CN114974931A - Preparation of manganese-based high-voltage window electrode material and super capacitor energy storage device - Google Patents
Preparation of manganese-based high-voltage window electrode material and super capacitor energy storage device Download PDFInfo
- Publication number
- CN114974931A CN114974931A CN202210614131.3A CN202210614131A CN114974931A CN 114974931 A CN114974931 A CN 114974931A CN 202210614131 A CN202210614131 A CN 202210614131A CN 114974931 A CN114974931 A CN 114974931A
- Authority
- CN
- China
- Prior art keywords
- acc
- mno
- electrode material
- carbon cloth
- electrolyte
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000007772 electrode material Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000003990 capacitor Substances 0.000 title claims description 22
- 239000011572 manganese Substances 0.000 title abstract description 14
- 229910052748 manganese Inorganic materials 0.000 title abstract description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title abstract description 3
- 238000004146 energy storage Methods 0.000 title description 9
- 238000000034 method Methods 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002848 electrochemical method Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 59
- 239000004744 fabric Substances 0.000 claims description 46
- 239000003792 electrolyte Substances 0.000 claims description 42
- 229910052799 carbon Inorganic materials 0.000 claims description 36
- JFDZBHWFFUWGJE-UHFFFAOYSA-N benzonitrile Chemical compound N#CC1=CC=CC=C1 JFDZBHWFFUWGJE-UHFFFAOYSA-N 0.000 claims description 30
- 239000013543 active substance Substances 0.000 claims description 27
- 238000004070 electrodeposition Methods 0.000 claims description 13
- 239000000758 substrate Substances 0.000 claims description 11
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 239000011245 gel electrolyte Substances 0.000 claims description 10
- 239000007773 negative electrode material Substances 0.000 claims description 10
- 239000007774 positive electrode material Substances 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 230000004913 activation Effects 0.000 claims description 9
- 238000005303 weighing Methods 0.000 claims description 9
- 229910021607 Silver chloride Inorganic materials 0.000 claims 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 17
- 230000007547 defect Effects 0.000 abstract description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract 1
- 238000001994 activation Methods 0.000 abstract 1
- 229910052751 metal Inorganic materials 0.000 abstract 1
- 239000002184 metal Substances 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 229910052707 ruthenium Inorganic materials 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000011734 sodium Substances 0.000 description 31
- 238000002484 cyclic voltammetry Methods 0.000 description 10
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000010586 diagram Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000009830 intercalation Methods 0.000 description 2
- 230000002687 intercalation Effects 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
Images
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
The invention relates to preparation of a manganese-based high-performance electrode material and assembly of an asymmetric supercapacitor device, in particular to MnO 2 The electrode material prepared by the electrochemical method is simple to synthesize, and the electrode material Na-MnO with a wide voltage window is formed through the electrochemical activation process 2 @ ACC, in Na-MnO 2 @ ACC is positive electrode, Fe 2 O 3 @ ACC has assembled asymmetric ultracapacitor device for the negative pole, belongs to chemical technical field. The invention has the advantages that 1, Mn is used as a raw material, water is used as a solvent, the price is low, and the defect that the price of metal ruthenium is high can be effectively avoided; 2. the electrochemical method is adopted for preparation, the process is simple and easy to prepare, and the technical difficulty is reduced; 3. the prepared electrode material has a wide voltage window and the assembled device has a wide voltage windowThe voltage window has good application prospect at the same time. In short, the prepared material has high cost performance and good electrochemical performance.
Description
Technical Field
The invention relates to preparation of a super capacitor electrode material, in particular to preparation of a high-performance anode material and assembly of a high-voltage window asymmetric super capacitor energy storage device, and belongs to the technical field of chemistry.
Background
With the continuous development of scientific technology, the consumption speed of non-renewable resources such as coal, oil, natural gas and the like is faster and faster, and although the new energy sources such as wind energy, solar energy, tidal energy and the like relieve the requirement of people on the energy sources, the exploration and storage of the new energy sources are difficult problems which are urgently needed to overcome. In addition, new electronic products such as mobile phones, watches, cameras and the like are updated, and the requirements on energy storage devices are also improved.
Batteries and supercapacitors are the main two energy storage devices. As main energy storage devices, the two have the advantages respectively, the battery has high energy density and is widely applied, but potential safety hazards exist in the using process. Compared with a battery, the super capacitor has the advantages of large capacitance, high charging and discharging speed, good cycling stability, environmental protection, safety and the like, and can be widely applied to various industries. Therefore, the focus of research should be on the development of supercapacitors, however the low energy density limits their further applications.
Electrode materials are the most critical factors affecting the performance of the supercapacitor, and commonly used electrode materials include carbon materials (graphene, carbon nanotubes, carbon fibers and the like), metal oxides (ruthenium oxide, iron oxide, manganese oxide and the like) and polymers (polyaniline, polypyrrole and the like). Among them, ruthenium oxide is a noble metal material, and has disadvantages of high price and environmental pollution, so that it cannot be widely used. The manganese dioxide material used as a substitute is low in price, simple to prepare and environment-friendly, so that a large amount of research and application are realized. It should be noted that, growing the electrode material directly on the current collector (such as carbon cloth and nickel foam, etc.) is a good choice, because the problems of resistance increase and inactive area increase caused by the binder can be avoided, so the binderless self-supporting electrode can significantly improve the conductivity of the electrode, shorten the electron transmission path and ion diffusion distance in the reaction process of the electrode material, and further improve the charge storage capacity. Therefore, designing and synthesizing multi-component electrode materials and forming the self-supporting electrode material without the adhesive is a key step for preparing the high-performance super-capacitor energy storage device.
Common methods for synthesizing manganese dioxide include hydrothermal method, solid phase method, sol-gel method and electrodeposition method. The electrodeposition method has the advantages of short time consumption, simple operation and the like. The current manganese dioxide electrode material has the defects of poor conductivity, low material utilization rate and the like, so that the capacitance is far lower than the theoretical capacitance, and the manganese dioxide material needs to be further processed to improve the material utilization rate and increase the capacitance. The ion embedding strategy is an effective method for improving the utilization rate of materials, and can obtain electrode materials with large capacitance and high voltage windows. From the formula of energy density (E-1/2 CV) 2 ) It can be known that the voltage window and the energy density are in a quadratic relation, so that constructing an electrode material into an asymmetric supercapacitor device with a high voltage window is an important method for improving the performance.
Disclosure of Invention
The invention aims to provide a method for preparing manganese dioxide material, which has simple process and is environment-friendly; forming a high voltage window positive electrode material through an ion embedding strategy; assembled high-performance high-voltage window asymmetric supercapacitor device
In order to achieve the above object, the present invention adopts the following technical solutions:
the method specifically comprises the following steps:
step 1: pretreating the purchased Carbon Cloth (CC) to obtain Activated Carbon Cloth (ACC);
step 2: mn (CH) is added at room temperature 3 COO) 2 ·4H 2 O and 4- (1H-imidazo [4, 5-f)][1,10]Mixing phenanthroline-2-yl) benzonitrile with deionized water to obtain an electrolyte;
step 3: placing ACC serving as a working electrode in electrolyte, and performing electrodeposition at 0.5-2V to form anchored MnO on an ACC substrate 2 Electrode material of (2), named MnO 2 @ACC；
Step 4: MnO of 2 @ ACC as working electrode, in Na 2 SO 4 Carrying out electrochemical activation in electrolyte to obtain Na-MnO 2 @ ACC electrode material.
Step 5: adding Na-MnO 2 @ ACC isPositive electrode material, Fe 2 O 3 With @ ACC as negative electrode material in Na 2 SO 4 Electrolyte or PVA/Na 2 SO 4 And matching the asymmetric super capacitor in the gel electrolyte.
The invention has the advantages that:
(1) the electrode material prepared by electrodeposition has the advantages of simple process, loose condition requirements, low cost, good repeatability, no environmental pollution and capability of mass production;
(2) the carbon cloth grows on the carbon cloth substrate in situ, so that the resistance between the active material and the substrate is reduced;
(3) the prepared material is subjected to ion embedding by an electrochemical method to obtain high capacitance and a wide voltage window;
(4) the assembled asymmetric super capacitor device has a wider voltage window and good application;
drawings
FIG. 1 is MnO 2 @ ACC and Na-MnO 2 The XRD pattern of @ ACC;
FIG. 2 is MnO 2 SEM picture of @ ACC;
FIG. 3 shows Na-MnO 2 SEM picture of @ ACC;
FIG. 4 shows Na-MnO 2 TEM image of @ ACC;
FIG. 5 shows MnO 2 @ ACC and Na-MnO 2 XPS plots of @ ACC;
FIG. 6 shows Na-MnO 2 Electrochemical Cyclic Voltammetry (CV) curves of @ ACC;
FIG. 7 shows Na-MnO 2 Electrochemical constant current charge and discharge (GCD) curve of @ ACC;
FIG. 8 shows Na-MnO 2 Electrochemical rate performance graph of @ ACC;
FIG. 9 shows Na-MnO 2 Electrochemical cycling stability plot of @ ACC;
FIG. 10 is a supercapacitor device electrochemical Cyclic Voltammetry (CV) curve;
FIG. 11 is a graph of electrochemical constant current charging and discharging (GCD) of a supercapacitor device;
FIG. 12 is a graph of electrochemical rate performance of a supercapacitor device;
FIG. 13 is a graph of electrochemical Ragon for a supercapacitor device;
fig. 14 is a diagram of a practical application of the supercapacitor device.
Detailed Description
The invention is described in detail below with reference to the figures and the embodiments.
Example 1:
step 1: pretreating the purchased Carbon Cloth (CC) to obtain Activated Carbon Cloth (ACC);
step 2: 0.01M Mn (CH) at room temperature 3 COO) 2 ·4H 2 O and 0.001M 4- (1H-imidazo [4, 5-f)][1,10]Mixing phenanthroline-2-yl) benzonitrile with deionized water to obtain an electrolyte;
step 3: ACC as a working electrode was placed in the electrolyte and electrodeposition was carried out at 0.5V for 30 minutes to form anchored MnO on the ACC substrate 2 Electrode material of (2), named MnO 2 @ACC；
Step 4: MnO of 2 @ ACC as working electrode, in Na 2 SO 4 Carrying out electrochemical activation in electrolyte to obtain Na-MnO 2 @ ACC electrode material;
step 5: adding Na-MnO 2 @ ACC as positive electrode material, Fe 2 O 3 @ ACC as negative electrode material in Na 2 SO 4 Electrolyte or PVA/Na 2 SO 4 The gel electrolyte is matched with an asymmetric super capacitor.
The mass of the active substance can be determined by treating the carbon cloth loaded with the active substance with acid and measuring the mass difference between the carbon cloth and the active substance before and after weighing.
Example 2:
step 1: pretreating the purchased Carbon Cloth (CC) to obtain Activated Carbon Cloth (ACC);
step 2: 0.03M Mn (CH) at room temperature 3 COO) 2 ·4H 2 O and 0.003M 4- (1H-imidazo [4, 5-f)][1,10]Mixing phenanthroline-2-yl) benzonitrile with deionized water to obtain an electrolyte;
step 3: ACC as a working electrode was placed in an electrolyte and electrodeposition was carried out at 0.8V for 40 minutes to form anchoring Mn on the ACC substrateO 2 Electrode material of (2), named MnO 2 @ACC；
Step 4: MnO of 2 @ ACC as working electrode, in Na 2 SO 4 Carrying out electrochemical activation in electrolyte to obtain Na-MnO 2 @ ACC electrode material;
step 5: adding Na-MnO 2 @ ACC as positive electrode material, Fe 2 O 3 @ ACC as negative electrode material in Na 2 SO 4 Electrolyte or PVA/Na 2 SO 4 The gel electrolyte is matched with an asymmetric super capacitor.
The mass of the active substance can be determined by treating the carbon cloth loaded with the active substance with acid and measuring the mass difference between the carbon cloth and the active substance before and after weighing.
Example 3:
step 1: pretreating the purchased Carbon Cloth (CC) to obtain Activated Carbon Cloth (ACC);
step 2: 0.05M Mn (CH) at room temperature 3 COO) 2 ·4H 2 O and 0.005M 4- (1H-imidazo [4, 5-f)][1,10]Mixing phenanthroline-2-yl) benzonitrile with deionized water to obtain an electrolyte;
step 3: ACC as a working electrode was placed in the electrolyte and electrodeposition was carried out at 1V for 30 minutes to form anchored MnO on the ACC substrate 2 Electrode material of (2), named MnO 2 @ACC；
Step 4: MnO of 2 @ ACC as working electrode, in Na 2 SO 4 The electrolyte is electrochemically activated to obtain Na-MnO 2 @ ACC electrode material;
step 5: adding Na-MnO 2 @ ACC as positive electrode material, Fe 2 O 3 @ ACC as negative electrode material in Na 2 SO 4 Electrolyte or PVA/Na 2 SO 4 And matching the asymmetric super capacitor in the gel electrolyte.
The mass of the active substance can be determined by treating the carbon cloth loaded with the active substance with acid and measuring the mass difference between the carbon cloth and the active substance before and after weighing.
Example 4:
step 1: pretreating the purchased Carbon Cloth (CC) to obtain Activated Carbon Cloth (ACC);
Step2: 0.08M Mn (CH) at room temperature 3 COO) 2 ·4H 2 O and 0.008M 4- (1H-imidazo [4, 5-f)][1,10]Mixing phenanthroline-2-yl) benzonitrile with deionized water to obtain an electrolyte;
step 3: ACC as a working electrode was placed in the electrolyte and electrodeposition was carried out at 1.3V for 30 minutes to form anchored MnO on the ACC substrate 2 Electrode material of (2), named MnO 2 @ACC；
Step 4: MnO of 2 @ ACC as working electrode, in Na 2 SO 4 Carrying out electrochemical activation in electrolyte to obtain Na-MnO 2 @ ACC electrode material;
step 5: adding Na-MnO 2 @ ACC as positive electrode material, Fe 2 O 3 With @ ACC as negative electrode material in Na 2 SO 4 Electrolyte or PVA/Na 2 SO 4 The gel electrolyte is matched with an asymmetric super capacitor.
The mass of the active substance can be determined by treating the carbon cloth loaded with the active substance with acid and measuring the mass difference between the carbon cloth and the active substance before and after weighing.
Example 5:
step 1: pretreating the purchased Carbon Cloth (CC) to obtain Activated Carbon Cloth (ACC);
step 2: 0.1M Mn (CH) at room temperature 3 COO) 2 ·4H 2 O and 0.01M 4- (1H-imidazo [4, 5-f)][1,10]Mixing phenanthroline-2-yl) benzonitrile with deionized water to obtain an electrolyte;
step 3: ACC as a working electrode was placed in the electrolyte and electrodeposition was carried out at 1.5V for 20 minutes to form anchored MnO on the ACC substrate 2 Electrode material of (2), named MnO 2 @ACC；
Step 4: MnO of 2 @ ACC as working electrode, in Na 2 SO 4 Carrying out electrochemical activation in electrolyte to obtain Na-MnO 2 @ ACC electrode material;
step 5: adding Na-MnO 2 @ ACC as positive electrode material, Fe 2 O 3 @ ACC as negative electrode material in Na 2 SO 4 Electrolyte or PVA/Na 2 SO 4 The gel electrolyte is matched with an asymmetric super capacitor.
The mass of the active substance can be determined by treating the carbon cloth loaded with the active substance with acid and measuring the mass difference between the carbon cloth and the active substance before and after weighing.
Example 6:
step 1: pretreating the purchased Carbon Cloth (CC) to obtain Activated Carbon Cloth (ACC);
step 2: 0.15M Mn (CH) at room temperature 3 COO) 2 ·4H 2 O and 0.015M 4- (1H-imidazo [4, 5-f)][1,10]Mixing phenanthroline-2-yl) benzonitrile with deionized water to obtain an electrolyte;
step 3: ACC as a working electrode was placed in the electrolyte and electrodeposition was carried out at 1.7V for 20 minutes to form anchored MnO on the ACC substrate 2 Electrode material of (2), named MnO 2 @ACC；
Step 4: MnO of 2 @ ACC as working electrode, in Na 2 SO 4 Performing electrochemical activation in electrolyte to obtain Na-MnO 2 @ ACC electrode material;
step 5: adding Na-MnO 2 @ ACC as positive electrode material, Fe 2 O 3 @ ACC as negative electrode material in Na 2 SO 4 Electrolyte or PVA/Na 2 SO 4 The gel electrolyte is matched with an asymmetric super capacitor.
The mass of the active substance can be determined by treating the carbon cloth loaded with the active substance with acid and measuring the mass difference between the carbon cloth and the active substance before and after weighing.
Example 7:
step 1: pretreating the purchased Carbon Cloth (CC) to obtain Activated Carbon Cloth (ACC);
step 2: 0.18M Mn (CH) at room temperature 3 COO) 2 ·4H 2 O and 0.018M 4- (1H-imidazo [4, 5-f)][1,10]Mixing phenanthroline-2-yl) benzonitrile with deionized water to obtain an electrolyte;
step 3: ACC as a working electrode was placed in the electrolyte and electrodeposition was carried out at 1.8V for 30 minutes to form anchored MnO on the ACC substrate 2 Electrode material of (2), named MnO 2 @ACC；
Step 4: MnO of 2 @ ACC as working electrode, in Na 2 SO 4 Obtaining Na-MnO by electrochemical activation in electrolyte 2 @ ACC electrode material;
step 5: adding Na-MnO 2 @ ACC as positive electrode material, Fe 2 O 3 @ ACC as negative electrode material in Na 2 SO 4 Electrolyte or PVA/Na 2 SO 4 The gel electrolyte is matched with an asymmetric super capacitor.
The mass of the active substance can be determined by treating the carbon cloth loaded with the active substance with acid and measuring the mass difference between the carbon cloth and the active substance before and after weighing.
Example 8:
step 1: pretreating the purchased Carbon Cloth (CC) to obtain Activated Carbon Cloth (ACC);
step 2: 0.2M Mn (CH) at room temperature 3 COO) 2 ·4H 2 O and 0.02M 4- (1H-imidazo [4, 5-f)][1,10]Phenanthroline-2-yl) benzonitrile and deionized water are mixed to obtain an electrolyte;
step 3: ACC as a working electrode was placed in the electrolyte and electrodeposition was carried out at 2V for 20 minutes to form anchored MnO on the ACC substrate 2 Electrode material of (2), named MnO 2 @ACC；
Step 4: MnO of 2 @ ACC as working electrode, in Na 2 SO 4 Obtaining Na-MnO by electrochemical activation in electrolyte 2 @ ACC electrode material;
step 5: adding Na-MnO 2 @ ACC as positive electrode material, Fe 2 O 3 @ ACC as negative electrode material in Na 2 SO 4 Electrolyte or PVA/Na 2 SO 4 The gel electrolyte is matched with an asymmetric super capacitor.
The mass of the active substance can be determined by treating the carbon cloth loaded with the active substance with acid and measuring the mass difference between the carbon cloth and the active substance before and after weighing.
Examples of the applications
To verify the electrochemical performance of the electrode material, the following series of tests were made:
the super capacitor is tested, and the multiplying power performance graph shows that the super capacitor has large specific capacitance and the current density is 1mA cm -2 The capacitance is 677mF cm -2 Wide voltage window2.5V. As can be seen from the cycling stability chart, the current density was 10mA cm -2 After 10000 cycles of time cycle, the capacity retention rate is 81%. The energy density of the super capacitor is 587 mu Wh cm -2 The time power density is 1.25mW cm -2 . It may last for about 24 hours to light up the electronic watch.
In conclusion, the electrode material prepared by the method and the assembled asymmetric supercapacitor have a high voltage window of 2.5V, high specific capacitance, excellent cycling stability and good practical application prospect.
The above embodiments are only preferred embodiments of the present invention, and do not limit the present invention.
We performed some relevant tests on the products of the examples, as follows:
FIG. 1 is MnO 2 @ ACC and Na-MnO 2 XRD pattern of @ ACC, by intercalation of sodium ions, conversion of material by MnO 2 Conversion of @ ACC to Na-MnO 2 @ACC。
FIGS. 2 and 3 are MnO 2 @ ACC and Na-MnO 2 The SEM image of @ ACC shows that after the sodium ions are embedded in the material, the material is converted from a compact surface into a three-dimensional network structure formed by connecting nano-sheets, and the sodium ion embedding is explained to change the morphology of the material.
FIG. 4 is Na-MnO 2 TEM image of @ ACC, indicating that the material is a sheet-like structure.
FIG. 5 shows MnO 2 @ ACC and Na-MnO 2 XPS of @ ACC, which is a full spectrum diagram showing the C, O, Mn element composition of material, passing through Na + After intercalation, the material detects the presence of sodium indicating Na + Successful embedding.
FIG. 6 shows Na-MnO 2 Electrochemical Cyclic Voltammetry (CV) plot of @ ACC at 1.5M Na 2 SO 4 The solution is an electrolyte, and Na-MnO is researched in a three-electrode system 2 Electrochemical Performance of @ ACC, Cyclic voltammogram at different scan rates showed that as the scan rate increased even at scan rates of up to 50mVs -1 The shape of the CV curve remained unchanged, indicating good kinetic reversibilityPerformance and rate performance.
FIG. 7 shows Na-MnO 2 The non-linearity of the electrochemical constant current charge-discharge (GCD) plot of @ ACC further verifies the existence of pseudocapacitive behavior, which is consistent with the results of the CV curve.
FIG. 8 shows Na-MnO 2 Electrochemical multiplying power diagram of @ ACC and current density of 5mAcm -2 The capacitance is 5875mFcm -2 . The current density is 5-30mAcm -2 The time magnification performance was 77%, and it was found that the film had good magnification performance.
FIG. 9 shows Na-MnO 2 The electrochemical cycle stability diagram of @ ACC shows that after 10000 cycles of cycle, the capacitance retention rate is over 90%, and the material can keep good electrochemical stability after electrochemical cycle, so that the material is an excellent electrode material of a super-capacitor energy storage device.
Fig. 10 is a graph of electrochemical Cyclic Voltammetry (CV) of a supercapacitor device, the shape of the cyclic voltammetry curve not changing significantly, indicating that the maximum voltage window of the device can reach 2.5V.
Fig. 11 is a graph of electrochemical constant current charge and discharge (GCD) of the supercapacitor device, and the change result of the charge and discharge curve is consistent with the cyclic voltammetry test result, which shows that the asymmetric supercapacitor energy storage device has excellent capacitance performance.
FIG. 12 is an electrochemical multiplying power diagram of a super capacitor device, with a current density of 1-10mAcm -2 The capacitance retention of 72% indicates that the assembled device has good rate performance.
FIG. 13 is a graph of electrochemical Ragon for a supercapacitor device with a supercapacitor energy density of 587 μ Wh cm -2 The time power density is 1.25mWcm -2 。
Fig. 14 is a diagram showing practical application of a supercapacitor device, and the device assembled in a water system can keep the period of lighting the electronic watch for about 24 hours, and has wide application prospects.
Claims (5)
1. The preparation method of the high-performance supercapacitor electrode material is characterized by comprising the following steps:
the preparation method adopts an electrochemical method, and specifically comprises the following steps:
step 1: pretreating the purchased Carbon Cloth (CC) to obtain Activated Carbon Cloth (ACC);
step 2: adding Mn (CH) at room temperature 3 COO) 2 ·4H 2 O and 4- (1H-imidazo [4, 5-f)][1,10]Mixing phenanthroline-2-yl) benzonitrile with deionized water to obtain an electrolyte;
step 3: placing ACC serving as a working electrode in electrolyte, and performing electrodeposition at 0.5-2V to form anchored MnO on an ACC substrate 2 Electrode material of (2), named MnO 2 @ACC；
Step 4: MnO of 2 @ ACC as working electrode, in Na 2 SO 4 Carrying out electrochemical activation in electrolyte to obtain Na-MnO 2 @ ACC electrode material.
Step 5: adding Na-MnO 2 @ ACC as positive electrode material, Fe 2 O 3 @ ACC as negative electrode material in Na 2 SO 4 Electrolyte or PVA/Na 2 SO 4 The gel electrolyte is matched with an asymmetric super capacitor.
The mass of the active substance can be determined by treating the carbon cloth loaded with the active substance with acid and measuring the mass difference between the carbon cloth and the active substance before and after weighing.
2. The method of claim 1, wherein in Step 1:
(1) selecting carbon cloth to be pretreated, wherein the size of the carbon cloth is 2 multiplied by 2cm 2 ；
(2) And pretreating the carbon cloth by a chemical method to obtain the activated carbon cloth.
3. The process according to claim 1, wherein Mn (CH) is contained in Step2 3 COO) 2 ·4H 2 The concentration of the O electrolyte is 0.01-0.5M and the solution is mixed evenly.
4. The method of claim 1, wherein the Step3 is performed by an electrochemical workstation using a carbon cloth as a working electrode, Ag/AgCl as a reference electrode, and a Pt sheet as a counter electrode.
5. The high-performance supercapacitor electrode material prepared by the preparation method of any one of claims 1 to 8.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210614131.3A CN114974931B (en) | 2022-05-31 | 2022-05-31 | Manganese-based high-voltage window electrode material and preparation of supercapacitor energy storage device |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210614131.3A CN114974931B (en) | 2022-05-31 | 2022-05-31 | Manganese-based high-voltage window electrode material and preparation of supercapacitor energy storage device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114974931A true CN114974931A (en) | 2022-08-30 |
| CN114974931B CN114974931B (en) | 2023-09-01 |
Family
ID=82959736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210614131.3A Active CN114974931B (en) | 2022-05-31 | 2022-05-31 | Manganese-based high-voltage window electrode material and preparation of supercapacitor energy storage device |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114974931B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7199997B1 (en) * | 2000-06-09 | 2007-04-03 | U.S. Nanocorp, Inc. | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| US20120262842A1 (en) * | 2010-10-12 | 2012-10-18 | The Regents Of The University Of Michigan | High Performance Transition Metal Carbide and Nitride and Boride Based Asymmetric Supercapacitors |
| CN103474255A (en) * | 2013-09-18 | 2013-12-25 | 中国科学院过程工程研究所 | Super capacitor high-voltage electrolyte and preparation method thereof |
| CN110223847A (en) * | 2019-06-11 | 2019-09-10 | 江苏先创新能源有限公司 | A kind of electrode material for super capacitor and preparation method |
| CN110581028A (en) * | 2019-08-30 | 2019-12-17 | 浙江工业大学 | Preparation method of manganese dioxide/carbon-based flexible electrode material |
| CN112908722A (en) * | 2021-01-21 | 2021-06-04 | 南京工业大学 | MnO for preparing high specific capacitance2Method for compounding flexible electrode material with carbon cloth |
| CN113394025A (en) * | 2021-05-17 | 2021-09-14 | 太原理工大学 | Flexible self-repairing supercapacitor based on activated carbon cloth/manganese dioxide composite material and preparation method thereof |
-
2022
- 2022-05-31 CN CN202210614131.3A patent/CN114974931B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7199997B1 (en) * | 2000-06-09 | 2007-04-03 | U.S. Nanocorp, Inc. | Asymmetric electrochemical supercapacitor and method of manufacture thereof |
| US20120262842A1 (en) * | 2010-10-12 | 2012-10-18 | The Regents Of The University Of Michigan | High Performance Transition Metal Carbide and Nitride and Boride Based Asymmetric Supercapacitors |
| CN103474255A (en) * | 2013-09-18 | 2013-12-25 | 中国科学院过程工程研究所 | Super capacitor high-voltage electrolyte and preparation method thereof |
| CN110223847A (en) * | 2019-06-11 | 2019-09-10 | 江苏先创新能源有限公司 | A kind of electrode material for super capacitor and preparation method |
| CN110581028A (en) * | 2019-08-30 | 2019-12-17 | 浙江工业大学 | Preparation method of manganese dioxide/carbon-based flexible electrode material |
| CN112908722A (en) * | 2021-01-21 | 2021-06-04 | 南京工业大学 | MnO for preparing high specific capacitance2Method for compounding flexible electrode material with carbon cloth |
| CN113394025A (en) * | 2021-05-17 | 2021-09-14 | 太原理工大学 | Flexible self-repairing supercapacitor based on activated carbon cloth/manganese dioxide composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| MENG CHEN等: "Alkali cation incorporated MnO2 cathode and carbon cloth anode for flexible aqueous supercapacitor with high wide-voltage and power density", ELECTROCHIMICA ACTA, vol. 342, pages 1 - 41 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114974931B (en) | 2023-09-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Lang et al. | Asymmetric supercapacitors based on stabilized α-Ni (OH) 2 and activated carbon | |
| Palaniappan et al. | Nano fibre polyaniline containing long chain and small molecule dopants and carbon composites for supercapacitor | |
| CN110010359B (en) | Preparation method of nickel/cobalt hydroxide composite electrode material | |
| CN103093967A (en) | Preparation and application of laminated structure cobalt and aluminum double hydroxide-reduction and oxidation graphene composite materials | |
| CN111689523B (en) | Metallic chromium doped delta-MnO2Preparation method of nanosheet | |
| Naresh et al. | Carbon coated SnO2 as a negative electrode additive for high performance lead acid batteries and supercapacitors | |
| Zhang et al. | Mild synthesis route to nanostructured α-MnO2 as electrode materials for electrochemical energy storage | |
| CN109741967A (en) | A kind of hybrid super capacitor based on graphite anode and zinc load | |
| CN111333129B (en) | Preparation method of nano nickel sulfide/nitrogen-doped porous carbon composite material for super capacitor | |
| CN105185978A (en) | Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof | |
| Tong et al. | Co2NiO4 nanoneedle networks for high performance pseudocapacitor | |
| CN109545573B (en) | Preparation method of metal 1T-phase rhenium sulfide hollow nanosphere supercapacitor electrode material | |
| CN101399120A (en) | Novel hybrid supercapacitor | |
| CN111268745A (en) | NiMoO4@Co3O4Core-shell nano composite material, preparation method and application | |
| CN108987125B (en) | Perovskite stannate supercapacitor electrode material, preparation method and application | |
| CN109346717B (en) | Self-supporting NaxMnO2Array sodium-ion battery positive electrode material and preparation method thereof | |
| CN112038106B (en) | Electrode material, preparation method thereof and supercapacitor electrode | |
| CN113496823B (en) | Symmetric hybrid supercapacitor and application thereof | |
| CN113628890B (en) | Bimetallic selenide composite Ti 3 C 2 Preparation method of material, product thereof and super capacitor | |
| CN113658809B (en) | Preparation method of amorphous manganese oxide electrode material | |
| CN114974931B (en) | Manganese-based high-voltage window electrode material and preparation of supercapacitor energy storage device | |
| CN104538206A (en) | Application of perovskite oxide in super capacitor | |
| CN104392848A (en) | Method for preparing element doped manganese dioxide electrode materials for super-capacitors | |
| CN109326452A (en) | A kind of preparation method and application of polypyrrole/polyaniline double-walled nanotubes electrode | |
| Zhao et al. | Synergistically Coupling Atomic‐Level Defect‐Manipulation and Nanoscopic‐Level Interfacial Engineering Enables Fast and Durable Sodium Storage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |