CN113241259B - Potassium ion capacitor and preparation method thereof - Google Patents
Potassium ion capacitor and preparation method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 title claims abstract description 60
- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 39
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000007772 electrode material Substances 0.000 claims abstract description 34
- 239000002131 composite material Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 239000004744 fabric Substances 0.000 claims abstract description 16
- 239000002135 nanosheet Substances 0.000 claims abstract description 16
- 238000000151 deposition Methods 0.000 claims abstract description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000008055 phosphate buffer solution Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002994 raw material Substances 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000004202 carbamide Substances 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 230000008021 deposition Effects 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000008363 phosphate buffer Substances 0.000 claims description 3
- 238000005137 deposition process Methods 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims 3
- 229910021641 deionized water Inorganic materials 0.000 claims 3
- 238000004146 energy storage Methods 0.000 abstract description 4
- 229910052961 molybdenite Inorganic materials 0.000 abstract 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- 239000000243 solution Substances 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- 230000001351 cycling effect Effects 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 102000004310 Ion Channels Human genes 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000013508 migration Methods 0.000 description 3
- 230000005012 migration Effects 0.000 description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920002799 BoPET Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- QDAYJHVWIRGGJM-UHFFFAOYSA-B [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Mo+4].[Mo+4].[Mo+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QDAYJHVWIRGGJM-UHFFFAOYSA-B 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
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- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000004434 sulfur atom Chemical group 0.000 description 1
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Images
Classifications
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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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- 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
- H01G11/46—Metal oxides
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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
- H01G11/84—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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- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to a potassium ion capacitor and a preparation method thereof, and belongs to the technical field of energy storage of super capacitors. The potassium ion capacitor comprises MoPO/MoS 2 Composite electrode material, the MoPO/MoS 2 The composite electrode material is prepared by the following method: with (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O、CH 3 CSNH 2 Urea, ethanol and water are used as raw materials, and MoS2 nanosheets are prepared on carbon cloth through a hydrothermal method; with the MoS 2 Nanosheet, phosphate buffer solution, (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Preparing MoPO/MoS by using O as raw material and adopting constant current deposition method 2 A composite electrode material. The potassium ion capacitor is a symmetrical super capacitor, the specific capacity is 150.5F/g, the energy density can reach 52.6Wh/kg, the cycle stability is good, and the capacity can still be kept 90% after 26000 cycles under the current density of 1A/g.
Description
Technical Field
The invention relates to the technical field of super capacitor energy storage, in particular to a potassium ion capacitor and a preparation method thereof.
Background
The super capacitor is a novel energy storage device following the traditional capacitor and the rechargeable battery, and has the advantages of high power density, long cycle life, high charging and discharging speed, high safety and the like. The metal ion capacitor formed by the battery-type anode (providing pseudo-capacitance) and the capacitor-type cathode (providing electric double layer capacitance) has high energy density and high power density, but is hindered in practical application due to the mismatch of dynamics of the anode and cathode materials, so that it is very important to find a suitable electrode material.
The electrode material is an important constituent part in the super capacitor and is an important factor influencing the comprehensive performance of the device. Existing research has shown that two-dimensional (2D) grading with large layer spacing is achieved by designThe structural material can improve various performances of the super capacitor. And MoS 2 The 2D layered material is composed of sheets formed by S-Mo-S, S atoms and Mo atoms form a sandwich structure, and the layers are connected together through weak van der Waals force, and simultaneously have double-layer capacitance and pseudo-capacitance behaviors. When the material is assembled into a symmetrical device, the problem of mismatching of dynamics of positive and negative electrode materials of the metal ion capacitor can be effectively solved, and the material has higher theoretical capacity and is an excellent energy storage material. And the radius of potassium ions in the potassium ion capacitor is
Can insert MoS 2 The intermediate layer (about 0.62 nm) of (a) provides a portion of the pseudocapacitance. However, because of MoS 2 Is conventionally in the 2H (hexagonal symmetry) semiconductor phase, has poor conductivity, and is K + Continuous intercalation/deintercalation in the electrode material, easily destroying MoS 2 Thus causing the fragmentation and collapse of the sheet material.
Disclosure of Invention
In view of the above technical problems, the present invention provides a potassium ion capacitor, which comprises MoPO/MoS 2 Composite electrode material, said MoPO/MoS 2 The composite electrode material is prepared by the following method:
preparation of MoS 2 Nanosheet: with (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O、CH 3 CSNH 2 Urea, ethanol and water are used as raw materials, and MoS is prepared on carbon cloth by a hydrothermal method 2 A nanosheet;
preparation of MoPO/MoS 2 Composite electrode material: with the MoS 2 Nanosheet, phosphate buffer solution, (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Preparing MoPO/MoS by constant current deposition method by using O as raw material 2 A composite electrode material.
The inventor easily destroys MoS on the potassium ion capacitor 2 The microstructure of (A) and the causes of the breakage and collapse of the sheet-like material were investigatedThe existing research shows that MoS 2 The electrochemical properties of which can be changed by combining with other conductive materials, the present inventors have found that molybdenum phosphate (MoPO) has stable chemical properties and excellent conductivity, and the structure includes MoO 6 Octahedron and PO 4 Tetrahedron, which forms open ion channel to ensure rapid ion migration, and can be inserted/extracted into/from aqueous potassium ion capacitor to realize multiple electron transfer reaction without destruction of MoS 2 A graphene-like layered structure of an electrode material.
The potassium ion capacitor is a symmetrical super capacitor, the specific capacity is 150.5F/g, the energy density can reach 52.6Wh/kg, the cycle stability is good, and the capacity can still be kept 90% after 26000 cycles under the current density of 1A/g. The potassium ion capacitor comprises the MoPO/MoS 2 Composite electrode material, said MoPO/MoS 2 The composite electrode material is prepared by a constant current deposition method, can form an open ion channel, ensures the rapid migration of ions, and is embedded/de-embedded in the aqueous potassium ion capacitor without damaging MoS 2 The graphene-like layered structure of the electrode material has the advantages of adsorption capacitance, embedded pseudo capacitance, high specific capacity, high energy density and excellent cycling stability, and the specific capacity is 552.8F/g under the current density of 1A/g.
In one embodiment, the (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O、CH 3 CSNH 2 The dosage ratio of the urea is 0.005 +/-0.002 mol:0.07 +/-0.02 mol:0.03 +/-0.01 mol, the volume ratio of the water to the ethanol is 20-40 ml: 0-20ml, the phosphate buffer solution and the (NH) are added 4 ) 6 Mo 7 O 24 ·4H 2 The dosage proportion of O is 5-30ml to 0.003-0.025mol. The precursor solution prepared from the raw materials can better synthesize MoPO/MoS 2 A composite material.
In one embodiment, the (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O、CH 3 CSNH 2 The dosage ratio of the urea is 0.005mol:0.07mol:0.03mol, the volume ratio of the water to the ethanol is 20ml:20ml, and the phosphoric acid isSalt buffer, (NH) 4 ) 6 Mo 7 O 24 ·4H 2 The dosage ratio of O is 20ml to 0.003mol. Preparing a precursor solution by adopting the raw materials with the dosage to generate MoS 2 Nanosheets capable of retaining MoS 2 Original layered structure, improved MoS 2 And contributes to the advantage of improving the cycling stability of the material.
In one embodiment, the preparation of MoS 2 The reaction temperature of the nano-sheets is 140-200 ℃, and the reaction time is 12-24 hours. MoS obtained by adopting the reaction conditions 2 The nano-sheet has better crystal structure and crystal form.
In one embodiment, the preparation of MoS 2 The reaction temperature of the nano-sheets is 200 ℃, and the reaction time is 18 hours. By adopting the reaction conditions, moS can be enabled 2 The nano-sheets uniformly grow on the carbon cloth.
In one embodiment, the pH of the phosphate buffer is 2.5-8.0, and the constant current deposition method has a current density of 1-3mA/cm 2 The deposition time is 300-1200 seconds. The MoPO/MoS can be well controlled by adopting the reaction conditions 2 The morphology of (2).
In one embodiment, the pH of the phosphate buffer is 5.8 and the constant current deposition process has a current density of 2mA/cm 2 The deposition time was 900 seconds. By adopting the reaction conditions, moPO/MoS with special nano structure can be obtained 2 The composite electrode material has higher specific capacity, and can simultaneously have an adsorption capacitor and an embedded pseudo capacitor.
In one embodiment, the preparation step of the potassium ion capacitor comprises: the MoPO/MoS 2 The composite electrode material is assembled in a 3mol/L KCl electrolyte solution.
In one embodiment, the carbon cloth is soaked in concentrated nitric acid for 1-3 days. By adopting the pretreatment, the hydrophilicity of the carbon cloth can be enhanced, so that MoS can be obtained 2 The nano-sheet is better loaded on the carbon cloth by a hydrothermal method.
The invention also provides the MoPO/MoS 2 Composite electrode materialThe specific capacity is high and is 552.8F/g under the current density of 1A/g; meanwhile, the capacitor has adsorption capacitance and embedded pseudo capacitance, and is suitable for potassium ion capacitors.
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a potassium ion capacitor, which is a symmetrical super capacitor, has the specific capacity of 150.5F/g, the energy density of 52.6Wh/kg and good cycling stability, and the capacity can still be kept at 90% after the capacitor is cycled for 26000 times under the current density of 1A/g. The potassium ion capacitor comprises MoPO/MoS 2 Composite electrode material, said MoPO/MoS 2 The composite electrode material is prepared by a constant current deposition method, can form an open ion channel, ensures the rapid migration of ions, and is embedded/de-embedded in the aqueous potassium ion capacitor without damaging MoS 2 Graphene-like layered structures of electrode materials. Meanwhile, the capacitor has an adsorption capacitor and an embedded pseudo capacitor, and also has higher specific capacity, energy density and excellent cycling stability, and the specific capacity is 552.8F/g under the current density of 1A/g.
Drawings
FIG. 1 shows MoS 2 SEM pictures of the material;
FIG. 2 shows MoPO/MoS 2 SEM images of the material;
FIG. 3 shows Carbon Cloth (CC) and MoS 2 [ solution ] CC and MoS 2 XRD pattern of/MoPO;
FIG. 4 shows MoPO/MoS 2 The contribution ratio of the composite electrode material adsorption capacitance and the embedded pseudo-capacitance is calculated;
FIG. 5 is a constant current charge-discharge diagram (GCD) of a potassium ion capacitor;
FIG. 6 is a plot of the specific capacity of a potassium ion capacitor;
FIG. 7 is a Cyclic Voltammogram (CV) of a potassium ion capacitor;
FIG. 8 is a Ragon diagram of a potassium ion capacitor;
fig. 9 is a graph of the cycling stability of a potassium ion capacitor.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
Defining:
the hydrothermal method of the invention refers to a method for preparing a material by dissolving and recrystallizing powder in a sealed pressure vessel by using water as a solvent.
Galvanostatic deposition methods refer to methods in which the deposition reaction occurs by applying a constant current of a certain magnitude.
Reagents, materials and equipment used in the present example are all commercially available sources unless otherwise specified; unless otherwise specified, all the experimental methods are routine in the art.
Example 1
Preparation of MoPO/MoS 2 A composite electrode material.
1. Soaking the carbon cloth in concentrated nitric acid, standing for one day, cleaning and drying for later use;
2. according to (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O∶CH 3 CSNH 2 Preparing a precursor solution according to the ratio of 0.005mol to 0.03mol to 0.07mol;
3. placing the carbon cloth treated in the step 1 in the precursor solution, adopting a hydrothermal method, wherein the reaction temperature is 200 ℃, the reaction time is 18h, and growing MoS on the carbon cloth 2 Cooling the materials to room temperature after the reaction is finished, taking out the carbon cloth, and cleaning and drying the carbon cloth for later use;
4. according to the ratio of phosphate buffer solution to water to (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Preparing a precursor solution with the proportion of O of 20ml to 80ml to 0.003mol, wherein the pH value of the phosphate buffer solution is 5.8, stirring for 2 hours, pouring the solution into a three-electrode tank, and adding the solution at the rate of 2mA/cm 2 And (4) carrying out constant current deposition for 900s to obtain the product.
MoPO/MoS prepared as described above 2 The composite electrode material has higher specific capacity, and the specific capacity is 552.8F/g under the current density of 1A/g.
The MoS synthesized on the carbon cloth 2 The microscopic morphology of the material is shown in FIG. 1; synthetic MoPO/MoS 2 The micro-topography of the composite electrode material is shown in FIG. 2; carbon Cloth (CC), synthetic MoS 2 Material (MoS) 2 /CC) and synthetic MoPO/MoS 2 XRD of the composite electrode material is shown in fig. 3.
Example 2
And preparing a symmetrical potassium ion capacitor.
MoPO/MoS prepared in example 1 2 The composite electrode material is assembled into a symmetrical potassium ion capacitor in a 3mol/L KCl electrolyte solution, and the assembly conditions are as follows: the device is composed of MoPO/MoS 2 Electrode (1 x 2cm) 2 ) As positive and negative electrodes and a piece of cellulose paper (1.5 x 2.5 cm) 2 ) The electrolyte is assembled as a separator, and 3mol/L KCl is used as the electrolyte. The device was then encapsulated using a flexible plastic PET film and connected to each electrode edge with two copper chips.
Example 3
Analysis of MoPO/MoS 2 Electrical properties of the composite electrode material.
Analysis of MoPO/MoS prepared in example 1 by kinetics 2 The contribution ratio of the composite electrode material, the adsorption capacitance and the embedded pseudo capacitance is analyzed under the following conditions: to study the MoPO/MoS 2 Capacitive contribution of the electrode according to i = a × v b The equation analyzes the relationship between current (i) and scan rate (v), and the relationship of anode and cathode currents (ia and ic) is logarithmic. At a potential of-1.0V vs. SCE, moPO/MoS was determined from currents obtained at different scanning rates of the CV diagram 2 Whether the capacitance of the electrode comes from adsorption or intercalation.
Analysis ofThe results are shown in FIG. 4: the MoPO/MoS 2 The composite electrode material has both adsorption capacitance and embedded pseudo capacitance, and is suitable for potassium ion capacitors.
Example 4
And detecting the electrical property of the symmetrical potassium ion capacitor.
The symmetric potassium ion capacitor prepared in example 2 was tested under the following conditions: 3mol/L potassium chloride (KCl, 99.5%) aqueous solution is used as electrolyte, and the current density is 2A g -1 To 10 ag -1 Constant current charge-discharge curve (GCD) and scanning speed of 10mV s -1 To 50mV s -1 Cyclic Voltammetry (CV).
And (3) detection results: the specific capacity of the symmetrical potassium ion capacitor is 150.5F/g, the energy density of the symmetrical potassium ion capacitor can reach 52.6Wh/kg, the symmetrical potassium ion capacitor has good circulation stability, and the capacity can still be kept 90% after 26000 times of circulation under the current density of 1A/g. The constant current charge-discharge diagram of the symmetric potassium ion capacitor is shown in fig. 5; the specific capacity of the capacitor is shown in fig. 6; the cyclic voltammogram of this capacitor is shown in FIG. 7; the Ragon diagram of the capacitor is shown in FIG. 8; the cycling stability of this capacitor is shown in figure 9.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent should be subject to the appended claims.
Claims (7)
1. A potassium ion capacitor is characterized by comprising MoPO/MoS 2 Composite electrodeMaterial, said MoPO/MoS 2 The composite electrode material is prepared by the following method:
preparation of MoS 2 Nanosheet: with (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O、CH 3 CSNH 2 Urea, absolute ethyl alcohol and deionized water are used as raw materials, and MoS is prepared on carbon cloth by a hydrothermal method 2 Nanosheets; said (NH) 4 ) 6 Mo 7 O 24 ·4H 2 O、CH 3 CSNH 2 The dosage proportion of the urea is 0.005 +/-0.002 mol:0.07 +/-0.02 mol:0.03 +/-0.01 mol, and the volume ratio of the deionized water to the absolute ethyl alcohol is 20-40 ml: 0-20ml; the preparation of MoS 2 The reaction temperature of the nano-sheets is 140-200 ℃, and the reaction time is 12-24 hours;
preparation of MoPO/MoS 2 Composite electrode material: with the MoS 2 Nanosheet, phosphate buffer solution, (NH) 4 ) 6 Mo 7 O 24 ·4H 2 Preparing MoPO/MoS by using O as raw material and adopting constant current deposition method 2 A composite electrode material; the phosphate buffer solution, (NH) 4 ) 6 Mo 7 O 24 ·4H 2 The dosage proportion of O is 5-30ml to 0.003-0.025mol; the pH value of the phosphate buffer solution is 2.5-8.0, and the current density of the constant current deposition method is 1-3mA/cm 2 The deposition time is 300-1200 seconds.
2. The potassium ion capacitor of claim 1, wherein the (NH) is 4 ) 6 Mo 7 O 24 ·4H 2 O、CH 3 CSNH 2 The dosage ratio of the urea is 0.005mol:0.07mol:0.03mol, the volume ratio of the deionized water to the absolute ethyl alcohol is 20ml:20ml, the phosphate buffer solution and the (NH) are added 4 ) 6 Mo 7 O 24 ·4H 2 The dosage ratio of O is 20ml to 0.003mol.
3. The potassium ion capacitor of claim 1, wherein the preparation of MoS is performed 2 The reaction temperature of the nano-sheets is 200 ℃, and the reaction is carried outThe time period required was 18 hours.
4. The potassium ion capacitor as claimed in claim 1, wherein the phosphate buffer has a pH of 5.8 and the galvanostatic deposition process has a current density of 2mA/cm 2 The deposition time was 900 seconds.
5. The potassium ion capacitor of claim 1, wherein the preparing step comprises: the MoPO/MoS 2 The composite electrode material is assembled in a 3mol/L KCl electrolyte solution.
6. The potassium ion capacitor of any one of claims 1-5, wherein the carbon cloth is soaked in concentrated nitric acid for 1-3 days.
7. MoPO/MoS according to claim 1 2 A composite electrode material.
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