CN112701280A - Preparation method of hollow bicrystal phase cobalt nickel selenide microsphere material - Google Patents
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Abstract
The invention discloses aThe preparation method of nickel cobalt selenide microsphere material is characterized by that it utilizes regulation of metal ion ratio, and controls the reaction temp. of solvothermal reaction and selenylation time to prepare hollow bicrystal phase nickel cobalt selenide (NiCoSe)4) The microsphere material consists of a siderite phase and a pyrite phase double-crystal phase, is a submicron hollow microsphere particle material formed by bonding nano particles, has the microsphere particle size of 300-800 nm and the electric conductivity of 1 multiplied by 10‑4―1×10‑3S cm‑1. At a current density of 0.5A g‑1When the specific capacitance reaches 1008F g‑1The current density was increased to 20.0 A.g‑1At this time, the specific capacitance value is still maintained at 845F g‑1The capacity retention rate reaches 85.2 percent; at 5A g‑1After 5000 cycles at the current density of (1), the specific capacitance value is still maintained at 719F g‑1The capacity retention rate is about 80%, the rate performance is excellent, the cycle stability is good, and the method can be applied to water system hybrid capacitors, asymmetric supercapacitors, alkali metal (lithium/sodium/potassium) ion batteries, electro-catalytic hydrogen evolution/oxygen evolution reactions and oxygen reduction reactions.
Description
Technical Field
The invention belongs to the technical field of preparation of novel energy storage materials, and particularly relates to a hollow bicrystal phase nickel cobalt selenide (NiCoSe)4) A preparation method and application of the microsphere.
Background
The development of efficient energy storage devices has attracted a great deal of attention in response to the ever-increasing demand for electric vehicles and consumer electronics. A hybrid capacitor composed of a battery-type faraday electrode material and a capacitor-type electric double layer electrode material has been a research focus because of the characteristics of both high power density of a super capacitor and high energy density of a secondary battery. The battery-type electrode material, which is one of the most important components of a hybrid capacitor, plays a crucial role in achieving high energy and power performance. Transition metal selenides, as a novel battery-type electrode material, involve reversible multi-electron faradaic reactions in electrochemical reactions, and can in principle provide high specific capacitance. Research shows that the metastable phase often has the characteristics and functions which are not possessed by the stable phase, and can effectively improve the activity of the electrode material and solve the problem of kinetic retardation of energy storage. The stable siderite phase and the metastable siderite phase are typical phase states of transition metal selenides, and selenides of iron, cobalt and nickel are most representative and all possess { M } Se6Octahedral coordination structures and dimeric pairs of Se-Se pairs. The band gap of the white iron ore phase is 0.34eV, which is obviousThe band gap is 0.835eV lower than that of the pyrite phase, and the hematite phase has high electronic conductivity and a low capacity. In contrast, the pyrite type phase generally exhibits lower conductivity and high capacity. Therefore, the composition of the pyrite phase and the hematite phase is beneficial to improving the overall performance of the material. Theoretical studies show that rotating { M } Se6The Se-Se bond in the octahedron can realize two-phase conversion, thereby easily achieving the aim of two-phase coexistence.
The bimetal synergistic effect can effectively improve the kinetics and enhance the electrochemical activity. For Ni and Co atoms with similar electronic structures, Co is used2+Ions and Ni2+The ions have valence electron exchange or charge jump phenomena, and the synergistic effect is particularly obvious. Shu et al first reported bimetallic nickel cobalt selenides (Ni)0.67Co0.33Se) exhibits superior rate capability and electrochemical activity compared to pure nickel selenide or pure cobalt selenide (Journal of Materials Chemistry A,2015,3(47): 23653-. Nickel cobalt selenides of various morphologies have also been reported, such as NiCoSe hollow submicrospheres (Advanced Functional Materials,2018,28(13):1705921), Ni0.67Co0.33Se2Nanoparticles/nanoplates (Journal of colloid and interface science,2020,558: 291-), CoNiSe2Nanorods (Chemical Engineering Journal,2019,364: 320-327). Shinder et al (Dipak V.Shinder, Luca De Trizio, Zhiya Dang, Mirko Prato, Robert Gaspari and Liberato Manna, Hollow and Porous Nickel Cobalt oxide Nanostructured nanoparticles for Enhanced electrochemical Oxygen Evolution, chem.Mater.2017,29,7032-7041) report a bimetallic selenide (NiCose) containing both Ni/Co-Se ionic bonds and Se-Se covalent bonds4) The conjugated characteristics of the ionic bond and the covalent bond are beneficial to improving the conductivity, and a remarkable result is achieved in electrocatalytic oxygen evolution. So far, the preparation and energy storage application of a white iron ore phase and a stable state pyrite selenide material are seen.
Disclosure of Invention
The invention takes nickel salt, cobalt salt, monohydric alcohol, dihydric alcohol and trihydric alcohol as raw materials, adopts the alkoxide mixed system solvothermal synthesis method combined with the selenization process,adjusting the mixture ratio, the solvothermal temperature, the selenizing temperature and the selenizing time to prepare the hollow double-crystal-phase nickel cobalt selenide (NiCoSe) with the composite phase of the metastable-state white iron ore phase and the stable-state pyrite phase4) A material.
The specific implementation scheme is as follows:
1. the method comprises the following processes of solvothermal synthesis, selenization, washing, drying and calcination: firstly, weighing nickel salt and cobalt salt according to a set stoichiometric molar ratio, dissolving the nickel salt and cobalt salt in a mixed polyhydric alcohol solution with a set volume ratio, transferring the solution into a high-pressure reaction kettle after the solution is clarified, heating to a set temperature for solvothermal synthesis, naturally cooling to room temperature after the reaction is carried out for a set time to obtain an alkoxide composite precursor precipitate with a spherical shape, washing with absolute ethyl alcohol, carrying out suction filtration, and drying to obtain the nickel-cobalt alkoxide spherical particle precursor. And then weighing a dried nickel-cobalt alkoxide spherical particle precursor and selenium source powder according to a proportion, mixing and adding the mixture into an alcohol solution with a set volume, uniformly stirring, transferring the mixture into a high-pressure reaction kettle for selenylation reaction, heating to a set temperature for selenylation reaction for a set time, naturally cooling to room temperature after selenylation is finished, washing the obtained precipitate with absolute ethyl alcohol and deionized water, carrying out suction filtration and drying, and calcining for 1-2 hours at the set temperature to obtain the black cobalt nickel selenides material. The preparation of the pure nickel selenide material only needs to select the nickel salt raw material to carry out the steps. The pure cobalt selenide material is prepared only by selecting cobalt salt raw materials and carrying out the steps.
2. The nickel salt in the above item 1 includes one or two of nickel nitrate, nickel chloride, nickel sulfate, nickel acetate and hydrates of the above nickel salts.
3. The cobalt salt in the above item 1 includes one or two of cobalt nitrate, cobalt chloride, cobalt sulfate, cobalt acetate and hydrates of the above cobalt salts.
4. Setting the stoichiometric molar ratio of the nickel salt to the cobalt salt in the step 1: 0.1: 9.9-9.9: 0.1, preferably 0.5: 8.0-8.0: 0.5, more preferably 1.0: 4.0-4.0: 1.0, most preferably 1.0: 2.0-1.0: 1.0.
5. The polyhydric alcohol solution system of monohydric alcohol, dihydric alcohol and trihydric alcohol of the solvent thermal synthesis precursor in the step 1 comprises: monohydric alcohol of ethanol, propanol, isopropanol and n-butanol, dihydric alcohol of ethylene glycol and propylene glycol, and trihydric alcohol of glycerol; a mixed solution of a monohydric alcohol or a dihydric alcohol and a trihydric alcohol in a volume ratio of 0.1:9.9 to 9.9:0.1, preferably 1.0:0.8 to 8.0:1.0, more preferably 1.0:3.0 to 3.0:2.0, most preferably 1.0:2.0 to 1.0: 1.0.
6. The total ion concentration of nickel ions and cobalt ions in the solvothermal synthesis precursor solution in the above 1 is 0.03mol/L to 3mol/L, preferably 0.1mol/L to 2mol/L, more preferably 0.4mol/L to 1.5mol/L, and most preferably 0.5mol/L to 1.0 mol/L.
7. Solvothermal synthesis temperature in the above 1: 140-220 c, preferably 160-200 c, most preferably 170-190 c.
8. Solvothermal synthesis reaction time in the above 1: 0.5h to 24.0h, preferably 4.0h to 12.0h, more preferably 6.0h to 10.0h, most preferably 6.0h to 8.0 h.
9. The selenium source for the selenization reaction in the step 1 is selenium dioxide (SeO)2) Sodium selenite (Na)2SeO3) And potassium selenite (K)2SeO3) One or two of them.
10. The weight ratio of the triol nickel-cobalt alkoxide spherical particle precursor to the selenium source in the step 1 is as follows: 1.0: 5.0-4.0: 5.0.
10. The alcoholic solution used in the selenization reaction in the step 1 is a mixed solution of monohydric alcohol or dihydric alcohol and trihydric alcohol in ethanol, propanol, isopropanol, n-butanol, ethylene glycol, propylene glycol and glycerol, and the volume ratio of the mixed alcoholic solution is 0.1: 9.9-9.9: 0.1, preferably 1.0: 0.8-8.0: 1.0, more preferably 1.0: 3.0-3.0: 2.0, and most preferably 1.0: 2.0-1.0: 1.0.
11. Selenization reaction temperature in the step 1: 120-220 deg.c, preferably 140-200 deg.c, more preferably 160-190 deg.c, most preferably 170-180 deg.c. The selenization reaction time is 6-14 h, preferably 7-12 h, more preferably 8-10 h, and most preferably 9-10 h.
12. Calcination temperature of selenization reaction product in 1 above: 250 ℃ -600 ℃, preferably 300 ℃ -500 ℃, more preferably 300 ℃ -500 ℃, most preferably 350 ℃ -400 ℃.
13. The cobalt nickel selenides material prepared in the steps 1-12 has a composite phase composition of a white iron ore phase and a pyrite phase.
14. The cobalt nickel selenides material prepared in the steps 1-12 has the shape of a hollow microsphere formed by bonding nano particles, and the size of the microsphere particles is 300-800 nm.
15. The conductivity of the cobalt nickel selenides material prepared in the steps 1 to 12 is 1 x 10-4S cm-1―1×10-3S cm-1。
16. And (2) establishing a three-electrode system for electrochemical performance analysis in a water-based electrolyte by using the cobalt nickel selenides hollow microsphere material prepared in the steps 1-12 as a working electrode, a platinum electrode as a counter electrode and a Hg/HgO electrode as a reference electrode.
17. The 16 aqueous electrolyte includes one of a 1.0M to 6.0M KOH solution and a 1.0M to 6.0M NaOH solution.
18. The invention discloses a preparation method of hollow bicrystal phase cobalt nickel selenite microspheres and a three-electrode test system assembled by using the hollow bicrystal phase cobalt nickel selenite microspheres as a working electrode, a platinum electrode as a counter electrode, a Hg/HgO electrode as a reference electrode and 6M KOH as an electrolyte solution for testing, wherein the current density is 0.5g-1―20.0A·g-1Then, a specific capacitance value of 1200F g is obtained-1―500F·g-1。
19. The invention has the following effects: the cobalt nickel selenide material obtained by the invention is a hollow microsphere submicron particle material formed by bonding nano particles, the particles are uniformly distributed, the size of the microsphere particles is distributed between 300nm and 800nm, and the nickel cobalt selenide material comprises a siderite phase and a pyrite phase double crystal phase. The cobalt nickel selenides hollow microspheres are used as electrode materials, and a large number of nanoparticle reaction sites exist, so that the reduction of the ion transmission distance is facilitated, and the capacity, the rate capability and the long cycle performance of the electrode materials are improved. The symbiotic dual-phase structure of the hematite phase and the pyrite phase forms a bimetal synergistic effect, and further improves the conductivity and the electrochemical activity, so that the sample obtains excellent rate capability and high specific capacity. The cobalt nickel selenide material has excellent electrochemical performance, so that the cobalt nickel selenide material is suitable for a water system super capacitor, a positive electrode material of a hybrid capacitor and an electrode material of an alkali metal (lithium/sodium/potassium) ion battery and is used for performing electro-catalytic hydrogen/oxygen evolution reaction and oxygen reduction reaction.
Drawings
FIG. 1 is an XRD pattern of the hollow bi-crystalline phase nickel cobalt selenide microsphere material of example 1.
FIG. 2 is an SEM photograph of the hollow bi-crystalline phase nickel cobalt selenide microsphere material of example 1.
FIG. 3 is a TEM image of the hollow bicrystal phase cobalt nickel selenide microsphere material of example 1.
Fig. 4 is an SEM photograph of the hollow bi-crystalline phase nickel cobalt selenide microsphere material of example 4.
Fig. 5 is a constant current charge and discharge curve of the hollow bicrystal phase cobalt nickel selenides microsphere material in example 1.
Detailed Description
The technical solution of the present invention will be described below with reference to specific embodiments of the present invention.
Example 1
Adding 1mmol of nickel nitrate hexahydrate and 2mmol of cobalt nitrate hexahydrate into a mixed solution of isopropanol and glycerol, stirring until a transparent solution is obtained, transferring the transparent solution into a high-pressure reaction kettle, heating to 180 ℃, reacting for 6 hours, and naturally cooling to room temperature. And washing and filtering the obtained spherical alkoxide composite precursor precipitate by absolute ethyl alcohol, and drying to obtain the nickel-cobalt alkoxide spherical particle precursor. 9mg of precursor and 112mgSeO were weighed2Adding into ethanol, stirring, transferring into high pressure reactor, heating to 180 deg.C, selenizing for 10 hr, and naturally cooling to room temperature. Washing the obtained precipitate with anhydrous ethanol and deionized water, filtering, drying, calcining at 300 deg.C for 1 hr to obtain black cobalt nickel selenide material with conductivity of 6.9 × 10-4S cm-2. The XRD, SEM and TEM photographs of the obtained cobalt nickel selenide are respectively shown in figure 1, figure 2 and figure 3, and show a hollow microspheric shape with a particle size of 500nm-800 nm. The obtained super selenide is cobalt nickel selenide with a siderite phase and a pyrite phase. The constant current charge and discharge curves at different current densities are shown in FIG. 5, with a current density of 0.5A g in 6M KOH electrolyte-1Specific capacitance of time is up to 1008F g-1Even when the current density increased to 20A g-1The specific capacity is stillUp to 859F g-1。
Example 2
Adding 1mol of nickel chloride hexahydrate and 2mol of cobalt sulfate hexahydrate into a mixed solution of isopropanol and glycerol, stirring until a transparent solution is obtained, transferring the transparent solution into a high-pressure reaction kettle, heating to 200 ℃, reacting for 6 hours, and naturally cooling to room temperature. And washing and filtering the obtained spherical alkoxide composite precursor precipitate by absolute ethyl alcohol, and drying to obtain the nickel-cobalt alkoxide spherical particle precursor. The subsequent operation is the same as that of example 1, and a black cobalt nickel selenide sample with the conductivity of 6.2 multiplied by 10 is obtained-4S cm-2. Current Density 0.5A g in 6M KOH electrolyte-1Specific capacitance of up to 980F g-1Even when the current density increased to 20A g-1The specific capacity is still as high as 837F g-1。
Example 3
Adding 1mol of nickel acetate tetrahydrate and 5mol of cobalt acetate tetrahydrate into a mixed solution of isopropanol and glycerol, stirring until a transparent solution is obtained, transferring the transparent solution into a high-pressure reaction kettle, heating to 180 ℃, reacting for 6 hours, and naturally cooling to room temperature. And washing and filtering the obtained spherical alkoxide composite precursor precipitate by absolute ethyl alcohol, and drying to obtain the nickel-cobalt alkoxide spherical particle precursor. The subsequent operation is the same as that of example 1, and a black cobalt nickel selenide sample with the conductivity of 9.6 multiplied by 10 is obtained-4S cm-2。
Example 4
Adding 1.5mol of nickel nitrate hexahydrate and 1.5mol of cobalt nitrate hexahydrate into a mixed solution of isopropanol and glycerol, stirring until a transparent solution is obtained, transferring the transparent solution into a high-pressure reaction kettle, heating to 160 ℃, reacting for 10 hours, and naturally cooling to room temperature. And washing and filtering the obtained spherical alkoxide composite precursor precipitate by absolute ethyl alcohol, and drying to obtain the nickel-cobalt alkoxide spherical particle precursor. The subsequent operation is the same as that of example 1, and a black cobalt nickel selenide sample with the conductivity of 7.7 multiplied by 10 is obtained-4S cm-2. The SEM photograph is shown in FIG. 4, which shows regular hollow microspheres with a particle size of 300nm-800 nm. Current Density 0.5A g in 6M KOH electrolyte-1Specific capacitance of time as high as 710F g-1Even when the current density increased to 20A g-1The specific capacity is still as high as 535F g-1。
Example 5
Adding 4mol of nickel nitrate hexahydrate and 1mol of cobalt nitrate hexahydrate into a mixed solution of isopropanol and glycerol, stirring until a transparent solution is obtained, transferring the transparent solution into a high-pressure reaction kettle, heating to 180 ℃, reacting for 6 hours, and naturally cooling to room temperature. And washing and filtering the obtained spherical alkoxide composite precursor precipitate by absolute ethyl alcohol, and drying to obtain the nickel-cobalt alkoxide spherical particle precursor. The subsequent operation is the same as that of example 1, and a black cobalt nickel selenide sample with the conductivity of 5.5 multiplied by 10 is obtained-4S cm-2. Current Density 0.5A g in 6M NaOH electrolyte-1Specific capacitance of 909F g-1Even when the current density increased to 20A g-1The specific capacity is still up to 545F g-1。
Example 6
Adding 1mol of nickel nitrate hexahydrate and 2mol of cobalt nitrate hexahydrate into a mixed solution of isopropanol and glycerol, stirring until a transparent solution is obtained, transferring the transparent solution into a high-pressure reaction kettle, heating to 180 ℃, reacting for 6 hours, and naturally cooling to room temperature. And washing and filtering the obtained spherical alkoxide composite precursor precipitate by absolute ethyl alcohol, and drying to obtain the nickel-cobalt alkoxide spherical particle precursor. 9g of precursor and 17.3g of NaSeO were weighed out3Adding the mixture into an ethanol solution, stirring uniformly, transferring the mixture into a high-pressure reaction kettle for a selenization reaction, heating to 180 ℃, carrying out the selenization reaction for 6 hours, and naturally cooling to room temperature after the selenization is finished. The subsequent operation is the same as that of example 1, and a black cobalt nickel selenide sample with the conductivity of 6.7 multiplied by 10 is obtained-4S cm-2. Current density in 6M KOH electrolyte 0.5A g-1Specific capacitance of 801F g-1Even when the current density increased to 20A g-1The specific capacity is still as high as 470F g-1。
Example 7
Adding 1mmol nickel nitrate hexahydrate and 2mmol cobalt nitrate hexahydrate into a mixed solution of isopropanol and glycerol, stirring to obtain a transparent solution, transferring into a high-pressure reaction kettle, and heatingRaising the temperature to 140 ℃, reacting for 6h, and naturally cooling to room temperature. And washing and filtering the obtained spherical alkoxide composite precursor precipitate by absolute ethyl alcohol, and drying to obtain the nickel-cobalt alkoxide spherical particle precursor. Weighing 90mg of precursor and 112mg of SeO2Adding the mixture into an ethanol solution, stirring uniformly, transferring the mixture into a high-pressure reaction kettle for selenylation reaction, heating to 200 ℃, carrying out the selenylation reaction for 6 hours, and naturally cooling to room temperature after the reaction is finished. The subsequent operation was the same as in example 1, to obtain a black powder sample having a conductivity of 6.5X 10-4S cm-2. Current Density 0.5A g in 6M KOH electrolyte-1Specific capacitance of time as high as 814F g-1Even when the current density increased to 20A g-1The specific capacity is still as high as 589F g-1。
Example 8
Adding 30mol of nickel nitrate hexahydrate and 10mol of nickel acetate hexahydrate into a mixed solution of n-butanol and glycerol, stirring until a transparent solution is obtained, transferring the transparent solution into a high-pressure reaction kettle, heating to 220 ℃, reacting for 6 hours, and naturally cooling to room temperature. And washing and filtering the obtained spherical alkoxide composite precursor precipitate by absolute ethyl alcohol, and drying to obtain the nickel alkoxide spherical particle precursor. 0.9kg of precursor and 11.2kg of SeO were weighed out2Adding the mixture into an ethanol solution, stirring uniformly, transferring the mixture into a high-pressure reaction kettle for a selenization reaction, heating to 160 ℃, carrying out the selenization reaction for 12 hours, and naturally cooling to room temperature after the selenization is finished. The subsequent operation is the same as that of example 1, and a black nickel selenite sample with the conductivity of 1.2 multiplied by 10 is obtained-4S cm-2. Current Density 0.5Ag in 6M KOH electrolyte-1Specific capacitance of 700F g-1When the current density increased to 20A g-1Specific capacity 200F g-1。
Example 9
Adding 1mol of cobalt chloride hexahydrate, 1mol of cobalt nitrate hexahydrate and 1mol of nickel acetate hexahydrate into a mixed solution of ethanol and glycerol, stirring until a transparent solution is obtained, transferring the transparent solution into a high-pressure reaction kettle, heating to 180 ℃, reacting for 6 hours, and naturally cooling to room temperature. Obtaining spherical alkoxide composite precursor precipitate, washing and filtering the precipitate by absolute ethyl alcohol, and then addingDrying to obtain the precursor of the cobalt alkoxide spherical particles. 9g of precursor and 20.5g K were weighed out2SeO3Adding the mixture into an ethanol solution, stirring uniformly, transferring the mixture into a high-pressure reaction kettle for a selenization reaction, heating to 220 ℃, carrying out the selenization reaction for 4 hours, and naturally cooling to room temperature after the selenization is finished. Washing the obtained precipitate with absolute ethanol and deionized water, filtering, drying, calcining at 400 deg.C for 2 hr to obtain black cobalt selenide material with conductivity of 7.9 × 10-4S cm-2. Current Density 0.5A g in 6M KOH electrolyte-1Specific capacitance of 400F g-1Even when the current density increased to 20A g-1The specific capacity reaches 350F g-1。
Claims (10)
1. A preparation method of a hollow bicrystal phase cobalt nickel selenide microsphere material comprises the processes of solvothermal synthesis, selenization, washing, drying and calcination, and is characterized in that: weighing nickel salt and cobalt salt according to a set stoichiometric molar ratio, dissolving the nickel salt and cobalt salt in a mixed polyhydric alcohol solution with a set volume ratio, transferring the solution into a high-pressure reaction kettle after the solution is clarified, heating to a set temperature for solvent thermal synthesis for a set time, naturally cooling to room temperature to obtain a triol nickel cobalt alkoxide precursor precipitate with a spherical shape, washing with absolute ethyl alcohol, performing suction filtration, and drying to obtain a triol nickel cobalt alkoxide spherical particle precursor; and then weighing the dried nickel-cobalt alkoxide spherical particle precursor and selenium source powder according to the weight ratio, mixing and adding the weighed precursor and selenium source powder into an alcohol solution with a set volume, uniformly stirring, transferring the mixture into a high-pressure reaction kettle for selenylation reaction, heating to a set temperature for selenylation reaction for a set time, naturally cooling to room temperature after selenylation is finished, washing with absolute ethyl alcohol and deionized water, carrying out suction filtration and drying, and calcining for 1-2 hours at the set temperature to obtain the black hollow bi-crystal phase cobalt nickel selenides microsphere material.
2. The nickel salt of claim 1 comprising nitrate, chloride, sulfate and acetate, and the cobalt salt comprises one or both of nitrate, chloride, sulfate and acetate.
3. The mixed polyol solution system of claim 1 comprising: monohydric alcohol of ethanol, propanol, isopropanol and n-butanol, dihydric alcohol of ethylene glycol and propylene glycol, and trihydric alcohol of glycerol; a mixed solution of monohydric alcohol or dihydric alcohol and trihydric alcohol; the volume ratio of the monohydric alcohol or the dihydric alcohol to the trihydric alcohol is 0.1: 9.9-9.9: 01.
4. The nickel salt and the cobalt salt according to claim 1, wherein the molar ratio of the nickel salt to the cobalt salt is 0.1: 9.9-9.9: 0.1, the nickel salt and the cobalt salt are weighed and uniformly mixed and dissolved in a polyol solution, and the total concentration of the nickel ion and cobalt ion alcohol solution is 0.03 mol/L-3 mol/L.
5. The solvothermal synthesis of claim 1, carried out at a temperature of from 140 ℃ to 220 ℃ for a time of from 0.5h to 24.0 h.
6. The weight ratio of the triol nickelous alkoxide spherical particle precursor to the selenium source in the claim 1 is 1.0: 5.0-4.0: 5.0, the materials are weighed and subjected to selenization reaction, the temperature of the selenization reaction is 120-220 ℃, and the selenization time is 6-14 h.
7. The source of selenium of claim 1 being selenium dioxide (SeO)2) Sodium selenite (Na)2SeO3) And potassium selenite (K)2SeO3) One or two of the components; the alcohol solution of the selenization reaction is a mixed solution of one or two of ethanol, propanol, isopropanol, n-butanol, ethylene glycol, propylene glycol and glycerol, and the volume ratio of the mixed alcohol solution is 0.1: 9.9-9.9: 0.1.
8. The dried selenizing precipitation product of claim 1, wherein the calcining temperature is 250 ℃ -600 ℃, and the calcining time is 1-2 hours, so as to obtain the black hollow bi-crystalline phase cobalt nickel selenides microsphere material.
9. The hollow bicrystal phase cobalt nickel selenide microsphere material of claim 1, which is composed of a siderite phase and a pyrite phase bicrystal phase and is formed by bonding nanoparticlesThe particle morphology of the submicron hollow microsphere is that the particle size of the microsphere is 300nm to 800nm, and the conductivity is 1 multiplied by 10-4―1×10-3S cm-1。
10. The hollow bicrystal phase cobalt nickel selenides microsphere material of claim 1, which is applied to the fields of medicine and food industry, and comprises the following components: water system hybrid capacitors, asymmetric supercapacitors, alkali metal (lithium/sodium/potassium) ion batteries, electrocatalytic hydrogen/oxygen evolution reactions and oxygen reduction reactions.
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