CN115411249A - Aluminum ion doped Co 9 S 8 Preparation method of/MXene heterostructure composite material - Google Patents
Aluminum ion doped Co 9 S 8 Preparation method of/MXene heterostructure composite material Download PDFInfo
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- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- -1 Aluminum ion Chemical class 0.000 claims abstract description 40
- 239000002135 nanosheet Substances 0.000 claims abstract description 23
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 18
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 claims abstract description 8
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 claims abstract description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 24
- 229910018185 Al—Co Inorganic materials 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 15
- 239000000843 powder Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000006228 supernatant Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 5
- 239000004809 Teflon Substances 0.000 claims description 3
- 229920006362 Teflon® Polymers 0.000 claims description 3
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910052976 metal sulfide Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000003990 capacitor Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 238000004729 solvothermal method Methods 0.000 abstract description 3
- 239000007772 electrode material Substances 0.000 abstract description 2
- 238000005530 etching Methods 0.000 abstract description 2
- 230000014759 maintenance of location Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 13
- 239000000463 material Substances 0.000 description 11
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- YIWGJFPJRAEKMK-UHFFFAOYSA-N 1-(2H-benzotriazol-5-yl)-3-methyl-8-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carbonyl]-1,3,8-triazaspiro[4.5]decane-2,4-dione Chemical compound CN1C(=O)N(c2ccc3n[nH]nc3c2)C2(CCN(CC2)C(=O)c2cnc(NCc3cccc(OC(F)(F)F)c3)nc2)C1=O YIWGJFPJRAEKMK-UHFFFAOYSA-N 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 239000004411 aluminium Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910002463 CoxSy Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000037427 ion transport Effects 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
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
Aluminum ion doped Co 9 S 8 A preparation method of/MXene heterostructure composite material relates to Co 9 S 8 A preparation method of the/MXene heterostructure composite material. It is to solve the existing Co x S y The @ MXene electrode material has the technical problems of low specific capacitance and poor cycle stability. The method comprises the steps of firstly obtaining MXene nanosheets by etching, and then stirring the MXene nanosheets, cobalt chloride hexahydrate, aluminum chloride hexahydrate and thiourea to perform one-step solvothermal reaction to generate aluminum ion doped Co 9 S 8 the/MXene composite material. The composite material has a capacitance at a current density of 2 ag ‑1 Is 1643 Cg ‑1 When the current density is from 2 ag ‑1 Increased to 15 ag ‑1 When the capacity retention ratio is 70%. Can be used in the field of super capacitors.
Description
Technical Field
The invention relates to Co 9 S 8 A preparation method of the/MXene heterostructure composite material.
Background
With the advancement of technology, people have increasingly high demand for electronic devices, and supercapacitors are receiving much attention due to their excellent electrochemical properties.
MXene has been shown to have great potential in the field of energy storage due to its unique layered structure and excellent electrical conductivity. Generally, the metal oxide/MXene composite material is prepared by adopting a hydrothermal and solvothermal method to generate the metal oxide/MXene composite on MXene nano-sheets. For example, the chinese patent application No. 202011579306.9, aluminum ion battery and its positive electrode material Cox sy @ MXene, discloses an aluminum ion battery and its positive electrode material Cox sy @ MXene, the positive electrode material is made by in-situ growth of micro-nano cobalt sulfide on MXene substrate material, the micro-nano cobalt sulfide is CoxSy, wherein x > 0, y > 0, and the mass of the micro-nano cobalt sulfide accounts for 5% -95% of the total mass of the positive electrode material. The dispersibility of the nano micro-nano cobalt sulfide is improved, crystal grains are refined, and the conductivity is improved, but the material has low specific capacity and poor cycle stability when being used for a super capacitor.
Disclosure of Invention
The invention aims to solve the problem of the existing Co x S y The technical problems of low specific capacitance and poor cycle stability of the @ MXene electrode material are solved, and the aluminum ion doped Co is provided 9 S 8 The preparation method of the/MXene heterostructure composite material comprises the steps of firstly obtaining MXene nanosheets through etching, and then carrying out one-step solvothermal reaction on the MXene nanosheets and a metal compound to generate Co doped with metal aluminum ions 9 S 8 the/MXene composite material provides a new idea for preparing a high-performance supercapacitor.
The aluminum ion of the invention is doped with Co 9 S 8 The preparation method of the/MXene heterostructure composite material comprises the following steps:
1. preparation of MXene nanosheets:
a. adding 1g of nickel fluoride into 20mL of 9M HCl, and mixing and stirring the 9M HCl and the nickel fluoride for 25-35 minutes to obtain a mixed solution;
b. adding titanium aluminum carbide into the mixed solution, heating to 35-45 ℃ and keeping for 85-95 hours;
c. centrifugally washing the product obtained in the step b by using 1M HCl, removing supernatant, centrifugally washing the precipitate by using deionized water until the pH value of the supernatant reaches 6-8, removing the supernatant, adding the precipitate into deionized water, carrying out ultrasonic treatment in an ice bath under nitrogen for 50-70 minutes, centrifugally treating the mixed solution, removing upper-layer suspension, taking the precipitate, and freeze-drying to obtain MXene nanosheet powder;
2. aluminum doped metal sulfide/MXene Al-Co 9 S 8 Preparation of MXene:
a. adding MXene nanosheet powder into a mixed solution of ethylene glycol and N, N-dimethylformamide, and carrying out ultrasonic treatment for 20-30 minutes; then adding cobalt chloride hexahydrate and aluminum chloride hexahydrate, stirring for 10-20 minutes, adding thiourea, and stirring for 25-35 minutes to obtain a precursor solution;
b. transferring the precursor solution into a Teflon high-pressure kettle, heating to 140-180 ℃, keeping for 10-14 hours, taking out the product, centrifugally cleaning the product by using ethanol and deionized water in sequence, and freeze-drying to obtain the aluminum ion doped Co 9 S 8 a/MXene heterostructure composite.
Further, the centrifugation in the step one c is performed for 5 to 10 minutes at a rotation speed of 3000 to 4000 rpm.
Further, the ratio of the mass of MXene nanosheet powder to the volume of ethylene glycol in step two a is 1g: (95-105) mL.
Further, the ratio of the mass of the MXene nanosheet powder to the volume of the N, N-dimethylformamide in step two a is 1g: (350-450) mL.
Furthermore, the mass ratio of MXene nanosheet powder to cobalt chloride hexahydrate in the second step a is 1: (5-7).
Furthermore, in the second step a, the molar ratio of cobalt chloride hexahydrate, aluminum chloride hexahydrate and thiourea is 1: (0.1-0.2): (3-3.5).
Furthermore, when ethanol and deionized water are used for centrifugal separation in the step two b, the centrifugal treatment is carried out for 5 to 20 minutes under the condition that the rotating speed is 10000 to 11000 rpm.
The invention takes MXene etched by nickel fluoride as a substrate to prepare Co doped with aluminum ions 9 S 8 a/MXene heterojunction material. The material of the invention enters into the crystal lattice of the metal sulfide by introducing aluminum ions, so that the crystal lattice defect is generated, and the specific capacitance is improved. The capacitance of the heterojunction material is 2 Ag at the current density -1 When it is 1643C g -1 When the current density is from 2 Ag -1 Increased to 15 ag -1 The capacity retention rate reaches 70%. Can be used in the field of super capacitors.
Drawings
FIG. 1 is a scanning electron micrograph of MXene obtained in step one of example 1;
FIG. 2 shows the aluminum ion-doped Co obtained in step two of example 1 9 S 8 Scanning electron microscope photos of the MXene heterostructure composite materials;
FIG. 3 shows the result of step two in example 1, which is doped with Co 9 S 8 Al-Co composite material with/MXene heterostructure 9 S 8 XRD spectrum of/MXene;
FIG. 4 shows the result of step two of example 1, which is obtained by doping Co with aluminum ions 9 S 8 /MXene heterogeneityStructural composite material Al-Co 9 S 8 XPS spectrum of/MXene;
FIG. 5 shows the result of step two in example 1, which is doped with Co 9 S 8 Constant current charge and discharge (GCD) curve diagram of/MXene heterostructure composite material;
FIG. 6 shows the result of step two of example 1, which is obtained by doping Co with aluminum ions 9 S 8 Multiplying power performance diagram of/MXene heterostructure composite material.
FIG. 7 shows aluminum ion-undoped Co prepared in comparative example 2 9 S 8 Constant current charge and discharge (GCD) curve of/MXene;
FIG. 8 shows aluminum ion-undoped Co prepared in comparative example 2 9 S 8 Multiplying power performance graph of/MXene.
Detailed Description
The following examples are used to demonstrate the beneficial effects of the present invention.
Example 1: the aluminum ion of this example was doped with Co 9 S 8 The preparation method of the/MXene heterostructure composite material comprises the following steps:
1. preparation of MXene nanosheets:
a. adding 1g of nickel fluoride into 20mL of 9M HCl, and mixing and stirring for 30 minutes to obtain a mixed solution;
b. adding 1g of titanium aluminum carbide into the mixed solution, heating to 40 ℃ and keeping for 90 hours;
c. centrifuging the product obtained in the step b by using 1M HCl at 3500rpm for 6 minutes, discarding the supernatant, centrifuging and washing the precipitate by using deionized water at 3500rpm for 6 minutes, repeatedly centrifuging until the pH value of the supernatant reaches 6, discarding the supernatant, adding the precipitate into 30mL of deionized water, ultrasonically treating for 60 minutes under nitrogen and under the condition of keeping the temperature at 8 ℃, finally centrifuging the mixed solution at 3500rpm for 60 minutes, discarding the supernatant, and freeze-drying the precipitate in a freeze-drying machine at-55 ℃ and the vacuum degree of 10Pa for 2 days to obtain MXene nanosheet powder;
2. doping of aluminum ions with Co 9 S 8 Al-Co composite material with/MXene heterostructure 9 S 8 Preparation of MXene:
a. adding 60mg of MXene nanosheet powder into a mixed solution of 6mL of ethylene glycol and 24mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 25 minutes; then adding 0.334g of cobalt chloride hexahydrate and 0.048g of aluminum chloride hexahydrate, stirring for 15 minutes, adding 0.3197g of thiourea, and stirring for 30 minutes to obtain a precursor solution;
b. transferring the precursor solution into a Teflon high-pressure kettle, heating to 160 ℃, keeping for 12 hours, taking out the product, sequentially centrifuging 3 times by using ethanol and deionized water at the rotating speed of 10500rpm, 15 minutes each time, after centrifuging and cleaning, freeze-drying in a freeze dryer at the temperature of-55 ℃ and the vacuum degree of 10Pa for 20 hours to obtain the aluminum ion doped Co 9 S 8 Composite material of/MXene heterostructure from Al-Co 9 S 8 the/MXene expression.
Comparative example 2: this comparative example is compared with example 1, with the difference that no aluminium ions are doped, and the preparation steps and parameters differ from example 1 in that the operation of step two a is replaced by the following operation: adding 60mg of MXene nanosheet powder into a mixed solution of 6mL of ethylene glycol and 24mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 25 minutes; then, 0.334g of cobalt chloride hexahydrate was added thereto, the mixture was stirred for 15 minutes, and 319.7mg of thiourea was added thereto, the mixture was stirred for 30 minutes, thereby obtaining a precursor solution. The other steps and parameters are the same as those of the example 1, and the material Co which is not doped with aluminum ions is obtained 9 S 8 /MXene。
Fig. 1 shows a scanning electron micrograph of MXene obtained in step one of this example 1, and it can be seen from fig. 1 that MXene has a distinct lamellar distribution.
Example 1 the aluminum ion obtained through step two is doped with Co 9 S 8 Al-Co composite material with/MXene heterostructure 9 S 8 The scanning electron micrograph of/MXene is shown in FIG. 2, and Al-Co can be seen from FIG. 2 9 S 8 the/MXene is distributed in a nano-sphere packing manner, the surface of the nano-sphere is rough, and successful introduction of aluminum ions is proved.
Example 1 aluminum ion Co doping obtained in step two 9 S 8 Composite material with/MXene heterostructureMaterial Al-Co 9 S 8 The XRD spectrum of/MXene is shown in figure 3, and several obvious peaks 38 degrees, 40 degrees, 47 degrees, 51 degrees and 61 degrees in figure 3 respectively represent Co 9 S 8 The (331), (420), (511), (440), and (533) crystal planes of (A) indicate Al-Co 9 S 8 Successful synthesis of/MXene.
Example 1 the aluminum ion obtained through step two is doped with Co 9 S 8 Al-Co composite material with/MXene heterostructure 9 S 8 The XPS spectrum of/MXene is shown in FIG. 4, co, al, O, C and S peaks can be seen from FIG. 4, further showing that Al-Co 9 S 8 Successful synthesis of/MXene.
Example 1 the aluminum ion obtained through step two is doped with Co 9 S 8 Al-Co composite material with/MXene heterostructure 9 S 8 The constant current charge-discharge curve (GCD) of/MXene is shown in FIG. 5. As can be seen from FIG. 5, al-Co 9 S 8 The voltage plateau of/MXene is very clear, indicating that it has pseudocapacitance, and can be calculated at a current density of 2 Ag -1 Ti Al-Co 9 S 8 The capacitance of/MXene is 1643 Cg -1 。
Example 1 the aluminum ion obtained through step two is doped with Co 9 S 8 Al-Co composite material with/MXene heterostructure 9 S 8 The rate performance graph of/MXene is shown in FIG. 6, and it can be seen from FIG. 6 that when the current density reaches 15 Ag -1 While its capacitance can be maintained at 2 Ag -1 About 70% of the total weight of Al and Co, al-Co was confirmed 9 S 8 the/MXene has excellent rate performance.
Comparative undoped aluminum ion material Co prepared from comparative example 2 9 S 8 The constant current charge-discharge curve chart of/MXene is shown in FIG. 7, and it can be seen from FIG. 7 that the current density is 2 Ag -1 Co of 9 S 8 Capacitance of/MXene 1427 Cg -1 . Co, a comparative undoped aluminum ion material 9 S 8 The rate performance graph of/MXene is shown in FIG. 8, and it can be seen from FIG. 8 that when the current density reaches 12 Ag -1 While its capacitance can only hold 2 ag -1 In the case of this, 53.5% was used. As can be seen, co is a material not doped with aluminum ions 9 S 8 The electrochemical performance of/MXene is far inferior to that of Al-Co prepared in example 1 9 S 8 the/MXene composite material.
Comparative example 3: this comparative example differs from example 1 in that the amount of aluminium ions incorporated is too low, and the procedure and parameters for the preparation differ from example 1 in that the procedure of step two a is replaced by the following procedure: adding 60mg of MXene nanosheet powder into a mixed solution of 6mL of ethylene glycol and 24mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 25 minutes; then, 0.334g of cobalt chloride hexahydrate and 0.0274g of aluminum chloride hexahydrate were added thereto and stirred for 15 minutes, and 319.7mg of thiourea was added thereto and stirred for 30 minutes, thereby obtaining a precursor solution. The other steps and parameters were the same as in example 1 to obtain aluminum ion-doped Co having a lower content of aluminum ions 9 S 8 /MXene。
Comparative example 4: the comparative example is compared with example 1, except that the amount of aluminum ions is too high, and the preparation steps and parameters are different from those of example 1 in that the operation of step two a is replaced by the following operation: adding 60mg of MXene nanosheet powder into a mixed solution of 6mL of ethylene glycol and 24mL of N, N-dimethylformamide, and carrying out ultrasonic treatment for 25 minutes; then, 0.334g of cobalt chloride hexahydrate and 0.0154g of aluminum chloride hexahydrate were added thereto and stirred for 15 minutes, and 319.7mg of thiourea was added thereto and stirred for 30 minutes, thereby obtaining a precursor solution. The other steps and parameters were the same as in example 1, to obtain aluminum ion-doped Co having a higher content of aluminum ions 9 S 8 /MXene。
Through constant current charge-discharge curve test comparison, the materials prepared in comparative example 3 and comparative example 4 have the current density of 2 Ag -1 The capacitance of each capacitor is 1308 Cg -1 And 1245C g -1 All are lower than Al-Co prepared in example 1 9 S 8 The reason for this is that, the addition of a proper amount of aluminum ions is beneficial to improve the electrochemical performance, but when the doping amount is too small, defects cannot be induced to generate, and if the doping amount is too large, the structure of the material itself is changed, so that the ion transport speed is slowed, the reaction kinetics is slowed, and the electrochemical performance is reduced.
Claims (7)
1. Aluminum ion doped Co 9 S 8 The preparation method of the/MXene heterostructure composite material is characterized by comprising the following steps:
1. preparation of MXene nanosheets:
a. adding 1g of nickel fluoride into 20mL of 9M HCl, and mixing and stirring the 9M HCl and the nickel fluoride for 25-35 minutes to obtain a mixed solution;
b. adding titanium aluminum carbide into the mixed solution, heating to 35-45 ℃ and keeping for 85-95 hours;
c. centrifuging and washing the product obtained in the step b by using 1M HCl, discarding the supernatant, centrifuging and washing the precipitate by using deionized water until the pH value of the supernatant reaches 6-8, discarding the supernatant, adding the precipitate into deionized water, performing ultrasonic treatment in an ice bath under nitrogen for 50-70 minutes, centrifuging the mixed solution, discarding the supernatant, and freeze-drying the precipitate to obtain MXene nanosheet powder;
2. aluminum doped metal sulfide/MXene Al-Co 9 S 8 Preparation of MXene:
a. adding MXene nanosheet powder into a mixed solution of ethylene glycol and N, N-dimethylformamide, and carrying out ultrasonic treatment for 20-30 minutes; then adding cobalt chloride hexahydrate and aluminum chloride hexahydrate, stirring for 10-20 minutes, adding thiourea, and stirring for 25-35 minutes to obtain a precursor solution;
b. transferring the precursor solution into a Teflon high-pressure kettle, heating to 140-180 ℃, keeping for 10-14 hours, taking out the product, sequentially centrifugally cleaning by using ethanol and deionized water, and then freeze-drying to obtain the aluminum ion doped Co 9 S 8 a/MXene heterostructure composite material.
2. The aluminum ion doped Co of claim 1 9 S 8 The preparation method of the/MXene heterostructure composite material is characterized in that the centrifugal separation in the step one c is performed for 5-10 minutes under the condition that the rotating speed is 3000-4000 rpm.
3. An aluminum ion doped Co as claimed in claim 1 or 2 9 S 8 /MXene isoThe preparation method of the texture structure composite material is characterized in that the ratio of the mass of MXene nanosheet powder to the volume of ethylene glycol in the step two a is 1g: (95-105) mL.
4. An aluminum ion doped Co according to claim 1 or 2 9 S 8 The preparation method of the/MXene heterostructure composite material is characterized in that the ratio of the mass of the MXene nanosheet powder to the volume of the N, N-dimethylformamide in the step two a is 1g: (350-450) mL.
5. An aluminum ion doped Co according to claim 1 or 2 9 S 8 The preparation method of the/MXene heterostructure composite material is characterized in that the mass ratio of MXene nanosheet powder to cobalt chloride hexahydrate in the second step a is 1: (5-7).
6. An aluminum ion doped Co as claimed in claim 1 or 2 9 S 8 The preparation method of the/MXene heterostructure composite material is characterized in that the molar ratio of cobalt chloride hexahydrate, aluminum chloride hexahydrate and thiourea in the step two a is 1: (0.1-0.2): (3-3.5).
7. An aluminum ion doped Co according to claim 1 or 2 9 S 8 The preparation method of the/MXene heterostructure composite material is characterized in that when ethanol and deionized water are used for centrifugal separation in the step two b, centrifugal treatment is carried out for 5-20 minutes under the condition that the rotating speed is 10000-11000 rpm.
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| CN117303467A (en) * | 2023-11-30 | 2023-12-29 | 河南科技学院 | Preparation method of hydroxy chloride MXene composite anode material and application of hydroxy chloride MXene composite anode material in sodium ion battery |
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| CN111599603A (en) * | 2020-05-21 | 2020-08-28 | 南京理工大学 | MXene/ZnMnNi LDH van der Waals heterostructure and preparation method and application thereof |
| WO2022032751A1 (en) * | 2020-08-10 | 2022-02-17 | 五邑大学 | Phosphorus-doped cose2/mxene composite material and preparation method therefor |
| WO2022032747A1 (en) * | 2020-08-10 | 2022-02-17 | 五邑大学 | Method for preparing sulfur-doped rese2/mxene composite material |
| CN114512653A (en) * | 2022-02-22 | 2022-05-17 | 广东工业大学 | Preparation method of nitrogen-doped MXene-loaded molybdenum disulfide composite material, product and application of product |
| CN114843510A (en) * | 2021-01-30 | 2022-08-02 | 苏州北科纳米科技有限公司 | Preparation method of metal-sulfur in-situ co-doped MXene electrode material |
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| CN111599603A (en) * | 2020-05-21 | 2020-08-28 | 南京理工大学 | MXene/ZnMnNi LDH van der Waals heterostructure and preparation method and application thereof |
| WO2022032751A1 (en) * | 2020-08-10 | 2022-02-17 | 五邑大学 | Phosphorus-doped cose2/mxene composite material and preparation method therefor |
| WO2022032747A1 (en) * | 2020-08-10 | 2022-02-17 | 五邑大学 | Method for preparing sulfur-doped rese2/mxene composite material |
| CN114843510A (en) * | 2021-01-30 | 2022-08-02 | 苏州北科纳米科技有限公司 | Preparation method of metal-sulfur in-situ co-doped MXene electrode material |
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| CN117303467A (en) * | 2023-11-30 | 2023-12-29 | 河南科技学院 | Preparation method of hydroxy chloride MXene composite anode material and application of hydroxy chloride MXene composite anode material in sodium ion battery |
| CN117303467B (en) * | 2023-11-30 | 2024-03-22 | 河南科技学院 | Preparation method of hydroxy chloride MXene composite anode material and application of hydroxy chloride MXene composite anode material in sodium ion battery |
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