CN114361445A - Cobalt diselenide composite material and preparation method and application thereof - Google Patents
Cobalt diselenide composite material and preparation method and application thereof Download PDFInfo
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- GAIMSHOTKWOMOB-UHFFFAOYSA-N [Se]=[Co]=[Se] Chemical compound [Se]=[Co]=[Se] GAIMSHOTKWOMOB-UHFFFAOYSA-N 0.000 title claims abstract description 100
- 239000002131 composite material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 20
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001354 calcination Methods 0.000 claims description 31
- CODVACFVSVNQPY-UHFFFAOYSA-N [Co].[C] Chemical compound [Co].[C] CODVACFVSVNQPY-UHFFFAOYSA-N 0.000 claims description 17
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
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- 230000001681 protective effect Effects 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims 1
- 239000000758 substrate Substances 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 239000011701 zinc Substances 0.000 description 10
- 239000012300 argon atmosphere Substances 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
- 229910052725 zinc Inorganic materials 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 238000003756 stirring Methods 0.000 description 8
- 238000000227 grinding Methods 0.000 description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 238000001035 drying Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- -1 polyethylene Polymers 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012621 metal-organic framework Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 238000010248 power generation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 150000003751 zinc Chemical class 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- BHHYHSUAOQUXJK-UHFFFAOYSA-L zinc fluoride Chemical compound F[Zn]F BHHYHSUAOQUXJK-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 239000006258 conductive agent Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- DCYOBGZUOMKFPA-UHFFFAOYSA-N iron(2+);iron(3+);octadecacyanide Chemical class [Fe+2].[Fe+2].[Fe+2].[Fe+3].[Fe+3].[Fe+3].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] DCYOBGZUOMKFPA-UHFFFAOYSA-N 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000004745 nonwoven fabric Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000004246 zinc acetate Substances 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- CITILBVTAYEWKR-UHFFFAOYSA-L zinc trifluoromethanesulfonate Chemical compound [Zn+2].[O-]S(=O)(=O)C(F)(F)F.[O-]S(=O)(=O)C(F)(F)F CITILBVTAYEWKR-UHFFFAOYSA-L 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention discloses a cobalt diselenide composite material and a preparation method and application thereof. The cobalt diselenide composite material comprises a cubic porous carbon substrate, wherein cobalt diselenide is loaded on the cubic porous carbon, and the cobalt diselenide is I-type cobalt diselenide and/or II-type cobalt diselenide; the cobalt diselenide composite material is formed by uniformly distributing cobalt diselenide on cubic porous carbon, and when I type cobalt diselenide and/or II type cobalt diselenide are/is distributed on the cubic porous carbon and used as the positive electrode of a zinc ion battery, the cobalt diselenide composite material has good conductivity, good rate performance, cycling stability and high specific capacity.
Description
Technical Field
The invention belongs to the technical field of energy storage materials, and particularly relates to a cobalt diselenide composite material and a preparation method and application thereof.
Background
With the continuous consumption of traditional energy sources such as coal and petroleum and the increasing severity of environmental pollution, energy crisis and environmental problems are considered as two major challenges facing the current society. In order to reduce the use of fossil fuels, improve the environmental quality and alleviate the energy crisis to a certain extent, it has become a common consensus to develop renewable green energy sources. Clean energy sources such as wind power generation and photovoltaic power generation are often restricted by time, regions, weather and the like, and cannot supply power continuously to meet the production requirements of people, so that intermittent electric energy needs to be stored and utilized. Therefore, research and development of new energy storage systems are needed to efficiently utilize clean energy, and secondary energy storage devices that can be recycled, have high efficiency and are environmentally friendly are important research directions of energy storage technology.
Compared with the existing lithium ion battery with wider application range, the water system zinc ion battery has great attention due to the advantages of abundant zinc resource reserves, low price, safe and environment-friendly water system electrolyte, high ion conductivity and the like. The most important part in the construction of an aqueous zinc ion battery is the electrodeThe material is characterized in that the negative electrode material is mainly metal zinc, and the positive electrode material is mainly a transition metal compound. Theoretical capacity (820mAh g) relatively higher than that of zinc cathode-1) In contrast, most of the metal compound cathode materials reported at present have relatively low capacity, for example, mainly include manganese-based compounds, vanadium-based compounds, prussian blue analogues, polymers, and the like, resulting in low energy density of the aqueous zinc-ion battery. The design and development of high-performance cathode materials become the key of the development of water-based zinc ion batteries.
Disclosure of Invention
The present invention is directed to solving at least one of the above problems in the prior art. Therefore, the invention provides a cobalt diselenide composite material.
The invention also provides a preparation method of the cobalt diselenide composite material.
The invention also provides an application of the cobalt diselenide composite material.
The invention provides a cobalt diselenide composite material, which comprises a cubic porous carbon matrix, wherein the cubic porous carbon is loaded with cobalt diselenide, and the cobalt diselenide is I-type cobalt diselenide and/or II-type cobalt diselenide; the cobalt diselenide I is orthorhombic, the space group is Pmnn, the unit cell parameters are a is 3.6, b is 4.84, c is 5.72, alpha is 90.0, beta is 90.0 and gamma is 90.0 degrees; the cobalt diselenide II is cubic, the space group is Pa-3, the unit cell parameters are a, b, c, 5.8588, alpha, 90.0, beta, 90.0 and gamma, 90.0.
The invention relates to a technical scheme of a cobalt diselenide composite material, which at least has the following beneficial effects:
the cobalt diselenide composite material is formed by uniformly distributing cobalt diselenide on cubic porous carbon, and when I type cobalt diselenide and/or II type cobalt diselenide are/is distributed on the cubic porous carbon and used as the positive electrode of a zinc ion battery, the cobalt diselenide composite material has good conductivity, rate capability, cycling stability and high specific capacity.
Research shows that when I-type cobalt diselenide and II-type cobalt diselenide in the cobalt diselenide exist in cubic porous carbon at the same time, the electrochemical performance and the specific capacity are highest, and probably because two crystal forms exist at the same time and have a synergistic effect, the electrochemical performance is enhanced.
According to some embodiments of the invention, the loading amount of the cobalt diselenide is 40-45%.
The second aspect of the invention provides a preparation method of a cobalt diselenide composite material, which comprises the following steps:
s1, carrying out primary calcination on a cobalt-containing MOF material under a protective atmosphere to obtain a carbon-cobalt composite material;
s2, fully mixing the carbon-cobalt composite material with selenium powder, and then carrying out secondary calcination in a protective atmosphere at the calcination temperature of 300-600 ℃ to obtain the cobalt diselenide composite material.
According to some embodiments of the invention, in step S2, the second calcination temperature is 400 to 550 ℃.
According to some embodiments of the invention, in step S2, the mass ratio of the carbon-cobalt composite material to the selenium powder is 1: (0.5-2).
According to some preferred embodiments of the present invention, in step S2, the mass ratio of the carbon-cobalt composite material to the selenium powder is 1: 1.
according to some embodiments of the invention, in step S2, the temperature increase rate of the second calcination temperature is 2 to 5 ℃/min.
According to some embodiments of the invention, in step S2, the holding time of the second calcination temperature is 1-2 h.
According to some embodiments of the invention, in step S1, the temperature of the first calcination is 500 to 800 ℃.
According to some embodiments of the invention, in step S1, the temperature increase rate of the first calcination is 1-5 ℃/min.
According to some embodiments of the invention, the cobalt-containing MOF material includes, but is not limited to ZIF-67.
According to some embodiments of the present invention, the ZIF-67 is prepared by the following method:
adding cobalt salt, 2-methylimidazole and hexadecyl trimethyl ammonium bromide into a solvent, and reacting to generate ZIF-67.
According to some embodiments of the invention, the reaction time is 0.5 to 2 hours.
According to some embodiments of the invention, the cobalt salt is at least one of cobalt nitrate, cobalt chloride or cobalt acetate.
According to some embodiments of the invention, the solvent is at least one of methanol, ethanol or water.
According to some embodiments of the invention, the protective atmosphere in steps S1 and S2 is an argon atmosphere.
The third aspect of the invention provides an application of the cobalt diselenide composite material in preparation of an aqueous zinc ion battery.
According to some embodiments of the invention, the aqueous zinc ion battery comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm, wherein the positive electrode adopts the cobalt diselenide composite material; or the cobalt diselenide composite material obtained by the method is prepared.
According to some embodiments of the invention, the negative electrode is one of a zinc sheet, zinc powder, electro-galvanized zinc, foamed zinc, or elemental zinc material.
According to some embodiments of the invention, the separator is selected from one or more of non-woven fabric, glass fiber, polyamide, polyester terephthalate, polyimide, polyethylene, polypropylene, polystyrene, polyvinyl chloride, acrylonitrile-butadiene-styrene copolymer, polypropylene, polytetrafluoroethylene, polyvinylidene fluoride, or polycarbonate.
According to some embodiments of the invention, the electrolyte comprises a soluble zinc salt.
According to some preferred embodiments of the invention, the soluble zinc salt is at least one of zinc sulfate, zinc chloride, zinc nitrate, zinc acetate, zinc fluoride, zinc hexafluoro-ate or zinc triflate.
Drawings
FIG. 1 is an SEM image of cobalt diselenide composite materials prepared in examples 1-4;
FIG. 2 is an X-ray diffraction pattern of cobalt diselenide composite materials prepared in examples 1-4;
FIG. 3 is a graph of electrochemical properties of cobalt diselenide composites prepared in examples 1 to 4, wherein a is 5 A.g-1Constant current charge and discharge curve diagram under current density; b is 20mV s-1Cyclic voltammogram under;
FIG. 4 is a diagram showing electrochemical properties of cobalt diselenide composite materials prepared in examples 1 to 4, wherein a is 5 A.g-1Cycle life plot under current density; b is a rate performance graph.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, but the embodiments of the present invention are not limited thereto.
The reagents, methods and equipment adopted by the invention are conventional in the technical field if no special description is given.
Example 1
Embodiment 1 provides a cobalt diselenide composite material, including a cubic porous carbon substrate, where cobalt diselenide is supported on the cubic porous carbon, and the cobalt diselenide is type I cobalt diselenide, and the preparation method is as follows:
preparation of ZIF-67: 4mmol of Co (NO)3)2·6H2O and 0.06mmol of hexadecyl trimethyl ammonium bromide are fully stirred and completely dissolved in 40mL of deionized water to form a solution A; and (2) fully stirring and dissolving 0.22mol of 2-methylimidazole in 280mL of deionized water to form a solution B, pouring the solution A into the solution B, magnetically stirring at room temperature for 1h, and then centrifugally drying to obtain ZIF-67.
S1, calcining ZIF-67 in an argon atmosphere to obtain a carbon-cobalt composite material; the calcination temperature is 800 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1 h;
s2, mixing the carbon-cobalt composite material obtained in the step S1 with selenium powder according to a mass ratio of 1: 1, fully grinding and mixing, calcining in an argon atmosphere at the calcining temperature of 300 ℃ and the heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain the cobalt diselenide composite material.
Example 2
Embodiment 2 provides a cobalt diselenide composite material, including a cubic porous carbon substrate, on which cobalt diselenide is supported, the cobalt diselenide being composed of type I cobalt diselenide and type ii cobalt diselenide, and the preparation method is as follows:
preparation of ZIF-67: 4mmol of Co (NO)3)2·6H2O and 0.06mmol of hexadecyl trimethyl ammonium bromide are fully stirred and completely dissolved in 40mL of deionized water to form a solution A; and (2) fully stirring and dissolving 0.22mol of 2-methylimidazole in 280mL of deionized water to form a solution B, pouring the solution A into the solution B, magnetically stirring at room temperature for 1h, and then centrifugally drying to obtain ZIF-67.
S1, calcining ZIF-67 in an argon atmosphere to obtain a carbon-cobalt composite material; the calcination temperature is 800 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1 h;
s2, mixing the carbon-cobalt composite material obtained in the step S1 with selenium powder according to a mass ratio of 1: 1, fully grinding and mixing, calcining in an argon atmosphere at the calcining temperature of 400 ℃ and the heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain the cobalt diselenide composite material.
Example 3
Embodiment 3 provides a cobalt diselenide composite material, including a cubic porous carbon substrate, on which cobalt diselenide is supported, the cobalt diselenide being composed of type i cobalt diselenide and type ii cobalt diselenide, and the preparation method is as follows:
preparation of ZIF-67: 4mmol of Co (NO)3)2·6H2O and 0.06mmol of hexadecyl trimethyl ammonium bromide are fully stirred and completely dissolved in 40mL of deionized water to form a solution A; and (2) fully stirring and dissolving 0.22mol of 2-methylimidazole in 280mL of deionized water to form a solution B, pouring the solution A into the solution B, magnetically stirring at room temperature for 1h, and then centrifugally drying to obtain ZIF-67.
S1, calcining ZIF-67 in an argon atmosphere to obtain a carbon-cobalt composite material; the calcination temperature is 800 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1 h;
s2, mixing the carbon-cobalt composite material obtained in the step S1 with selenium powder according to a mass ratio of 1: 1, fully grinding and mixing, calcining in an argon atmosphere at the calcining temperature of 500 ℃ at the heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain the cobalt diselenide composite material.
Example 4
Embodiment 2 provides a cobalt diselenide composite material, including a cubic porous carbon substrate, where cobalt diselenide is supported on the cubic porous carbon, and the cobalt diselenide is type ii cobalt diselenide, and the preparation method is as follows:
preparation of ZIF-67: 4mmol of Co (NO)3)2·6H2O and 0.06mmol of hexadecyl trimethyl ammonium bromide are fully stirred and completely dissolved in 40mL of deionized water to form a solution A; and (2) fully stirring and dissolving 0.22mol of 2-methylimidazole in 280mL of deionized water to form a solution B, pouring the solution A into the solution B, magnetically stirring at room temperature for 1h, and then centrifugally drying to obtain ZIF-67.
S1, calcining ZIF-67 in an argon atmosphere to obtain a carbon-cobalt composite material; the calcination temperature is 800 ℃, the heating rate is 5 ℃/min, and the temperature is kept for 1 h;
s2, mixing the carbon-cobalt composite material obtained in the step S1 with selenium powder according to a mass ratio of 1: 1, fully grinding and mixing, calcining in an argon atmosphere at the calcining temperature of 400 ℃ and the heating rate of 2 ℃/min, and preserving heat for 2 hours to obtain the cobalt diselenide composite material.
Example 5
Example 5 is the same as the production method of example 1 except that the temperature increase rate in step S2 is 5 ℃/min.
Example 6
Example 6 was prepared in the same manner as in example 1 except that the keeping time in step S2 was 1 h.
Example 7
Example 7 is the same as the preparation method of example 1 except that the carbon-cobalt composite material and the selenium powder of step S1 are mixed in the mass ratio of 1: 2 grinding and mixing fully.
Example 8
Example 8 is the same as the preparation method of example 1, except that the carbon-cobalt composite material and the selenium powder of step S1 are mixed in the mass ratio of 1: 0.5, fully grinding and mixing.
Performance testing
The cobalt diselenide composite material prepared in the above embodiment is prepared into a positive electrode material of a water system zinc ion battery, and is used for testing electrochemical performance: preparation of a mixture containing 80 wt% CoSe in DMF2300(400, 500, 600), 10 wt% acetylene black (conductive agent) and 10 wt% PVDF (binder) homogeneous slurry, then uniformly coated on conductive substrate carbon paper, then vacuum-dried overnight at 60 ℃ to form working electrode, the active material loading on the working electrode is about 1.6-1.8 mg-cm-2. The following electrochemical performance tests were all performed in an electrolytic cup environment with 3M KOH and 0.2M Zn (Ac)2The aqueous solution, positive electrode was prepared carbon paper coated with active material, negative electrode was zinc sheet, electrochemical station was CHI 660E.
Fig. 1 is an SEM image of cobalt diselenide composite materials prepared in examples 1 to 4, where examples 1 to 4 are a to d, respectively, and it can be seen that there is no significant difference in the SEM image of products at different temperatures, and all cobalt diselenide is uniformly distributed in the cubic porous carbon.
As is apparent from the XRD pattern in fig. 2, the cobalt diselenide composite material with different crystal forms has been successfully prepared, and the crystal form of cobalt diselenide in example 1 is CoSe2#10-0408 (hereinafter referred to as cobalt diselenide form I), cobalt diselenide form I being an orthorhombic system, the space group being Pmnn, the unit cell parameters being a ═ 3.6, b ═ 4.84, c ═ 5.72, α ═ 90.0, β ═ 90.0, γ ═ 90.0 °, cobalt diselenide in example 2 being in two crystal forms, cobalt diselenide form I and cobalt diselenide form II, the (211) (311) (230) (321) peak of cobalt diselenide form II beginning to form gradually; example 5 also two crystal forms exist, the predominant crystal form being CoSe2#09-0234 (hereinafter referred to as cobalt diselenide form II), cobalt diselenide form II is a cubic system, the space group is Pa-3, the unit cell parameters are a ═ b ═ c ═ 5.8588, α ═ 90.0 °, β ═ 90.0 °, γ ═ 90.0 °, mainly cobalt diselenide form II, and in the XRD image of the product of example 6, the characteristic peak (012) (121) corresponding to cobalt diselenide form I has gradually disappeared, almost completely, cobalt diselenide form II.
From FIG. 3, it can be seen that each area of the cobalt diselenide composite material with different crystal formsThere is a clear difference that the area of the curve is significantly smaller in examples 1 and 2 than in examples 3 and 4. Example 1 and example 3 in FIG. 3a at 5Ag-1The constant current charging and discharging curves under the current density have obvious difference.
From the cycle life plot of FIG. 4a, the initial 810mAh m of example 5 can be seen-2After 2000 cycles, 511 mAh.m is still maintained-2The area specific capacitance of the material shows the most excellent electrochemical performance in four selenization materials with different temperatures. The rate capability and coulombic efficiency of examples 5 and 6 are shown in fig. 4b, and it can be seen that the better example 5, in which both crystal forms are mixed, shows better specific capacitance and rate capability than example 6, in which almost only characteristic peaks of form II, under the condition that both crystal forms are dominated by form II and the performance is similar.
Example 5 the temperature rise rate is too fast, resulting in an obvious peak shape of elemental selenium in an XRD pattern, indicating that the selenium powder has more residue and is not completely reacted; example 6 the heat preservation time is too short, which causes that the characteristic peak of the carbon-cobalt composite of the preorder product does not completely disappear and the reaction is incomplete; example 7 excessive selenium powder residue results in reduced material conductivity, and the difference of EIS images is obvious; example 8 the selenium powder is too little and is not completely reacted, and the characteristic peak of the preorder product of the XRD image is not completely disappeared.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. Any modification, equivalent replacement, and improvement made within the spirit and principle of the present invention should be included in the protection scope of the claims of the present invention.
Claims (10)
1. The cobalt diselenide composite material is characterized by comprising a cubic porous carbon matrix, wherein cobalt diselenide is loaded on the cubic porous carbon matrix, and the cobalt diselenide is I-type cobalt diselenide and/or II-type cobalt diselenide; the cobalt diselenide I is orthorhombic, the space group is Pmnn, the unit cell parameters are a is 3.6, b is 4.84, c is 5.72, alpha is 90.0, beta is 90.0 and gamma is 90.0 degrees; the cobalt diselenide II is cubic, the space group is Pa-3, the unit cell parameters are a, b, c, 5.8588, alpha, 90.0, beta, 90.0 and gamma, 90.0.
2. The cobalt diselenide composite material according to claim 1, wherein the loading amount of the cobalt diselenide is 40-45%.
3. The method for preparing the cobalt diselenide composite material according to claim 1, comprising the steps of:
s1, carrying out primary calcination on a cobalt-containing MOF material under a protective atmosphere to obtain a carbon-cobalt composite material;
s2, mixing the carbon-cobalt composite material with selenium powder, and then carrying out secondary calcination in a protective atmosphere, wherein the calcination temperature is 300-600 ℃.
4. The method for preparing a cobalt diselenide composite material according to claim 3, wherein in step S2, the second calcination temperature is 400-500 ℃.
5. The method for preparing a cobalt diselenide composite material as claimed in claim 3, wherein in step S2, the mass ratio of the cobalt carbonate composite material to the selenium powder is 1: (0.5-2).
6. The method for preparing a cobalt diselenide composite material according to claim 3, wherein in step S2, the temperature rise rate of the second calcination is 2-5 ℃/min.
7. The preparation method of the cobalt diselenide composite material as claimed in claim 3, wherein in the step S2, the heat preservation time of the second calcination is 1-2 h.
8. The method for preparing a cobalt diselenide composite material according to claim 3, wherein in step S1, the temperature of the first calcination is 500-800 ℃.
9. The use of the cobalt diselenide composite material according to claim 1 in the preparation of an aqueous zinc ion battery.
10. An aqueous zinc ion battery, which comprises a positive electrode, a negative electrode, an electrolyte and a diaphragm, and is characterized in that the positive electrode adopts the cobalt diselenide composite material as claimed in claim 1 or 2; or the cobalt diselenide composite material obtained by the method of any one of claims 3 to 8.
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| CN109037617A (en) * | 2018-07-10 | 2018-12-18 | 厦门理工学院 | A kind of cobaltous selenide/nitrogen-doped carbon composite material and preparation method, application |
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| CN113277484A (en) * | 2020-02-19 | 2021-08-20 | 松山湖材料实验室 | High-performance alkaline zinc battery cathode material and preparation method thereof |
| CN113410440A (en) * | 2021-05-14 | 2021-09-17 | 华南理工大学 | Cobalt diselenide @ porous nitrogen-doped carbon nanocomposite, potassium ion battery and preparation method of cobalt diselenide @ porous nitrogen-doped carbon nanocomposite |
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