRD) are adopted for the prepared transition metal selenide Cu 2 FeSnSe 4 The material was analyzed.
Fig. 6 is an SEM image of the transition metal selenide material obtained in example 5, from which it can be seen that the material is a cluster particle consisting of a large number of distinct condensed structures of lamella-shaped nanosheets. The large number of pores and the rough surface appearance of the cluster-shaped multilayer nanoparticles increase the specific surface area of the material, so that the transition metal selenide material fully exposes redox active sites, the conduction of electrolyte ions is facilitated, the effective contact between the material and the electrolyte is accelerated, and the capacitance is improved.
Fig. 7 (a) is an XRD pattern of the transition metal selenide material obtained in example 5, and the pattern shows diffraction peaks having higher intensities at 28.21 °, 46.99 °, 55.30 ° and 66.09 °, which can be indexed to Cu 2 FeSnSe 4 (ICDD-PDF # 52-0998) (112), (204), (312) and (400) crystal faces, and the standard XRD spectrogram is tin antimonyThe mineral structure and the space group of 1-42m have no abnormal and impure peak and narrow peak width, which shows that the material has no other impurities, has crystallinity and stability, and proves that the transition metal selenide Cu is successfully synthesized 2 FeSnSe 4 A material.
In conclusion, the product of example 5 is confirmed to be the transition metal selenide Cu 2 FeSnSe 4 。
And (3) testing electrical properties:
transition metal selenide Cu prepared as in example 5 2 FeSnSe 4 The material tests the electrochemical performance of the three electrodes, and the specific operation is as follows.
(1) 80mg of Cu are weighed 2 FeSnSe 4 Putting 10mg of polyvinylidene fluoride and 10mg of dry powder of conductive carbon into a fluorination bottle, and dropwise adding 0.02mol of N-methyl pyrrolidone, magnetically stirring for about 12 hours, and uniformly mixing;
(2) The stirred slurry was uniformly dipped on the washed nickel foam (dipping area about 1 cm) 2 ) And drying the mixture in a vacuum drying oven at 60 ℃ for 12 hours to prepare a working electrode.
(3) A three-electrode electrochemical test was performed at room temperature using an electrochemical workstation (CHI 660E) with 2mol/L KOH as the electrolyte, a platinum sheet electrode (1X 1 cm) as the counter electrode, and a saturated calomel electrode as the reference electrode.
FIG. 8 shows the transition metal selenide Cu obtained in example 5 2 FeSnSe 4 The electrochemical performance test chart of the material, FIG. 8 (a), shows that each curve has a pair of obvious redox peaks when the sweep rate is 5-50mV/s, which is related to the reversible oxidation reaction between the electrode and the electrolyte, and confirms the pseudo capacitance mechanism of the material, wherein the higher the redox reaction rate is, the faster the electrolyte is diffused, and the larger the specific capacitance is. With the increase of the sweep rate, the shape of the CV curve is basically unchanged and still has good symmetry, and the redox characteristic remains unchanged, which indicates that the electrode material has good capacitance performance. As shown in FIG. 8 (b), the constant DC charge-discharge diagram (GCD) of the material shows that when the current density is 0.5-5A/g, the GCD curves show the approximate symmetrical pseudocapacitance electrochemical characteristics and the voltage plateau of the pseudocapacitance properties. Due to strong synergistic effect among Cu, fe, sn and Se and unique nano condensationThe contribution of the aggregate structure to the active utilization, all GCD curves show a symmetrical appearance without significant IR drop, indicating higher rate performance, coulombic efficiency and good reversibility of the material. The outstanding dynamic performance of the redox reaction and the excellent electronic conductivity of the material are fully demonstrated. Electrochemical Impedance Spectroscopy (EIS) is considered to be an effective method for analyzing electrochemical impedance characteristics of electrochemical devices, such as internal resistance, charge transport in electrodes/electrolytes, electrode material interfacial behavior, and ion diffusion.
FIG. 9 shows the transition metal selenide Cu obtained in example 5 2 FeSnSe 4 The EIS plot of the material at open circuit potential, as shown, the diameter of the curved semicircle in the high frequency range is related to the charge transfer resistance and faraday resistance of the electrode. The absence of a sharp curved semicircle in the high frequency range means a lower charge transfer resistance and faraday resistance of the material. The change of the slope of the curve in the low-frequency range is small, which shows that ions are diffused in the electrolyte quickly, adsorbed on the surface of the electrode and have good capacitance performance.
FIG. 10 shows the transition metal selenide Cu obtained in example 5 2 FeSnSe 4 2000 times of constant current charge-discharge graphs of the material show that the material can keep 51% of capacitance retention rate after continuous 2000 times of charge-discharge cycles, and the material is seen to have certain electrochemical stability.
Example 6
(1) 2mmol of CuCl as a precursor of the reactant 2 ·2H 2 O、1mmol FeCl 2 ·4H 2 O、1mmol SnCl 4 ·4H 2 Adding O and 4mmol Se powder into a polytetrafluoroethylene lining of a reaction kettle in sequence, adding 0.625mol of N, N-dimethylformamide and 0.125mol of triethylenetetramine into the lining to prepare a precursor solution, and magnetically stirring the precursor solution at the rotating speed of 1500r/min for 30min to fully dissolve the precursor solution. Then, the polytetrafluoroethylene lining containing the uniformly mixed precursor solution is hermetically placed into a matched reaction kettle, and the reaction kettle is placed into a 220 ℃ oven for reaction for 20 hours;
(2) Taking out the reaction kettle after the materials in the reaction kettle are reacted, naturally cooling to room temperature, then discarding supernatant, and collecting a black target product at the bottom of the reaction kettle;
(3) Alternately washing the target product with deionized water and absolute ethyl alcohol for 3 times respectively, centrifuging the supernatant at a rotating speed of 3500r/min for 20min after washing each time, and drying the cleaned target product in a vacuum drying oven with a vacuum degree relative value of 0.08MPa at 60 ℃ for 15h to obtain the transition metal selenide material.
FIG. 7 (b) shows a graph containing the transition metal selenide Cu obtained in example 6 2 FeSnSe 4 XRD pattern of the material, the image shows that the material has high-strength transition metal selenide Cu 2 FeSnSe 4 Diffraction peaks, which prove the successful synthesis of the material.
The binary supercapacitor electrode material is prepared by adopting a one-step solvothermal method, the method is mild in condition and simple to operate, and the problems that the operation steps of the preparation method in the prior art are complex and tedious, the environment is polluted and the like can be solved. The invention provides a new idea for exciting the electrochemical performance of a material by utilizing the mutual synergistic action of binary substances.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. A method for preparing a transition metal selenide, characterized by comprising the steps of:
copper chloride dihydrate, nickel compound or ferrous chloride tetrahydrate, stannide and selenium powder are used as a reactant precursor, an organic solvent is added for solvothermal reaction, the reaction product is cooled to room temperature after the reaction is finished, and the reaction product is washed and dried to obtain the transition metal selenide;
the organic solvent is a mixed solution of N, N-dimethylformamide and triethylenetetramine.
2. The method for preparing transition metal selenide according to claim 1, wherein the molar ratio of copper chloride dihydrate, nickel compound or ferrous chloride tetrahydrate, tin compound and selenium powder is 1.8-2.5.
3. The method for preparing transition metal selenide according to claim 1, wherein the ratio of the sum of the molar amounts of the reactant precursors to the molar amount of the organic solvent is 9.4 to 14.
4. The method for preparing transition metal selenide according to claim 1, wherein the nickel compound is nickel chloride hexahydrate, nickel sulfate hexahydrate, or nickel acetate tetrahydrate.
5. The method for producing transition metal selenide according to claim 1, wherein the stannide is tin chloride tetrahydrate, tin chloride pentahydrate, or stannous chloride dihydrate.
6. The method for preparing transition metal selenide according to claim 1, wherein the molar ratio of N, N-dimethylformamide to triethylenetetramine is 0 to 1.
7. The method for preparing transition metal selenide according to claim 1, wherein the solvothermal reaction is carried out at 180 to 240 ℃ for 12 to 30 hours.
8. The method for preparing transition metal selenide of claim 1, wherein the drying is vacuum drying, the drying temperature is 60-70 ℃, the drying time is 10-15h, and the relative value of the vacuum degree is 0.07-0.09MPa.
9. A transition metal selenide prepared by the preparation process as claimed in any one of claims 1 to 8.
10. Use of the transition metal selenide of claim 9 as a supercapacitor electrode material.
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Citations (3)
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|---|---|---|---|---|
| CN105692567A (en) * | 2016-03-16 | 2016-06-22 | 中南大学 | Stannite structure Cu2FeSnSe4 powder material and liquid phase preparation method thereof |
| CN106315522A (en) * | 2016-08-11 | 2017-01-11 | 浙江大学 | NiSe three-dimensional porous nanosheet material used for superconductor and preparation method thereof |
| CN114671414A (en) * | 2022-03-25 | 2022-06-28 | 浙江大学 | Iron-copper-tin ternary selenide nano material for sodium ion battery and preparation method thereof |
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2023
- 2023-02-20 CN CN202310156031.5A patent/CN115947315A/en active Pending
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| CN105692567A (en) * | 2016-03-16 | 2016-06-22 | 中南大学 | Stannite structure Cu2FeSnSe4 powder material and liquid phase preparation method thereof |
| CN106315522A (en) * | 2016-08-11 | 2017-01-11 | 浙江大学 | NiSe three-dimensional porous nanosheet material used for superconductor and preparation method thereof |
| CN114671414A (en) * | 2022-03-25 | 2022-06-28 | 浙江大学 | Iron-copper-tin ternary selenide nano material for sodium ion battery and preparation method thereof |
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| ASHOK KUMAR KAKARLA ET AL.: "Carbon-Shielded Selenium-Rich Trimetallic Selenides as Advanced Electrode Material for Durable Li-Ion Batteries and Supercapacitors", 《ADVANCED SCIENCE NEWS》, vol. 7, pages 1 - 15 * |
| BINLEI ZHANG ET AL.: ""Facile synthesis of Cu2FeSnSe4 sheets with a simple solvothermal method"", 《MATERIALS LETTERS》, vol. 93, pages 111 - 114 * |
| JICHENG ZHOU ET AL.: "Preparation of photovoltaic absorption material Cu2FeSnSe4 microparticles via an atmospheric pressure liquid reflux method", 《MATERIALS LETTERS》, vol. 184, pages 216 - 218, XP029760723, DOI: 10.1016/j.matlet.2016.08.019 * |
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