CN110942919B - Water system zinc ion hybrid supercapacitor capable of being rapidly charged and discharged and preparation method thereof - Google Patents
Water system zinc ion hybrid supercapacitor capable of being rapidly charged and discharged and preparation method thereof Download PDFInfo
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/42—Powders or particles, e.g. composition thereof
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-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
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention discloses a water system zinc ion hybrid super capacitor capable of being charged and discharged rapidly and a preparation method thereof, and belongs to the technical field of electrochemical energy storage devices. The invention discloses a water system zinc ion hybrid super capacitor capable of being charged and discharged quickly, which comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, electrolyte and a shell, wherein: the positive active material and the negative active material are mesoporous carbon hollow spheres; the electrolyte consists of zinc salt, sodium salt and deionized water. The water system zinc ion hybrid supercapacitor provided by the invention can provide 226F/g specific capacity when working in a voltage range of 0-1.6V, has good rate capability, and can be rapidly charged/discharged within 17 seconds, so that the hybrid supercapacitor provided by the invention has excellent cycle stability, has a capacity retention rate of 99.4% in 2500 cycles, and is very suitable for safe, high-rate and ultra-long-life rechargeable energy storage.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage devices, and particularly relates to a water system zinc ion hybrid supercapacitor capable of being charged and discharged rapidly and a preparation method thereof.
Background
As the world population continues to grow, the contradiction between the demand for energy and the consumption of fuel energy for global sustainable development is increasing. To solve this conflict, people are more concerned about developing higher-performance energy storage devices. Super capacitor as a kind between rechargeable battery and conventional capacitorThe novel energy storage device has the advantages of high power density, excellent cycle performance and the like, is considered to be an important electrochemical energy storage device, and has become a research hotspot in the field of electrochemical energy storage in recent years. However, the relatively low energy output of supercapacitors limits their convenience and large-scale application. Therefore, most of the research on the super capacitor is mainly focused on how to increase the energy density of the super capacitor, mainly by the following methods: (1) synthesizing electrode materials with good supercapacitive properties, (2) construction of hybrid supercapacitors consisting of one battery-like electrode and one capacitor-like electrode by constructing asymmetric supercapacitors is an effective strategy to achieve high energy density while maintaining large powder density. For example, it has been reported that high performance lithium ion hybrid supercapacitors of pre-lithiated carbon anodes and bifunctional cathodes developed by Xianzhong Sun et al, high voltage/high power potassium ion capacitors achieved by potassium intercalation into graphite by Shinichi Komaba et al, and Eunho Lim et al studies are based on Nb2O5The potential window of the sodium ion mixed super capacitor of the carbon and graphene nano composite material is 0.01-3.0V, and the voltage of the sodium ion mixed super capacitor is 0.025 A.g-1Shows 285mAh g at a current density of-1High capacity and high power density. Wherein, all are based on monovalent metal cations (Li)+，K+And Na+) The electrolyte and the electrode system which are charge carriers have the problem that the requirement for further improving the energy density cannot be met; the used organic electrolyte has high decomposition voltage, but has high toxicity, high cost, flammability and high requirement on the process.
For the above reasons, the present application has been made.
Disclosure of Invention
In view of the problems or defects of the prior art, the invention aims to provide a water system zinc ion hybrid supercapacitor capable of being rapidly charged and discharged and a preparation method thereof. The invention ensures the high safety of the capacitor by using non-toxic electrode materials and aqueous electrolyte.
In order to achieve the above purpose of the present invention, the technical solution adopted by the present invention is as follows:
a water system zinc ion hybrid super capacitor capable of being rapidly charged and discharged comprises a positive electrode, a negative electrode, a diaphragm arranged between the positive electrode and the negative electrode, electrolyte and a shell, wherein: the positive active material and the negative active material are mesoporous carbon hollow spheres; the electrolyte consists of zinc salt, sodium salt and deionized water.
Further, according to the technical scheme, the positive electrode is formed by uniformly mixing the positive active substance, the conductive agent and the adhesive and then coating and/or filling the mixture on the surface of the current collector; the negative electrode is formed by uniformly mixing a negative electrode active substance, a conductive agent and a binder and then coating and/or filling the mixture on the surface of a current collector. The positive electrode and the negative electrode can be prepared by uniformly dispersing active substances, a conductive agent and a binder in a solvent to prepare slurry and coating the slurry on a current collector by using a common method for preparing a battery pole piece.
Preferably, in the above technical solution, the conductive agent is any one of acetylene black, graphene, conductive carbon black, carbon nanotubes, and the like. The adhesive is any one of polytetrafluoroethylene, polyvinylidene fluoride, cellulose, styrene butadiene rubber and the like. The current collector is any one of foamed nickel, a copper sheet or foamed copper.
Further, according to the above technical solution, the membrane is a porous polymer membrane with ion diffusion, and may be any one of a polyethylene membrane, a polypropylene membrane, a polyethylene and polypropylene composite membrane, and a cellulose membrane.
Further, in the technical scheme, the zinc salt in the electrolyte is any one of zinc sulfate, zinc nitrate and zinc chloride. More preferably, the zinc salt is zinc sulfate.
Further, in the above technical scheme, the sodium salt in the electrolyte is any one of sodium sulfate, sodium nitrate and sodium chloride. More preferably, the sodium salt is sodium sulfate.
Further, according to the technical scheme, the mesoporous carbon hollow sphere is prepared by the following method, and the method specifically comprises the following steps:
dissolving propyl orthosilicate in a mixed solvent consisting of absolute ethyl alcohol, deionized water and ammonia water, and thenSequentially adding resorcinol and formaldehyde into the obtained mixed solution, continuously stirring and reacting for 18-30 h at the temperature of 30-40 ℃, carrying out suction filtration, washing and drying to obtain SiO2a/RF composite material; then the SiO is put into2Placing the/RF composite material in a tube furnace, heating to 600-800 ℃ under the protection of inert gas, and reacting for 4-6 h at constant temperature to obtain SiO2a/C composite material; finally, the SiO is mixed2Placing the/C composite material in a dilute alkali solution to obtain SiO2And (4) completely etching, filtering, washing and drying to obtain mesoporous carbon hollow sphere powder.
Preferably, in the technical scheme, the mass ratio of the propyl orthosilicate to the resorcinol to the formaldehyde is (2-4): (0.2-0.4): 0.4: 0.6.
the second object of the invention is to provide a preparation method of the above-mentioned water-based zinc ion hybrid supercapacitor capable of being rapidly charged and discharged, specifically, a positive electrode, a negative electrode, an electrolyte and a diaphragm are assembled into a shell, the electrolyte is injected, and the water-based zinc ion hybrid supercapacitor is prepared by packaging.
Compared with the prior art, the invention has the following beneficial effects:
(1) the mesoporous carbon hollow spheres are used as the active substances of the positive electrode and the negative electrode, and the regular network formed by the mesoporous channels communicated with the mesoporous carbon hollow spheres can promote the ion migration, shorten the diffusion path and the like, thereby overcoming the defects of the conventional carbon material.
(2) The invention takes the mesoporous carbon hollow sphere as the positive and negative poles of the zinc ion mixed super capacitor, further optimizes the mesoporous carbon hollow sphere through the adjustment of electrolyte components, and introduces Na into the zinc salt electrolyte+And (4) taking zinc salt and sodium salt as electrolytes. Reversible Zn on mesoporous carbon anodes+/Na+/H+Ion adsorption/desorption of Zn (Zn) on mesoporous carbon cathodes2+) Deposition/exfoliation enables aqueous zinc ion hybrid supercapacitors to reversibly store/transfer electrical energy, with higher energy storage capacity and good rate characteristics and excellent cycling stability. The safe, high-speed and ultra-long-life rechargeable aqueous zinc ion hybrid supercapacitor made of mesoporous carbon// zinc salt + sodium salt// mesoporous carbon provides a new energy storage problemThe solution of (1).
(3) The water system zinc ion hybrid supercapacitor provided by the invention can provide 226F/g specific capacity when working in a voltage range of 0-1.6V, has good rate capability, and can be rapidly charged/discharged within 17 seconds, so that the water system zinc ion hybrid supercapacitor provided by the invention shows excellent cycle stability and has a capacity retention rate of 99.4% in 2500 cycles.
Drawings
FIG. 1 (a) shows SiO prepared in example 12SEM pictures of/RF composite material, (b) and (c) are SEM pictures of the mesoporous carbon hollow sphere (MPC) prepared in example 1.
In FIG. 2, (a) is SiO2/RF composite material, SiO2X-ray diffraction patterns of/C composites and mesoporous carbon hollow Spheres (MPCs); (b) XPS peak profiles for MPCs prepared in example 1; (c) n of MPC prepared for example 12Adsorption and desorption curves; (d) the pore size distribution curve of MPC prepared in example 1 was calculated from adsorption branches using BJH model.
FIG. 3 shows MPC// ZnSO in practical example 14+Na2SO4the/MPC water zinc ion mixed super capacitor has cyclic voltammetry characteristic curves under the conditions that the scanning voltage window is 0-1.6V, and the scanning rates are 5mV/s, 10mV/s, 20mV/s, 30mV/s, 50mV/s, 70mV/s and 100mV/s respectively.
FIG. 4 shows MPC// ZnSO in practical example 14+Na2SO4And// MPC water zinc ion mixed super capacitor constant current charge and discharge curve under different current density conditions.
FIG. 5 shows MPC// ZnSO in application example 14+Na2SO4A multiplying power performance diagram of a MPC water system zinc ion mixed super capacitor.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". Accordingly, unless expressly indicated otherwise, the numerical parameters set forth in the specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Example 1
The preparation method of the mesoporous carbon hollow sphere provided by the embodiment comprises the following specific steps:
3.46ml of propyl orthosilicate is weighed and dissolved in a mixed solvent consisting of 70ml of absolute ethyl alcohol, 10ml of deionized water and 3ml of ammonia water; then adding 0.4g of resorcinol and 0.56ml of formaldehyde into the mixed solution, stirring for 24 hours at 35 ℃ by using a magnetic stirrer, performing suction filtration and washing (three times of deionized water and two times of absolute ethyl alcohol), and drying at normal temperature to obtain SiO2a/RF composite material. Then increasing the preset temperature of the tube furnace to 700 ℃ at the heating rate of 2 ℃/min at 30 ℃, and then increasing the SiO2N of/RF composite material at 700 DEG C2Keeping the temperature for 300min under the condition to obtain SiO2a/C composite material. 4mol/L diluted NaOH aqueous solution is prepared, and each 0.1g of Si is addedO2250ml of the dilute NaOH solution of the/C composite material is stirred at room temperature for 12 hours to prepare SiO2Etching, carrying out suction filtration washing (three times of deionized water and two times of absolute ethyl alcohol), and drying to obtain mesoporous carbon hollow sphere (MPC) powder.
Characterization of the Material
The resulting samples were subjected to crystal structure analysis using a Philips X' Pert Pro type X-ray diffractometer (XRD) and the size and morphology of the nanoparticles were characterized using field emission scanning electron microscopy (FESEM, JSM 7100F Hitachi) and transmission electron microscopy (TEM, Tecnai 20ST, FEG). For SEM characterization, mesoporous carbon hollow sphere (MPC) powder was coated on the one hand on conductive gel and on the other hand on foamed nickel. For TEM characterization, Transmission Electron Microscopy (TEM), high resolution TEM (hrtem), energy dispersive X-ray spectroscopy (EDX) and High Angle Annular Dark Field (HAADF) Scanning Transmission Electron Microscopy (STEM) analysis the electron emission source was performed using a JEOL ARM 200F microscope equipped with a cold field, and an image Cs corrector (CE0S GmbH) was run at 200 kV. Specific surface area and porosity were measured using a specific surface area and porosity analyzer (Micromeritics ASAP2020) and calculated by the Brunauer-Emmett-Teller (BET) method. X-ray photoelectron spectroscopy (XPS) measurements were characterized using a Thermo Fisher scientific Calab 250Xi spectrometer with AlKa radiation.
From the SEM low-power image of the mesoporous carbon hollow sphere (MPC) of fig. 1(b), it was found to have a spherical morphology and to exist as a monodispersion with a concentrated particle size distribution. As can be seen from the high power image in FIG. 1(c), the MPC has a uniform particle size and an average diameter of about 350 nm; the porous membrane has a relatively rough surface, can provide more active sites to modify some functional groups on the surface, effectively avoids the occurrence of pore channel blockage, and is very favorable for quickly adsorbing/desorbing electrolyte ions. And the transmission electron microscope photo further proves that the MPC is uniform and non-agglomerated and presents an independent spherical shape; the hollow structure formed by the channel system can endow the material with ultrahigh porosity and excellent molecular sieving performance, so that the action between the material and atoms, molecules and even larger objects can be limited on the outer surface of the material, and the material can penetrate through the whole material, thereby being more beneficial to molecular diffusion and transmission.
Figure 2(a) is an X-ray diffraction diagram of a three-phase sample of MPC formation. Comparative SiO2/RF composite material, SiO2The spectra of the/C composite material and the MPC show obvious diffraction peaks at the temperature of about 24 ℃. According to the position (2 theta) of the diffraction peak, the crystal plane orientation of the unit cell can be obtained, wherein the vicinity of 24 degrees corresponds to the (002) crystal plane of the graphite crystal; the characteristic diffraction peak of the MPC increased, indicating an increase in crystallinity. In addition, in the diffraction pattern of MPC, a distinct diffraction peak was also present near 43 °, corresponding to the (101) crystal plane of graphite, thereby indicating that the prepared carbon material had graphitization characteristics in a crystalline state, and in addition, no other diffraction pattern maxima were observed. Fig. 2(b) is an XPS peak profile of MPC, which provides information about the bonding structure of each component, and the presence of C ═ C (284.6eV), C — O (286.1eV), C ═ O (288.3eV) was observed. FIG. 2(c) is the N of MPC2Adsorption and desorption curves at P/P0>0.7H showing a columnar channel2Hysteresis loop, indicating that MPC has a uniform mesoporous structure. Has a large specific surface area of about 800m2The volume/g is higher than that of the 427m of the mesoporous carbon spheres reported in the document of Yan Yan et al2The value of/g is related to the presence of a large number of pores on the surface of the mesoporous carbon particles. Fig. 2(d) is a pore size distribution curve of the mesoporous carbon hollow sphere calculated by the adsorption branch by adopting a BJH model, and the pore size distribution is concentrated and uniform, most of porous structures are distributed at about 10nm, and the pore size distribution is favorable for diffusion of electrolyte ions and improvement of electrochemical performance of an electrode material.
Application example 1
The MPC prepared in example 1 was used as an active material, a suspension of poly (tetrafluoroethylene) (PTFE) as a binder (60 wt%) and acetylene black as a conductive additive were mixed in a ratio of 8: 1: 1 by weight ratio. And cutting a foamed nickel wafer with the diameter of 12mm, coating the mixed slurry on the foamed nickel surface, performing vacuum drying at 70 ℃ for 12 hours, and pressing under 10MPa to obtain the mesoporous carbon electrode plate. The mass of the active material on the electrode sheet is about 3-4mg/cm2. Sequentially stacking the positive plate, the diaphragm, the negative plate, the gasket and the elastic sheet,placing in button shell, and applying 2M ZnSO4+1M Na2SO4The mixed solution is used as electrolyte and is sealed and assembled into MPC// ZnSO4+Na2SO4v/MPC water zinc ion mixed super capacitor. Electrochemical testing was performed using CHI760E electrochemical station. The electrochemical measurement comprises cyclic voltammetry, constant current charge and discharge, electrochemical impedance spectroscopy and the like, and the specific capacity, the energy density and the like of the device are calculated based on the weight of the mesoporous carbon.
FIG. 3 shows MPC// ZnSO in practical example 14+Na2SO4The scanning speed of the/MPC water zinc ion hybrid super capacitor is 5mV/s, 10mV/s, 20mV/s, 30mV/s, 50mV/s, 70mV/s and 100mV/s in a scanning voltage window of 0-1.6V. The figure shows, MPC// ZnSO4+Na2SO4The CV curve of the/MPC aqueous zinc ion hybrid supercapacitor appeared in a rectangular-like shape, indicating that it had electric double layer capacitance. As the scanning speed is gradually increased, the rectangle has no large deviation, and the anions and cations with small sizes are still easier to transmit and diffuse among MPC pore channels, so that the MPC porous membrane has good rate performance even if the scanning speed is high. The average specific capacitance value is calculated by the following formula:
(1) where m, dV, I, dt are the mass (kg) of the active electrode material, the voltage range (V) of the sweep, the oxidation or reduction current (A), respectively, as a derivative with respect to time. In addition, the capacitance can also be directly and qualitatively described by a closed curve of cyclic voltammetry, and the larger the area of the closed graph is, the larger the capacitance value is. The cyclic voltammetry curve at 5mv/s can obtain MPC// ZnSO4+Na2SO4The// MPC water system zinc ion hybrid supercapacitor has a specific capacitance value of 226F/g.
FIG. 4 shows MPC// ZnSO in practical example 14+Na2SO4And// MPC water zinc ion mixed super capacitor constant current charge and discharge curve under different current density conditions. The figure shows MPC// ZnSO4+Na2SO4The zinc ion mixed super capacitor of the// MPC water system can be 2At a current of 0A/g, charge/discharge was rapidly carried out within 17 seconds. Exhibit good specific capacitance characteristics.
FIG. 5 shows MPC// ZnSO in application example 14+Na2SO4A multiplying power performance diagram of a MPC water system zinc ion mixed super capacitor. MPC// ZnSO4+Na2SO4The reason why the specific capacitance of the zinc ion mixed supercapacitor of the MPC water system is gradually reduced along with the increase of the current density is that when the current density is high, electrolyte ions do not have enough time to enter the mesopores, the generated electric double layer capacitance and faraday pseudo capacitance are reduced, and the charging and discharging time is shortened, so that the specific capacitance is reduced. From this, MPC// ZnSO was found4+Na2SO4The rate capability of the MPC water system zinc ion hybrid super capacitor is excellent.
MPC// ZnSO of the present invention4+Na2SO4The zinc ion hybrid supercapacitor integrating water system of/MPC has a series of advantages: it has a greater capacity and energy density than ordinary supercapacitors, better rate performance and cycling stability than most rechargeable supercapacitors, and in addition, the application of non-toxic electrode materials and aqueous electrolytes gives the new system a high degree of safety to human health and the ecological environment. In summary, the MPC// ZnSO provided by the present invention4+Na2SO4the/MPC water system zinc ion hybrid supercapacitor is well suited for safe, high rate and ultra-long life rechargeable energy storage.
In conclusion, MPC// ZnSO with high efficiency and good cycle stability4+Na2SO4The zinc ion mixed super capacitor of the MPC water system ensures high safety by using non-toxic electrode materials and aqueous electrolyte. Hybrid zinc ion supercapacitors operating in the voltage range of 0-1.6V can provide a specific capacity of 226F/g. Has good rate capability and can be charged/discharged quickly within 17 seconds. The water-based zinc ion mixed supercapacitor disclosed by the invention shows excellent cycle stability and has a capacity retention rate of 99.4% in 2500 cycles. Wherein, the mesoporous carbon material and ZnSO4、Na2SO4The mixed aqueous solution is used as cathode, anode and electricity respectivelyReversible Zn on a mesoporous carbon cathode+/Na+/H+Ion adsorption/desorption of Zn (Zn) on mesoporous carbon anodes2+) Deposition/stripping is considered to be MPC// ZnSO4+Na2SO4The core mechanism of the energy storage of the MPC water system zinc ion hybrid supercapacitor. In conclusion, the excellent electrochemical performance and high safety make MPC// ZnSO4+Na2SO4The zinc ion hybrid supercapacitor based on the MPC water system has a great prospect.
Claims (7)
1. A water system zinc ion hybrid super capacitor capable of being charged and discharged rapidly is characterized in that: including positive pole, negative pole, set up diaphragm, electrolyte and the casing between the positive negative pole, wherein: the positive active material and the negative active material are mesoporous carbon hollow spheres; the electrolyte consists of zinc salt, sodium salt and deionized water;
the mesoporous carbon hollow sphere is prepared by the following method, and the specific steps are as follows:
dissolving propyl orthosilicate in a mixed solvent composed of absolute ethyl alcohol, deionized water and ammonia water, then sequentially adding resorcinol and formaldehyde into the obtained mixed solution, continuously stirring and reacting for 18-30 h at the temperature of 30-40 ℃, performing suction filtration, washing and drying to obtain SiO2a/RF composite material; then the SiO is put into2Placing the/RF composite material in a tube furnace, heating to 600-800 ℃ under the protection of inert gas, and reacting for 4-6 h at constant temperature to obtain SiO2a/C composite material; finally, the SiO is mixed2Placing the/C composite material in a dilute alkali solution to obtain SiO2Completely etching, filtering, washing and drying to obtain mesoporous carbon hollow sphere powder; the mass ratio of the propyl orthosilicate to the resorcinol to the formaldehyde is (2-4): (0.2-0.4): 0.4: 0.6.
2. the rapidly chargeable and dischargeable aqueous zinc ion hybrid supercapacitor according to claim 1, characterized in that: the positive electrode is formed by uniformly mixing a positive active substance, a conductive agent and an adhesive and then coating and/or filling the mixture on the surface of a current collector; the negative electrode is formed by uniformly mixing a negative electrode active substance, a conductive agent and a binder and then coating and/or filling the mixture on the surface of a current collector.
3. The rapidly chargeable and dischargeable aqueous zinc ion hybrid supercapacitor according to claim 2, characterized in that: the conductive agent is any one of graphene, conductive carbon black and carbon nano tubes; the adhesive is any one of polytetrafluoroethylene, polyvinylidene fluoride, cellulose and styrene butadiene rubber; the current collector is any one of foamed nickel, a copper sheet or foamed copper.
4. The rapidly chargeable and dischargeable aqueous zinc ion hybrid supercapacitor according to claim 1, characterized in that: the diaphragm is any one of a polyethylene diaphragm, a polypropylene diaphragm, a polyethylene and polypropylene composite diaphragm and a cellulose diaphragm.
5. The rapidly chargeable and dischargeable aqueous zinc ion hybrid supercapacitor according to claim 1, characterized in that: the zinc salt in the electrolyte is any one of zinc sulfate, zinc nitrate and zinc chloride.
6. The rapidly chargeable and dischargeable aqueous zinc ion hybrid supercapacitor according to claim 1, characterized in that: the sodium salt in the electrolyte is any one of sodium sulfate, sodium nitrate and sodium chloride.
7. The method for producing the rapidly chargeable and dischargeable aqueous zinc ion hybrid supercapacitor according to any one of claims 1 to 6, comprising: assembling a positive electrode, a negative electrode, electrolyte and a diaphragm into a shell, injecting the electrolyte, and packaging to obtain the water-system zinc ion hybrid supercapacitor.
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| CN103086346A (en) * | 2011-10-28 | 2013-05-08 | 沈阳药科大学 | Preparation method and applications of mesoporous carbon |
| CN103545123A (en) * | 2013-10-30 | 2014-01-29 | 中国第一汽车股份有限公司 | Hybrid energy storage device with zinc ion battery and supercapacitor |
| CN108172415A (en) * | 2017-12-26 | 2018-06-15 | 深圳先进技术研究院 | Aluminium ion hybrid super capacitor and preparation method thereof |
| CN109524248A (en) * | 2018-12-06 | 2019-03-26 | 中国科学院兰州化学物理研究所 | A kind of construction method of zinc ion mixed capacitor |
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