CN114743805A - ZIF-67 graphene attapulgite composite material and preparation method and application thereof - Google Patents
ZIF-67 graphene attapulgite composite material and preparation method and application thereof Download PDFInfo
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- CN114743805A CN114743805A CN202210365883.0A CN202210365883A CN114743805A CN 114743805 A CN114743805 A CN 114743805A CN 202210365883 A CN202210365883 A CN 202210365883A CN 114743805 A CN114743805 A CN 114743805A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 66
- 229960000892 attapulgite Drugs 0.000 title claims abstract description 42
- 229910052625 palygorskite Inorganic materials 0.000 title claims abstract description 42
- 239000002131 composite material Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims description 25
- 239000000243 solution Substances 0.000 claims description 23
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 9
- 238000004729 solvothermal method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 6
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 239000003990 capacitor Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 239000007774 positive electrode material Substances 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 abstract description 7
- 238000005054 agglomeration Methods 0.000 abstract description 5
- 230000002776 aggregation Effects 0.000 abstract description 5
- 239000011149 active material Substances 0.000 abstract description 4
- 230000002427 irreversible effect Effects 0.000 abstract description 4
- 238000009825 accumulation Methods 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 239000007773 negative electrode material Substances 0.000 abstract description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 15
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 229910052573 porcelain Inorganic materials 0.000 description 6
- 229910052759 nickel Inorganic materials 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 description 5
- 239000006260 foam Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002734 clay mineral Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/46—Metal oxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
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- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a ZIF-67 graphene/attapulgite composite material, which is formed by combining graphene and attapulgite on the basis of ZIF-67, wherein transition metal oxide is combined with graphene to prepare a high-efficiency durable supercapacitor electrode material, a three-dimensional porous graphene structure is used as a framework to contain an active material, the defects of irreversible agglomeration or re-accumulation and the like of the graphene can be eliminated, and the rate performance and the cycle stability of a negative electrode material are improved.
Description
Technical Field
The invention relates to a composite material, in particular to a ZIF-67 graphene attapulgite composite material and a preparation method and application thereof, and belongs to the technical field of composite materials.
Background
The graphene as a carbon material has the advantages of high specific surface area, high electron transmission rate, low density and the like, and shows wide application prospects in the field of super capacitors. However, the simple graphene surface is difficult to wet by electrolyte due to high stability, and the application of the graphene in production is limited due to irreversible agglomeration caused by strong van der waals force between graphene sheets. The attapulgite is a hydrous magnesium-aluminum-rich silicate clay mineral, has a unique layer chain structure, has a large specific surface inside, has good affinity to an electrode solvent, and can improve the wettability of an electrolyte and prolong the service life of a battery by adding the attapulgite into an electrode. ZIF-67 is a framework material of an imidazole molecular sieve, takes cobalt ions as metal nodes, and belongs to a porous crystal material.
The ZIF-67 is compounded with the graphene and the attapulgite to obtain the composite material with the characteristics of high specific volume and high conductivity, so that the specific surface area of the composite material can be increased, the multiplying power of a battery is improved, and the defects of irreversible agglomeration or re-accumulation of the graphene and the like are overcome.
Disclosure of Invention
The invention aims to provide a ZIF-67 graphene attapulgite composite material, a preparation method and application thereof, and aims to solve the problems in the background art.
In order to achieve the purpose, the invention provides the following technical scheme: a ZIF-67 graphene attapulgite composite material is formed by combining graphene and attapulgite on the basis of ZIF-67.
As a preferred technical scheme of the invention, the preparation method of the ZIF-67 graphene attapulgite composite material comprises the following steps:
s1: preparing ZIF-67, namely respectively dissolving 2-methylimidazole and cobalt nitrate in a good solvent, and uniformly stirring to obtain a solution A and a solution B; mixing the solution A and the solution B to obtain a mixed solution C; putting the mixed solution C into a high-pressure reaction kettle, and reacting under certain conditions to obtain a precursor of a product ZIF-67;
s2: preparing ZIF-67 graphene, namely adding a certain amount of graphene micro powder in the step of preparing ZIF-67, and adding a proper amount of solvent to prepare a precursor of the ZIF-67 graphene composite material;
s3: preparing ZIF-67 graphene attapulgite, namely adding a certain amount of graphene micro powder and attapulgite in the step of preparing ZIF-67, and adding a proper amount of solvent to prepare a precursor of the ZIF-67 graphene attapulgite composite material;
s4: and (5) putting the precursors obtained in the steps S1, S2 and S3 into inert gas to be calcined to obtain the composite material.
In a preferred embodiment of the present invention, the good solvent in step S1 is methanol, the ZIF-67 is prepared by a solvothermal method in step S1, and the mass ratio of the cobalt nitrate to the 2-methylimidazole is 1.1 to 1.5: 1.
in a preferred embodiment of the present invention, in step S2, the solvothermal process is performed at 100-120 ℃ for 10-15 hours.
As a preferred technical scheme of the invention, the ZIF-67 graphene attapulgite composite material and the preparation method and the application thereof are characterized in that: the calcination temperature in the step S3 is 350-550 ℃ and the calcination time is 2-4 h, and the inert gas in the step S3 is N2 or Ar.
As a preferred technical scheme of the invention, the application of the ZIF-67 graphene attapulgite composite material is characterized in that: the composite material is applied to the positive electrode material of the super capacitor.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention relates to a ZIF-67 graphene/attapulgite composite material and a preparation method and application thereof, wherein a transition metal oxide is combined with graphene to prepare a high-efficiency durable supercapacitor electrode material, a three-dimensional porous graphene structure is used as a framework to contain an active material, the defects of irreversible agglomeration or re-accumulation of the graphene and the like can be eliminated, and the rate performance and the cycle stability of a negative electrode material are improved.
Drawings
FIG. 1 is an XRD pattern of the resulting ZIF-67, ZIF-67/graphene and ZIF-67/graphene/attapulgite rods;
FIG. 2 is SEM images of the resulting ZIF-67, ZIF-67/graphene and ZIF-67/graphene/attapulgite rods;
FIG. 3 is a cyclic voltammogram of the prepared ZIF-67, ZIF-67/graphene and ZIF-67/graphene/attapulgite;
FIG. 4 is a graph showing data on the specific capacitance measured using ZIF-67 prepared in comparative example 1, ZIF-67/graphene prepared in comparative example 2, and ZIF-67/graphene/attapulgite prepared in example 1 as electrode materials.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Referring to fig. 1 to 4, the invention provides a ZIF-67 graphene attapulgite composite material, a preparation method and an application thereof, wherein the technical scheme comprises the following steps:
example 1
The preparation method of the nano composite material comprises the following steps:
(1) preparation of ZIF-67 material: weighing 3.30g of 2-methylimidazole, dissolving in 20mL of methanol solution, and uniformly stirring to obtain a solution A; dissolving 2.90g of cobalt nitrate in 20mL of methanol solution, and uniformly stirring to obtain a solution B; and mixing the solution A and the solution B to obtain a solution C.
(2) Preparing a precursor: and (3) putting the mixed solution C into a high-pressure kettle, carrying out solvothermal reaction at the temperature of 120 ℃ for 12 hours, and drying in an oven at the temperature of 60 ℃ for one night after the solvothermal reaction is finished to obtain the precursor.
(3) Preparation of ZIF-67 material: and (3) placing the precursor obtained in the step (2) in a porcelain boat, heating the porcelain boat to 350 ℃ from room temperature at the speed of 1 ℃/min under the condition of introducing N2, and calcining the porcelain boat for 2 hours to obtain a sample ZIF-67.
(4) Preparing a ZIF-67/graphene composite material: the preparation of the ZIF-67/graphene is to add 0.05g of polytetrafluoroethylene micro powder in the preparation process of the ZIF-67, and the rest experimental steps are the same as the steps for preparing the ZIF-67.
(5) Preparing a ZIF-67/graphene/attapulgite composite material: the preparation of the ZIF-67/graphene is to add 0.05g of polytetrafluoroethylene micro powder and 0.5g of attapulgite in the preparation process of the ZIF-67, and the other experimental steps are the same as the steps for preparing the ZIF-67.
When the ZIF-67 material of step (5) obtained in this example was subjected to X-ray diffraction, the obtained XRD spectrum showed distinct diffraction peaks at 2 θ of 7.4 °, 12.7 °, 14.7 ° and 19.0 ° compared with the standard card.
The ZIF-67, ZIF-67/graphene and ZIF-67/graphene/attapulgite composite material prepared in step (2) of the present embodiment are observed by a scanning electron microscope, and the obtained SEM morphology is shown in fig. 2, which shows that the ZIF-67 material prepared in example 1 of the present invention is a polyhedral structure, but has an agglomeration phenomenon, the ZIF-67/graphene is granular, and the ZIF-67/graphene/attapulgite composite material shows a porous network structure connected with each other, and such a structure can provide more exposed electrically active sites, accelerate electron and ion transfer, and thereby improve the electrochemical performance of the material.
Example 2
The preparation method of the nano composite material comprises the following steps:
(1) preparation of MOF material: weighing 3.30g of 2-methylimidazole, dissolving in 20mL of methanol solution, and uniformly stirring to obtain a solution A; dissolving 4.35g of cobalt nitrate in 20mL of methanol solution, and uniformly stirring to obtain a solution B; and mixing the solution A and the solution B to obtain a solution C.
(2) Preparing a precursor: and (3) putting the mixed solution C into a high-pressure kettle, carrying out solvothermal reaction at the temperature of 120 ℃ for 15 hours, and drying in an oven at the temperature of 60 ℃ for one night after the solvothermal reaction is finished to obtain the precursor.
(3) Preparation of ZIF-67 material: and (3) placing the precursor obtained in the step (2) in a porcelain boat, heating the porcelain boat to 550 ℃ from room temperature at the speed of 1 ℃/min under the condition of introducing N2, and calcining the porcelain boat for 4 hours to obtain a sample ZIF-67.
(4) Preparing a ZIF-67/graphene composite material: the preparation of the ZIF-67/graphene is to add 0.05g of polytetrafluoroethylene micro powder in the process of preparing the ZIF-67, and the other experimental steps are the same as the steps for preparing the ZIF-67.
(5) Preparing a ZIF-67/graphene/attapulgite composite material: the preparation of the ZIF-67/graphene is to add 0.05g of polytetrafluoroethylene micro powder and 0.5g of attapulgite in the preparation process of the ZIF-67, and the other experimental steps are the same as the steps for preparing the ZIF-67.
Application example
The composite material prepared in the example is applied to an anode electrode material of a supercapacitor and subjected to electrochemical test.
The electrochemical performance tests are all completed on the Shanghai Chenghua CHI660 electrochemical workstation. A three-electrode system is adopted: the nickel foam coated with the active material is used as a working electrode, the platinum sheet electrode is used as a counter electrode, and the Saturated Calomel Electrode (SCE) is used as a reference electrode. In the experiments, all potentials were relative to SCE and all experiments were performed at room temperature. Before the use of the foamed nickel, the foamed nickel is sequentially cleaned by absolute ethyl alcohol and distilled water in an ultrasonic mode and dried for later use.
Preparing an electrode: weighing the prepared electrode active material, conductive carbon black and polytetrafluoroethylene micro powder according to the mass ratio of 8:1:1, mixing, adding a proper amount of isopropanol serving as a dispersing agent, and stirring and ultrasonically treating until the mixture is uniformly dispersed. The material with moderate viscosity is evenly coated on the surface (1cm multiplied by 1cm) of the foam nickel which is pretreated by a glass rod, and finally the foam nickel is put into an oven and taken out for standby after being completely dried.
The specific capacitance of the example is calculated by using the formula C-I/v, Cs-C/m-I/m/v, where Cs is the specific capacitance (F/g), I is the current (a), m is the electrode material mass (g), v is the scanning speed (v/s), and the specific capacitance means the amount of electricity that can be discharged per unit weight of the battery or active material, as shown in fig. 4, and the specific capacitance of the ZIF-67 material is 140F/g at 5 mV/s; the specific capacitance of the ZIF-67/graphene composite material is 300F/g under 5 mV/s; the specific capacitance of ZIF-67/graphene/attapulgite is 697F/g under 5mV/s, and the specific value is shown in FIG. 4; the specific capacitance of ZIF-67/graphene/attapulgite is obviously larger than that of other two materials.
When the ZIF-67/graphene/attapulgite composite material prepared by the method is applied to an anode material of a super capacitor, an electrode material with large specific capacitance and low pollution can be effectively generated, because the shape of the composite material is of a mutually connected porous network structure, the structure can provide more exposed electroactive sites, and accelerate electron and ion transfer, thereby improving the electrochemical performance of the material.
In the description of the present invention, it is to be understood that the indicated orientations or positional relationships are based on the orientations or positional relationships shown in the drawings and are only for convenience in describing the present invention and simplifying the description, but are not intended to indicate or imply that the indicated devices or elements must have a particular orientation, be constructed and operated in a particular orientation, and are not to be construed as limiting the present invention.
In the present invention, unless otherwise explicitly specified or limited, for example, it may be fixedly attached, detachably attached, or integrated; can be mechanically or electrically connected; the terms may be directly connected or indirectly connected through an intermediate agent, and may be used for communicating the inside of two elements or interacting relation of two elements, unless otherwise specifically defined, and the specific meaning of the terms in the present invention can be understood by those skilled in the art according to specific situations.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (6)
1. The ZIF-67 graphene attapulgite composite material is characterized in that the composite material is formed by combining graphene and attapulgite on the basis of ZIF-67.
2. A preparation method of a ZIF-67 graphene attapulgite composite material is characterized by comprising the following steps:
s1: preparing ZIF-67, namely respectively dissolving 2-methylimidazole and cobalt nitrate in a good solvent, and uniformly stirring to obtain a solution A and a solution B; mixing the solution A and the solution B to obtain a mixed solution C; putting the mixed solution C into a high-pressure reaction kettle, and reacting under certain conditions to obtain a precursor of a product ZIF-67;
s2: preparing ZIF-67 graphene, namely adding a certain amount of graphene micro powder in the step of preparing ZIF-67, and adding a proper amount of solvent to prepare a precursor of the ZIF-67 graphene composite material;
s3: preparing ZIF-67 graphene attapulgite, namely adding a certain amount of graphene micro powder and attapulgite in the step of preparing ZIF-67, and adding a proper amount of solvent to prepare a precursor of the ZIF-67 graphene attapulgite composite material;
s4: and (5) putting the precursors obtained in the steps S1, S2 and S3 into inert gas to be calcined to obtain the composite material.
3. The preparation method of the ZIF-67 graphene attapulgite composite material according to claim 2, characterized in that: the good solvent in the step S1 is methanol, the ZIF-67 is prepared by a solvothermal method in the step S1, and the mass ratio of the cobalt nitrate to the 2-methylimidazole is 1.1-1.5: 1.
4. the preparation method of the ZIF-67 graphene attapulgite composite material according to claim 2, characterized in that: in the step S2, the solvothermal process is performed at 100-120 ℃ for 10-15 h.
5. The preparation method of the ZIF-67 graphene attapulgite composite material according to claim 2, characterized in that: the calcination temperature in the step S3 is 350-550 ℃ and the time is 2-4 hours, and the inert gas in the step S3 is N2 or Ar.
6. An application of a ZIF-67 graphene attapulgite composite material is characterized in that: the composite material is applied to the positive electrode material of the super capacitor.
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| WO2024065662A1 (en) * | 2022-09-30 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Secondary battery, electric device and use of composite silicate |
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| WO2024065662A1 (en) * | 2022-09-30 | 2024-04-04 | 宁德时代新能源科技股份有限公司 | Secondary battery, electric device and use of composite silicate |
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