CN111508728A - Long-life manganese-based water system mixed zinc ion capacitor and preparation method thereof - Google Patents
Long-life manganese-based water system mixed zinc ion capacitor and preparation method thereof Download PDFInfo
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- CN111508728A CN111508728A CN202010356304.7A CN202010356304A CN111508728A CN 111508728 A CN111508728 A CN 111508728A CN 202010356304 A CN202010356304 A CN 202010356304A CN 111508728 A CN111508728 A CN 111508728A
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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
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- H—ELECTRICITY
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- 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
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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
- H01G11/22—Electrodes
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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
- H01G11/22—Electrodes
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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
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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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
Abstract
The invention discloses a long-life manganese-based water system mixed zinc ion capacitor and a preparation method thereof, and belongs to the technical field of electrochemical energy storage devices. The capacitor comprises a manganese-based positive electrode, electrolyte, a zinc sheet negative electrode, a diaphragm arranged between the positive electrode and the negative electrode and a shell, wherein: the manganese-based positive electrode is Mn3O4a/C nanosheet array composite structure; the electrolyte consists of soluble zinc salt, soluble sodium salt and deionized water; the Mn is3O4the/C nanosheet array composite structure takes carbon cloth as a matrix, and Mn is obtained by utilizing an electrodeposition method3O4The nano-sheet array is uniformly deposited on the carbon cloth. The capacitor prepared by the invention can provide a specific capacity of 200mAh/g when working in a voltage range of 0-1.8V, and the manganese-based water system mixed zinc ion capacitor disclosed by the invention shows excellent cycling stability, has a capacity retention rate of 81% in 1500 cycles, and is low in cost and simple in preparation process.
Description
Technical Field
The invention belongs to the technical field of electrochemical energy storage devices, and particularly relates to a long-life manganese-based water system mixed zinc ion capacitor and a preparation method thereof.
Background
It is well known that energy storage is an important problem facing human society. In recent years, electric vehicles and portable electronic products have been developed rapidly, and energy storage devices with high energy density, high power output, long service life and high safety have become urgent needs. At present, existing energy storage devices include batteries (such as lithium ion batteries and alkaline zinc-manganese oxide batteries), supercapacitors and the like, but the safety risk and lithium resource of the lithium ion batteries are limited, the cycle stability of the alkaline zinc-manganese oxide batteries is poor, and the like, so that researchers are prompted to find a cheap alternative energy storage system of the ion batteries. Notably, the zinc metal electrode had an 823mah g-1(Zn/Zn2+) The high-capacity and-0.76 v (V.S. standard hydrogen electrode) low oxidation-reduction potential has the outstanding advantages of high safety, low cost and environmental protection, so that the water system zinc ion battery becomes one of the most potential energy storage devices. However, the zinc ion battery has the problem of poor power density, and the problem of lithium resource limitation is avoided based on the advantages of high energy density and high power density of the lithium ion capacitor, so that the design of the water system zinc ion hybrid capacitor with high energy density and high power density has important application value.
Manganese-based oxides are used as the most promising positive electrode material for aqueous zinc ion batteries due to their higher energy density, but their structural instability leads to poor cycling stability. For example, the dissolution, irreversible lattice distortion and electrostatic interaction of the cathode in the charging and discharging process lead to serious battery capacity attenuation and poor cycle stability, which seriously restrict the development and popularization of the zinc ion battery and are not effectively solved at present.
The present application has been made for the above reasons.
Disclosure of Invention
In view of the problems or disadvantages of the prior art, it is an object of the present invention to provide a long-life manganese-based waterA mixed zinc ion capacitor and a method for manufacturing the same are provided. The invention uses nontoxic modified manganese-based anode material and aqueous Na+And Zn2+The mixed ion electrolyte and the zinc sheet cathode ensure the high performance and the high safety of the capacitor.
In order to achieve the above purpose of the present invention, the technical solution adopted by the present invention is as follows:
the utility model provides a long-life manganese base water system mixes zinc ion capacitor, includes manganese base positive pole, electrolyte, zinc sheet negative pole, sets up diaphragm and casing between the positive negative pole, wherein: the manganese-based positive electrode is trimanganese tetroxide/carbon (Mn)3O4/C) a nanosheet array composite structure; the electrolyte consists of soluble zinc salt, soluble sodium salt and deionized water.
Further, according to the technical scheme, the soluble zinc salt is any one of zinc sulfate, zinc nitrate, zinc chloride and the like. More preferably, the soluble zinc salt is zinc sulfate.
Further, in the above technical scheme, the soluble sodium salt is any one of sodium sulfate, sodium nitrate, sodium chloride and the like. More preferably, the soluble sodium salt is sodium sulfate.
Further, in the above technical solution, the Mn is3O4the/C nanosheet array composite structure is prepared by taking Carbon Cloth (CC) as a matrix and utilizing an electrodeposition method to prepare mangano-manganic oxide (Mn)3O4) The nano-sheet array is uniformly deposited on the carbon cloth. In which Mn is present3O4The two-dimensional nanosheet array can shorten an ion diffusion path and promote rapid ion transfer, because such an array morphology is very beneficial to the ion intercalation/deintercalation process in the zinc ion battery. The good conductivity of the carbon cloth can ensure the uniform deposition of the active substances and can also improve the considerable surface area for the effective contact of the electrolyte and the surface of the cathode material.
Specifically, in the above technical scheme, the Mn is3O4the/C nanosheet array composite structure is prepared by the following method, comprising the following steps:
firstly, the carbon cloth is pretreated, and then an electrochemical deposition process is adopted after the pretreatmentMn grows on the surface of the carbon cloth3O4A nanosheet array; and after the electrodeposition is finished, repeatedly cleaning the substrate by using deionized water, and finally naturally drying the substrate at room temperature.
Preferably, in the above technical scheme, the carbon cloth pretreatment process specifically comprises the following steps:
and soaking the cut empty carbon cloth in concentrated nitric acid for 1-2 h at a constant temperature of 60-100 ℃, taking out the carbon cloth after soaking is finished, repeatedly cleaning the carbon cloth by using absolute ethyl alcohol and deionized water, and finally drying the carbon cloth for later use.
More preferably, in the above technical solution, the carbon cloth is preferably a carbon cloth having a carbon nanosheet array.
More preferably, in the technical scheme, the concentration of the concentrated nitric acid is 6-12 mol/L.
Preferably, in the above technical solution, the electroplating solution used in the electrochemical deposition includes manganese salt, sodium sulfate and deionized water, wherein: the manganese salt and sodium sulfate were at the same concentration.
Preferably, in the above technical solution, the manganese salt is any one of manganese acetate, manganese sulfate, manganese chloride, or the like.
More preferably, in the above technical means, the concentration of the manganese salt in the plating solution is 0.05 to 0.2 mol/L.
Preferably, in the above technical scheme, the electrochemical deposition process may be electrodeposition for 10-30 min at room temperature under a constant potential condition; or circulating for 20-50 circles at a scanning rate of 50-100 mV/s under a potential window of 0-1.3V by using a linear Cyclic Voltammetry (CV) method to obtain a target product.
Preferably, in the above technical solution, the deposition potential adopted by the potentiostatic method is-2.5 to-1.3V.
The second purpose of the invention is to provide the preparation method of the manganese-based water-system mixed zinc ion capacitor with long service life, which is to assemble the manganese-based positive electrode, the zinc sheet negative electrode and the diaphragm into a shell, inject electrolyte and package.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uses a four-layer growth on carbon clothTrimanganese oxide/carbon (Mn)3O4/C) nanosheet array as the positive electrode, wherein Mn3O4The nanosheet array structure can shorten an ion diffusion path and promote rapid ion transfer, because such an array morphology is very beneficial to the ion intercalation/deintercalation process in the zinc ion battery. The good conductivity of the carbon cloth (especially the carbon cloth with a nanosheet array) ensures that the active substance is uniformly deposited, and can also increase considerable surface area for the effective contact of the electrolyte and the surface of the cathode material. When the method is applied to a zinc ion capacitor, the potential window is higher, the cycle stability is better, the capacity is higher, and the multiplying power characteristic is better.
(2) In the invention, Mn is added3O4On the basis that the/C nanosheet array composite structure is used as the positive electrode of the water system mixed zinc ion capacitor, the electrolyte composition is adjusted and further optimized, and Na is introduced into the zinc salt electrolyte+And (4) taking zinc salt and sodium salt as electrolytes. Mn3O4Reversible Zn on/C positive electrode2+Intercalation/deintercalation, and Zn2+/Na+/H+Ion adsorption/desorption, and high-efficiency energy storage is realized. Zn (Zn) on zinc simple substance cathode2+) Deposition/exfoliation enables aqueous hybrid zinc ion capacitors to reversibly store/transfer electrical energy, with higher energy storage capacity and good rate characteristics and excellent cycling stability. Safe, ultra-long life Mn3O4the/C// zinc salt + sodium salt// Zn simple substance chargeable manganese-based water system mixed zinc ion capacitor provides a new solution for the energy storage problem.
(3) The manganese-based water system mixed zinc ion capacitor disclosed by the invention can provide a specific capacity of 200mAh/g when working in a voltage range of 0-1.8V, shows excellent cycle stability, has a capacity retention rate of 81% in 1500 cycles, and is low in cost and simple in preparation process.
Drawings
FIG. 1 shows Mn in example 1 of the present invention3O4SEM image of/C nanosheet array composite structure, wherein: (a) high power; (b) the weight is low;
FIG. 2 shows the present inventionMn of example 23O4XPS spectrum of/C nano sheet array composite structure: wherein (a) is a full spectrum; (b) is Mn2 p; (c) is O1 s; (d) is C1 s;
FIG. 3 is a plot of cyclic voltammetry for manganese-based aqueous hybrid zinc ion capacitors prepared in example 1 of the present invention at different scan rates;
FIG. 4 is a charge-discharge curve diagram of the manganese-based aqueous mixed zinc ion capacitor prepared in example 2 of the present invention at different charge-discharge times;
fig. 5 is a graph showing cycle life of the manganese-based aqueous hybrid zinc ion capacitor prepared in example 2 of the present invention.
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 utility model provides a long-life manganese base water system mixes zinc ion capacitor, includes manganese base positive pole, electrolyte, zinc sheet negative pole, sets up diaphragm and casing between the positive negative pole, wherein: the manganese-based positive electrode is trimanganese tetroxide/carbon (Mn)3O4/C) a nanosheet array composite structure; the electrolyte consists of 2M ZnSO4With 0.5M Na2SO4The mixed aqueous solution of (1); wherein:
the Mn is3O4the/C nanosheet array composite structure is prepared by the following method, comprising the following steps:
(1) 100M L containing 0.1M manganese acetate tetrahydrate (Mn (CH)3COO)2·4H2O), 0.1M sodium sulfate (Na)2SO4) The mixed aqueous solution of (a) is used as an electroplating solution;
(2) pretreating carbon cloth: cutting multiple sizes of 3 × 3cm2The empty carbon cloth with the nano-sheet array is soaked in concentrated nitric acid with the concentration of 6 mol/L, heated for 1 hour in a constant-temperature water bath kettle at the temperature of 80 ℃, repeatedly cleaned in absolute ethyl alcohol and deionized water in sequence after being soaked by the concentrated nitric acid, and finally dried for later use.
(3) Placing the carbon cloth pretreated in the step (2) as a working electrode in the electroplating solution obtained in the step (1) for constant potential electrodeposition, controlling the constant potential to be-1.8V, performing electrodeposition for 20min at room temperature, repeatedly cleaning the obtained product with deionized water after the deposition is finished, and placing the product in a room temperature environment for overnight drying to obtain the Mn3O4the/C nanosheet array composite structure.
The manganese-based aqueous mixed zinc ion capacitor described in this embodiment is manufactured by assembling a manganese-based positive electrode, a zinc sheet negative electrode, and a separator into a case, injecting an electrolyte, and encapsulating to obtain Mn3O4The zinc ion capacitor comprises a water system mixed zinc ion capacitor based on/C// zinc salt + sodium salt// Zn manganese.
Testing with Scanning Electron Microscope (SEM)Mn prepared as described above in this example3O4Microstructure of/C nanoplate array, FIG. 1(a) shows the nanoplate thickness is about 20nm, FIG. 1(b) shows Mn3O4the/C nanosheet array uniformly grows on the surface of the carbon fiber, and the size of the carbon fiber is about 1-2 mu m. In which Mn is present3O4The nanosheet array structure can shorten an ion diffusion path and promote rapid ion transfer, because such an array morphology is very beneficial to the ion intercalation/deintercalation process in the zinc ion battery. The carbon cloth with the carbon nanosheet array has good conductivity, ensures uniform deposition of active substances, and can improve considerable surface area for effective contact between electrolyte and the surface of a cathode material.
The manganese-based aqueous hybrid zinc ion capacitor prepared in this example was electrochemically tested using the CHI760E electrochemical station. The electrochemical measurement comprises cyclic voltammetry, constant current charge-discharge, electrochemical impedance spectrum and the like, and is based on Mn3O4The specific capacity, energy density and the like of the device are calculated by weight of/C.
Fig. 3 is a cyclic voltammetry curve of the manganese-based aqueous mixed zinc ion capacitor prepared in this example without a scan rate, which shows that the capacitor prepared in this example has excellent rate capability, and thus, the capacitor has a higher power density.
Example 2
The utility model provides a long-life manganese base water system mixes zinc ion capacitor, includes manganese base positive pole, electrolyte, zinc sheet negative pole, sets up diaphragm and casing between the positive negative pole, wherein: the manganese-based positive electrode is trimanganese tetroxide/carbon (Mn)3O4/C) a nanosheet array composite structure; the electrolyte consists of 2M Zn (NO)3)2With 0.5M NaNO3The mixed aqueous solution of (1); wherein:
the Mn is3O4the/C nanosheet array composite structure is prepared by the following method, comprising the following steps:
(4) 100M L containing 0.1M manganese acetate tetrahydrate (Mn (CH)3COO)2·4H2O), 0.1M sodium sulfate (Na)2SO4) The mixed aqueous solution of (a) is used as an electroplating solution;
(5) carbon cloth preAnd (3) treatment: cutting multiple sizes of 3 × 3cm2The empty carbon cloth is soaked in concentrated nitric acid with the concentration of 12 mol/L, heated for 1 hour in a constant-temperature water bath kettle at the temperature of 80 ℃, repeatedly cleaned in absolute ethyl alcohol and deionized water in sequence after being soaked in the concentrated nitric acid, and finally dried for later use.
(6) Placing the carbon cloth pretreated in the step (2) as a working electrode in the electroplating solution obtained in the step (1) for constant potential electrodeposition, controlling the constant potential to be-1.4V, performing electrodeposition for 25min at room temperature, repeatedly cleaning the obtained product with deionized water after the deposition is finished, and placing the product in a room temperature environment for overnight drying to obtain the Mn3O4the/C nanosheet array composite structure.
The manganese-based aqueous mixed zinc ion capacitor described in this embodiment is manufactured by assembling a manganese-based positive electrode, a zinc sheet negative electrode, and a separator into a case, injecting an electrolyte, and encapsulating to obtain Mn3O4The zinc ion capacitor comprises a water system mixed zinc ion capacitor based on/C// zinc salt + sodium salt// Zn manganese.
Mn prepared as described above in this example3O4The microstructure of the/C nanosheet array composite structure is substantially the same as the microstructure of the material of example 1. Further, Mn in the present example3O4The X-ray photoelectron energy spectrum (XPS) of the/C nanosheet array composite structure is shown in FIG. 2. Figure 2(a) shows the XPS survey spectrum of this material. FIG. 2(b) shows a spectrum of Mn2p, indicating that Mn exists in +2 and +3 valence states. FIGS. 2(C) and (d) show spectra for O1s and C1s, respectively, indicating the presence of C-O bonds, and Mn-O bonds.
The manganese-based aqueous hybrid zinc ion capacitor prepared in this example was electrochemically tested using the CHI760E electrochemical station. The electrochemical measurement comprises cyclic voltammetry, constant current charge-discharge, electrochemical impedance spectrum and the like, and is based on Mn3O4The specific capacity, energy density and the like of the device are calculated by weight of/C.
FIG. 4 shows Mn prepared in this example3O4The charge-discharge curves of the/C// zinc salt + sodium salt// Zn manganese-based water system mixed zinc ion capacitor at different charge-discharge times are combined with the cycle life curve of the device shown in FIG. 5, which shows that the capacitor prepared by the embodiment has excellent cycle stability and electricityThe working life of the container is ideal.
Example 3
The utility model provides a long-life manganese base water system mixes zinc ion capacitor, includes manganese base positive pole, electrolyte, zinc sheet negative pole, sets up diaphragm and casing between the positive negative pole, wherein: the manganese-based positive electrode is trimanganese tetroxide/carbon (Mn)3O4/C) a nanosheet array composite structure; the electrolyte consists of 1M ZnCl2Mixed aqueous solution with 1M NaCl; wherein:
the Mn is3O4the/C nanosheet array composite structure is prepared by the following method, comprising the following steps:
(7) 100M of L manganese sulfate (MnSO) with 0.05M is prepared4) 0.05M sodium sulfate (Na)2SO4) The mixed aqueous solution of (a) is used as an electroplating solution;
(8) pretreating carbon cloth: cutting multiple sizes of 3 × 3cm2The empty carbon cloth with the nano-sheet array is soaked in concentrated nitric acid with the concentration of 10 mol/L, heated for 2 hours in a constant-temperature water bath kettle at the temperature of 60 ℃, repeatedly cleaned in absolute ethyl alcohol and deionized water in sequence after being soaked by the concentrated nitric acid, and finally dried for later use.
(9) Placing the carbon cloth pretreated in the step (2) as a working electrode in the electroplating solution obtained in the step (1) for electrodeposition, circulating for 20 circles at a scanning rate of 100mV/s under a potential window of 1V by using a linear Cyclic Voltammetry (CV), repeatedly cleaning the obtained product by using deionized water after the deposition is finished, and placing the product in a room temperature environment for overnight drying to obtain Mn3O4the/C nanosheet array composite structure.
The manganese-based aqueous mixed zinc ion capacitor described in this embodiment is manufactured by assembling a manganese-based positive electrode, a zinc sheet negative electrode, and a separator into a case, injecting an electrolyte, and encapsulating to obtain Mn3O4The zinc ion capacitor comprises a water system mixed zinc ion capacitor based on/C// zinc salt + sodium salt// Zn manganese.
Mn prepared as described above in this example3O4The microstructure of the/C nanosheet array composite structure is substantially the same as the microstructure of the material of example 1. And Mn prepared in this example3O4The charge-discharge curves and the cycle life curves of the/C// zinc salt + sodium salt// Zn manganese-based water system mixed zinc ion capacitor at different charge-discharge times are basically the same as those of the example 2, and the cyclic voltammetry curves are basically consistent with the test results of the example 1. The capacitor prepared by the embodiment has excellent cycling stability, and the working life of the capacitor is ideal.
Example 4
The utility model provides a long-life manganese base water system mixes zinc ion capacitor, includes manganese base positive pole, electrolyte, zinc sheet negative pole, sets up diaphragm and casing between the positive negative pole, wherein: the manganese-based positive electrode is trimanganese tetroxide/carbon (Mn)3O4/C) a nanosheet array composite structure; the electrolyte consists of 2M ZnSO4With 1M Na2SO4The mixed aqueous solution of (1); wherein:
the Mn is3O4the/C nanosheet array composite structure is prepared by the following method, comprising the following steps:
(10) 100M of L manganese chloride (MnCl) with 0.2M is prepared2) 0.2M sodium sulfate (Na)2SO4) The mixed aqueous solution of (a) is used as an electroplating solution;
(11) pretreating carbon cloth: cutting multiple sizes of 3 × 3cm2The empty carbon cloth is soaked in concentrated nitric acid with the concentration of 10 mol/L, heated for 1 hour in a constant-temperature water bath kettle at the temperature of 100 ℃, repeatedly cleaned in absolute ethyl alcohol and deionized water in sequence after being soaked in the concentrated nitric acid, and finally dried for later use.
(12) Placing the carbon cloth pretreated in the step (2) as a working electrode in the electroplating solution obtained in the step (1) for electrodeposition, circulating for 50 circles at a scanning rate of 50mV/s under a potential window of 0.5V by using a linear Cyclic Voltammetry (CV), repeatedly washing the obtained product by using deionized water after the deposition is finished, and placing the product in a room temperature environment for overnight drying to obtain Mn3O4the/C nanosheet array composite structure.
The manganese-based aqueous mixed zinc ion capacitor described in this embodiment is manufactured by assembling a manganese-based positive electrode, a zinc sheet negative electrode, and a separator into a case, injecting an electrolyte, and encapsulating to obtain Mn3O4C// zincSalt + sodium salt// Zn manganese-based aqueous hybrid zinc ion capacitor.
Mn prepared as described above in this example3O4The microstructure of the/C nanosheet array composite structure is substantially the same as the microstructure of the material of example 1. And Mn prepared in this example3O4The charge-discharge curves and the cycle life curves of the/C// zinc salt + sodium salt// Zn manganese-based water system mixed zinc ion capacitor at different charge-discharge times are basically the same as those of the example 2, and the cyclic voltammetry curves are basically consistent with the test results of the example 1. The capacitor prepared by the embodiment has excellent cycling stability, and the working life of the capacitor is ideal.
In view of the above, Mn having high efficiency and long life3O4the/C// zinc salt + sodium salt// Zn manganese-based aqueous mixed zinc ion capacitor ensures high safety by using a non-toxic electrode material and an aqueous electrolyte. Using trimanganese tetroxide/carbon nanosheet arrays (Mn) grown on carbon cloth3O4/C) composite structure as positive electrode, in which Mn is present3O4The nanosheet array structure can shorten an ion diffusion path and promote rapid ion transfer, because such an array morphology is very beneficial to the ion intercalation/deintercalation process in the zinc ion battery. The working voltage can provide a specific capacity of 200mAh/g within a voltage range of 0-1.8V, and the manganese-based water system mixed zinc ion capacitor disclosed by the invention has excellent cycle stability and has a capacity retention rate of 81% in 1500 cycles. Mn3O4Reversible Zn on/C positive electrode2+Intercalation/deintercalation, and Zn2+/Na+/H+Ion adsorption/desorption, and high-efficiency energy storage is realized. Zn (Zn) on zinc simple substance cathode2+) Deposition/exfoliation enables manganese-based aqueous hybrid zinc ion capacitors to reversibly store/transfer electrical energy, with higher energy storage capacity and good rate characteristics and excellent cycle stability. In conclusion, excellent electrochemical properties and high safety make Mn desirable3O4the/C// zinc salt + sodium salt// Zn manganese-based water system mixed zinc ion capacitor has a great prospect.
Claims (10)
1. Long-life manganeseThe base water system mixed zinc ion capacitor is characterized in that: including manganese base positive pole, electrolyte, zinc sheet negative pole, set up diaphragm and casing between the positive negative pole, wherein: the manganese-based positive electrode is Mn3O4a/C nanosheet array composite structure; the electrolyte consists of soluble zinc salt, soluble sodium salt and deionized water.
2. The long life manganese-based aqueous hybrid zinc-ion capacitor of claim 1, wherein: the Mn is3O4the/C nanosheet array composite structure is prepared by adopting the following method: firstly, pretreating the carbon cloth, and then growing Mn on the surface of the pretreated carbon cloth by adopting an electrochemical deposition process3O4A nanosheet array; and after the electrodeposition is finished, repeatedly cleaning the substrate by using deionized water, and finally naturally drying the substrate at room temperature.
3. The long life manganese-based aqueous hybrid zinc-ion capacitor of claim 2, wherein: the carbon cloth pretreatment process comprises the following specific steps: and soaking the cut empty carbon cloth in concentrated nitric acid for 1-2 h at a constant temperature of 60-100 ℃, taking out the carbon cloth after soaking is finished, repeatedly cleaning the carbon cloth by using absolute ethyl alcohol and deionized water, and finally drying the carbon cloth for later use.
4. The long life manganese-based aqueous hybrid zinc-ion capacitor of claim 2, wherein: the electroplating solution adopted by the electrochemical deposition comprises manganese salt, sodium sulfate and deionized water, wherein: the manganese salt and sodium sulfate were at the same concentration.
5. The long life manganese-based aqueous hybrid zinc-ion capacitor of claim 4, wherein: the manganese salt is any one of manganese acetate, manganese sulfate or manganese chloride.
6. The long-life manganese-based aqueous hybrid zinc-ion capacitor as claimed in claim 4, wherein the concentration of manganese salt in said plating solution is 0.05 to 0.2 mol/L.
7. The long life manganese-based aqueous hybrid zinc-ion capacitor of claim 2, wherein: the electrochemical deposition process is to carry out electrodeposition for 10-30 min under the conditions of room temperature and constant potential; or circulating for 20-50 circles at a scanning rate of 50-100 mV/s under a potential window of 0-1.3V by using a linear cyclic voltammetry method to obtain a target product.
8. The long life manganese-based aqueous hybrid zinc-ion capacitor of claim 1, wherein: the deposition potential adopted by the potentiostatic method is-2.5 to-1.3V.
9. The long life manganese-based aqueous hybrid zinc-ion capacitor of claim 1, wherein: the soluble zinc salt is any one of zinc sulfate, zinc nitrate and zinc chloride; the soluble sodium salt is any one of sodium sulfate, sodium nitrate and sodium chloride.
10. The method for producing a long-life manganese-based aqueous mixed zinc ion capacitor as claimed in any one of claims 1 to 9, wherein: specifically, the manganese-based anode, the zinc sheet cathode and the diaphragm are assembled into a shell, and then the shell is filled with electrolyte and packaged.
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| CN112466677A (en) * | 2020-10-13 | 2021-03-09 | 暨南大学 | Zinc ion hybrid capacitor based on ruthenium oxide/carbon material composite positive electrode and construction method thereof |
| CN113066674A (en) * | 2021-03-24 | 2021-07-02 | 辽宁大学 | Nickel-cobalt-zinc ternary transition metal hydroxide electrode material with multistage nanostructure and preparation method and application thereof |
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| CN113066674A (en) * | 2021-03-24 | 2021-07-02 | 辽宁大学 | Nickel-cobalt-zinc ternary transition metal hydroxide electrode material with multistage nanostructure and preparation method and application thereof |
| CN114824236A (en) * | 2022-06-06 | 2022-07-29 | 安徽工业大学 | Water-based zinc ion battery cathode material with functional protective layer and preparation method thereof |
| CN114824236B (en) * | 2022-06-06 | 2023-09-15 | 安徽工业大学 | Water-based zinc ion battery anode material with functional protective layer and preparation method thereof |
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