CN117711837B - Based on SiO-containing material2Electrode material of solid waste of (2), preparation method thereof and application thereof in super capacitor - Google Patents
Based on SiO-containing material2Electrode material of solid waste of (2), preparation method thereof and application thereof in super capacitor Download PDFInfo
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 23
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- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60L—PROPULSION OF ELECTRICALLY-PROPELLED VEHICLES; SUPPLYING ELECTRIC POWER FOR AUXILIARY EQUIPMENT OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRODYNAMIC BRAKE SYSTEMS FOR VEHICLES IN GENERAL; MAGNETIC SUSPENSION OR LEVITATION FOR VEHICLES; MONITORING OPERATING VARIABLES OF ELECTRICALLY-PROPELLED VEHICLES; ELECTRIC SAFETY DEVICES FOR ELECTRICALLY-PROPELLED VEHICLES
- B60L50/00—Electric propulsion with power supplied within the vehicle
- B60L50/40—Electric propulsion with power supplied within the vehicle using propulsion power supplied by capacitors
-
- 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
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Transportation (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
Abstract
An electrode material based on SiO 2 -containing solid waste, a preparation method thereof and application thereof in super capacitors. The invention belongs to the technical field of super capacitors. The invention aims to solve the technical problem that the energy density of a super capacitor device is low because the specific capacitance of the existing electrode material based on solid wastes containing SiO 2 is not high. The invention takes solid waste containing SiO 2 as raw material, and the solid waste is calcined into silicate material at high temperature after being doped with Al/B; then carrying out ion exchange under the action of (CHCOO) 2Mn·4H2 O through hydrothermal reaction to obtain manganese hydroxysilicate; and finally, soaking in Na 2S2O8 solution to introduce manganese vacancy, thus obtaining the supercapacitor electrode material with high specific capacitance, good stability and low cost, and assembling the supercapacitor into the asymmetric supercapacitor with high energy density.
Description
Technical Field
The invention belongs to the technical field of supercapacitors, and particularly relates to an electrode material based on SiO 2 -containing solid waste, a preparation method thereof and application thereof in supercapacitors.
Background
The super capacitor has the outstanding advantages of high power density, long cycle life, short charge and discharge time, high safety and the like, and has a huge application prospect in the future energy storage field. However, the energy density of the super capacitor is still at a lower level than that of the secondary battery at present, and it is difficult to meet urgent application demands of large-sized hybrid power equipment, electric vehicles and the like with higher requirements on both power density and energy density. Therefore, it is an important problem to further strengthen the electrochemical performance of the supercapacitor electrode material and further greatly improve the energy density of the supercapacitor device. As a reference, the published battery energy density of the 2023, bitedi (tang) official network was 150Wh/kg.
The solid waste mainly comprises tailings, fly ash, coal cinder, coal gangue, smelting waste residue, red mud, sludge, waste siliceous materials and the like, and the aim of carrying out high-value green application and conversion on the solid waste is always pursued. The solid waste contains a large amount of SiO 2 and metal oxides (Al 2O3, caO, mgO, feO and the like), and has extremely low conductivity, so that the fly ash which is not subjected to any treatment and conversion is directly added into the material to be used as the electrode material of the supercapacitor, and the performance is poor. Transition metal silicate materials are valued for their low cost, abundant sources and excellent theoretical specific capacitance. The solid waste containing SiO 2 with rich sources and low cost is converted into the transition metal silicate material, and further has great development potential for being used as the electrode material of the super capacitor. In addition, the metal oxide in the solid waste is fully utilized in the preparation of the electrode material, which is also beneficial to the high-value green application. However, the transition metal silicate which is not further treated has the defects of low conductivity, poor cycle stability and the like, and the specific capacitance of the prepared electrode material is not ideal. Therefore, the electrochemical performance of the converted transition metal silicate is further improved, and the method has important significance for greatly improving the energy density of the supercapacitor device.
Disclosure of Invention
The invention aims to provide a super capacitor electrode material with high specific capacitance prepared from solid wastes containing SiO 2 as a raw material and an asymmetric super capacitor assembled by using the material, which has high energy density, high power density, good stability and low cost.
The technical scheme of the invention is realized by the following steps:
One of the purposes of the invention is to provide a preparation method of an electrode material based on SiO 2 -containing solid waste, which comprises the following steps:
S1: mixing solid waste containing SiO 2 with Na 2CO3、CaCO3、Al2O3、B2O3, grinding, and calcining at high temperature to obtain an Al/B doped silicate material, namely NAS/CS@FA;
s2: carrying out ion exchange on NAS/CS@FA, (CHCOO) 2Mn·4H2O、NH4Cl、NH4·H2 O and deionized water through hydrothermal reaction, and drying after the reaction is finished to obtain manganese hydroxysilicate, which is called MS@FA for short;
S3: and (3) soaking the MS@FA in a Na 2S2O8 solution, and drying to obtain the electrode material, namely M 2-xS/Mx O@FA for short.
Further limited, the solid waste containing SiO 2 in S1 comprises fly ash, biomass ash, coal gangue, red mud, gasification ash and blast furnace slag.
Further defined, the mass ratio of the solid waste containing SiO 2 to Na 2CO3、CaCO3、Al2O3、B2O3 in S1 is (1-10): (1-10): (0.5-2.5): (0-2.5): (0-0.5).
Further limited, the high-temperature calcination temperature in S1 is 700-900 ℃ and the time is 2-3h.
Further defined, the mass ratio of NAS/CS@FA, (CHCOO) 2Mn·4H2O、NH4Cl、NH4·H2 O to deionized water in S2 is (0.5-1): (2-6): (1.2-3): (20-50): (400-800).
Further limited, the hydrothermal reaction temperature in S2 is 120-180 ℃ and the time is 20-24 hours.
Further defined, the concentration of Na 2S2O8 solution in S3 is 0.5-4wt.%.
Further defined, soaking in S3 for 2-5 hours.
It is a second object of the present invention to provide an electrode material M 2-xS/Mx o@fa prepared as described above, having a heterostructure and manganese vacancies, x=0.5-1.
Further limited, the electrode material presents a composite morphology, the interior of the electrode material is provided with microspheres with petal-shaped lamellar structures, and the exterior of the electrode material is wrapped with lamellar substances.
The invention also provides an application of the electrode material prepared by the method in a super capacitor.
The fourth object of the invention is to provide a high-energy-density asymmetric supercapacitor, wherein the asymmetric supercapacitor takes M 2-xS/Mx O@FA as a positive electrode and takes a carbon material as a negative electrode.
The fifth purpose of the invention is to provide an application of the asymmetric super capacitor with high energy density in large-scale hybrid power equipment and electric automobiles.
Compared with the prior art, the invention has the remarkable effects that:
According to the invention, the effect of Al element and B element doping on the electrochemical performance of the manganese hydroxy silicate, the effect of manganese vacancy on the electrochemical performance of the manganese hydroxy silicate and the effect of heterostructures formed in the in-situ deposition process on the electrochemical performance of the manganese hydroxy silicate are researched, and further found that: al element and B element are co-doped into the manganese hydroxy silicate, and the formation of a heterostructure changes the internal electric field structure of the material, so that electron transmission is promoted; the introduction of the manganese vacancy exposes more active sites, so that the energy storage effect is enhanced; the heterostructure improves the surface interface property of the M 2-xS/Mx O@FA electrode material, and enhances the adsorption of ions in electrolyte and the transmission of electrons at an interface; the positive electrode material of the asymmetric supercapacitor has good conductivity and surface interface characteristics by cooperative regulation and control of various strategies.
The invention provides a method for preparing a supercapacitor electrode material with high specific capacitance, good stability and low cost by taking solid wastes containing SiO 2 as raw materials, and the supercapacitor electrode material is assembled into an asymmetric supercapacitor with high energy density. The prepared M 2-xS/Mx O@FA electrode material has high specific capacity and good cycling stability, the specific capacity is 547F/g under the current density of 0.5A/g, and the capacity retention rate is 85% after being cycled 10000 times under the current density of 5A/g. The energy density of the assembled asymmetric supercapacitor can reach 144Wh/kg, the power density can reach 375W/kg, the assembled asymmetric supercapacitor has excellent cycling stability, and the capacity of the assembled asymmetric supercapacitor can still be kept 100% for 10000 times under the current density of 5A/g.
Drawings
FIG. 1 is a scanning electron microscope image of fly ash from example 1;
FIG. 2 is an X-ray diffraction pattern of fly ash of example 1;
FIG. 3 is a scanning electron microscope image of the NAS/CS@FA electrode material of example 1;
FIG. 4 is an X-ray diffraction pattern of the NAS/CS@FA electrode material of example 1;
FIG. 5 is a scanning electron microscope image of the MS@FA electrode material in example 1;
FIG. 6 is an X-ray diffraction pattern of the MS@FA electrode material and M 2-xS/Mx O@FA electrode material in example 1;
FIG. 7 is a scanning electron microscope image of the M 2-xS/Mx O@FA electrode material obtained in example 1;
FIG. 8 is a transmission electron microscope image of the M 2-xS/Mx O@FA electrode material obtained in example 1;
FIG. 9 is an electron paramagnetic resonance spectrum of the MS@FA in example 1 and the M 2-xS/Mx O@FA electrode material obtained in example 1;
FIG. 10 is an X-ray photoelectron spectrum of the M 2-xS/Mx O@FA electrode material obtained in example 1;
FIG. 11 is a Mott-Schottky curve of the M 2-xS/Mx O@FA electrode material obtained in example 1;
FIG. 12 is a GCD curve of the M 2-xS/Mx O@acid-FA electrode material obtained in comparative example 1, the b-M 2-xS/Mx O@FA electrode material obtained in comparative example 2, and the M 2-xS/Mx O@FA electrode material obtained in example 1;
FIG. 13 is a GCD curve of the M 2-xS/Mx O@FA electrode material and MS@FA obtained in example 1;
FIG. 14 is a GCD curve of the Mn (OH) 2/Mn3O4 electrode material obtained in comparative example 3 and the M 2-xS/Mx O@FA electrode material obtained in example 1;
FIG. 15 is a graph showing the cycle performance of the M 2-xS/Mx O@FA electrode material obtained in example 1;
FIG. 16 is a cyclic voltammogram of an asymmetric supercapacitor assembled according to an example of application;
FIG. 17 is a constant current charge-discharge graph of an asymmetric supercapacitor assembled according to an example of application;
FIG. 18 is a graph of cycling stability of an asymmetric supercapacitor assembled according to an example of application;
fig. 19 is a Ragone diagram of an asymmetric supercapacitor assembled according to an example of application.
Detailed Description
The invention provides the following specific embodiments: the preparation method of the electrode material based on the solid waste containing SiO 2 comprises the following steps:
(1) Solid waste (including fly ash, biomass ash, coal gangue, red mud, gasified ash, blast furnace slag and the like) containing SiO 2 and Na 2CO3、CaCO3、Al2O3、B2O3 are mixed according to the following ratio of (1-10): (1-10): (0.5-2.5): (0-2.5): (0-0.5) mixing, grinding for 2-3h, calcining at 700-900 ℃ for 2-3h, repeatedly cleaning the calcined mixture to remove soluble substances, and obtaining an Al/B doped silicate material, namely NAS/CS@FA for short;
The high-temperature calcination process converts SiO 2 in the solid waste into water-insoluble silicate, and Al 2O3 and CaCO 3 in the mixed raw materials convert SiO 2 into NaAlSiO 4 and CaSiO 4, and simultaneously realize co-doping of hetero-atom Al element and B element.
(2) NAS/CS@FA, (CHCOO) 2Mn·4H2O、NH4Cl、NH4·H2 O and deionized water were mixed in the following ratio (0.5-1): (2-6): (1.2-3): (20-50): (400-800) mixing and stirring for 30-60min, transferring into a reaction kettle, performing hydrothermal reaction for 20-24h at 120-180 ℃, repeatedly cleaning the product until the filtrate is neutral after suction filtration, and finally drying for 12-14h at 80-90 ℃ to obtain manganese hydroxy silicate Mn 2(SiO3)(OH)2(H2 O, which is called MS@FA for short;
During the ion exchange process, the silicate is converted into manganese hydroxysilicate with electrochemical energy storage activity, and the hetero atoms Al and B are retained and doped into the manganese hydroxysilicate.
(3) Soaking MS@FA in Na 2S2O8 solution with the concentration of 0.5-4wt.% for 2-5h, repeatedly cleaning the product until the filtrate is neutral after suction filtration, and finally drying at 80-90 ℃ for 12-14h to obtain an electrode material with a heterostructure and manganese vacancies, wherein the electrode material is called M 2-xS/Mx O@FA for short, and x=0.5-1;
In the in situ deposition process, part of the positive divalent manganese ions are oxidized to a higher valence state to form manganese vacancies and are deposited in situ in the form of Mn 3O4, and the two materials form heterostructures while forming manganese vacancies at the oxidized manganese ion sites.
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
The experimental methods used in the following examples are conventional methods unless otherwise specified. The materials, reagents, methods and apparatus used, without any particular description, are those conventional in the art and are commercially available to those skilled in the art.
The preparation method of the electrode material based on the solid waste containing SiO 2 in the embodiment 1 and the embodiment is carried out according to the following steps:
(1) 2g of fly ash is mixed with 2g of Na 2CO3、0.5g CaCO3 and 0.1: 0.1g B 2O3 and then ground for 2 hours, and then calcined at a high temperature of 800 ℃ for 2 hours, and soluble substances are removed to obtain an Al/B doped silicate material, which is called NAS/CS@FA for short;
Wherein, the microscopic morphology scanning electron microscope image of the fly ash is shown in figure 1, has a spherical structure and has a firm and smooth surface; the phase composition X-ray diffraction pattern of the fly ash is shown in figure 2, and is two substances of crystalline SiO 2 and mullite Al 2(Al2.8Si1.2)O9.6.
The microcosmic appearance scanning electron microscope image of the NAS/CS@FA material prepared is shown in figure 3, and the surface is provided with short bar-shaped bulges and pores; the phase composition X-ray diffraction pattern is shown in figure 4, and NaAlSiO 4 and CaSiO 4 converted from SiO 2 in the fly ash.
(2) 40mg NAS/CS@FA、240mg(CHCOO)2Mn·4H2O、107mg NH4Cl、1820mg NH4·H2O And 30000mg of deionized water are mixed and stirred for 30min, then the mixture is transferred into a reaction kettle, and subjected to hydrothermal reaction at 180 ℃ for 24h, and after suction filtration, neutral filtrate is obtained, the mixture is dried for 12h to obtain manganese hydroxy silicate Mn 2(SiO3)(OH)2(H2 O) which is called MS@FA for short;
The microscopic morphology scanning electron microscope image of the prepared MS@FA material is shown in fig. 5, and the surface is a sheet material; the phase composition X-ray diffraction pattern is shown in fig. 6 and is manganese hydroxy silicate Mn 2(SiO3)(OH)2(H2 O).
(3) Soaking MS@FA in a Na 2S2O8 solution with the concentration of 0.5wt.% for 3 hours, filtering to obtain neutral filtrate, and drying for 12 hours to obtain an electrode material with a heterostructure and manganese vacancies, wherein the electrode material is abbreviated as M 2-xS/Mx O@FA, and x=0.75;
The X-ray diffraction pattern of the prepared M 2-xS/Mx O@FA electrode material is shown in figure 6, and part of manganese ions in the oxidized manganese hydroxy silicate Mn 2(SiO3)(OH)2(H2 O) are oxidized into Mn 3O4;
The microscopic morphology scanning electron microscope image of the M 2-xS/Mx O@FA electrode material is shown as a figure 7, and the lamellar substance is coated on the surface of the lamellar structure;
The microscopic appearance transmission electron microscope image of the M 2-xS/Mx O@FA electrode material is shown in figure 8, the surface of the fly ash microsphere is provided with a flower-like lamellar structure, and the outermost layer is a lamellar structure; the distortion and fusion phenomenon of lattice fringes in the high-resolution transmission microscope image is related to the doping of Al element and B element and manganese vacancy in the M 2-xS/Mx O@FA electrode material; boundaries of two different morphological substances are obviously observed at the edge of the M 2-xS/Mx O@FA electrode material, which indicates that a heterostructure exists;
The electron paramagnetic resonance spectrum of the M 2-xS/Mx O@FA electrode material is shown in FIG. 9, and compared with the MS@FA material, the obvious manganese vacancy signal of the M 2-xS/Mx O@FA electrode material is detected;
The X-ray photoelectron spectrum of the M 2-xS/Mx O@FA electrode material is shown in FIG. 10, and the existence of chemical bonds Si-B, si-O-Al, B-Mn and B-Al proves that Al element and B element are doped into the M 2-xS/Mx O@FA electrode material, and the existence of Mn 3+ proves that partial manganese ions in the manganese hydroxy silicate Mn 2(SiO3)(OH)2(H2 O) are successfully oxidized;
The Mott-Schottky curve of the M 2-xS/Mx O@FA electrode material is shown in FIG. 11, and the inverted V-shaped curve structure proves that a heterostructure exists in the prepared M 2-xS/Mx O@FA electrode material.
Comparative example 1: this comparative example differs from example 1 in that: before using, the fly ash in the step (1) is pickled by HCl to remove metal elements. Other steps and parameters were the same as in example 1. The obtained electrode material is simply called M 2-xS/Mx O@acid-FA.
Comparative example 2: this comparative example differs from example 1 in that: b 2O3 is not added in the step (1). Other steps and parameters were the same as in example 1. The electrode material obtained is simply called b-M 2-xS/Mx O@FA.
Comparative example 3: this comparative example differs from example 1 in that: omitting the step (1), and directly treating the fly ash in the step (2) and the step (3). Other steps and parameters were the same as in example 1. The electrode material obtained is abbreviated as Mn (OH) 2/Mn3O4.
Detection example 1: the electrochemical properties of the M 2-xS/Mx O@FA electrode materials, M 2-xS/Mx O@acid-FA material, b-M 2-xS/Mx O@FA material, MS@FA material and Mn (OH) 2/Mn3O4 material prepared in example 1 and comparative examples 1-3 were examined.
In a three-electrode test system, a platinum sheet electrode is used as a counter electrode, an Hg-HgO electrode is used as a reference electrode, a constant current charge-discharge (CV) curve of a test material is tested when the current density is 0.5A/g, and a circulating charge-discharge test curve of the M 2-xS/Mx O@FA electrode material is tested under the current density of 5A/g.
As shown in fig. 12, the specific capacitance of the prepared M 2-xS/Mx o@fa electrode material is 547F/g; as shown in fig. 13, the specific capacitance of the ms@fa material is 233F/g; as shown in fig. 15, the remaining capacity after 10000 charge-discharge cycles at a current density of 5A/g was 85%.
As shown in FIG. 12, the specific capacitance of the prepared M 2-xS/Mx O@acid-FA material is 125F/g.
As shown in FIG. 12, the specific capacitance of the prepared b-M 2-xS/Mx O@FA material was 84F/g.
As shown in FIG. 14, the specific capacitance of the prepared Mn (OH) 2/Mn3O4 material was 116F/g.
Comparative analysis found that: the Al element and the B element are doped into an internal electric field structure of the hydroxy manganese silicate material to promote the transmission of electrons, so that the specific capacitance of the electrode material is increased. The manganese vacancy is introduced into the hydroxy manganese silicate material to change the internal electric field structure and promote the transmission of electrons; the introduction of manganese vacancies exposes more active sites, resulting in enhanced energy storage. The heterostructure formed in the in-situ deposition process enables the electrode material to have good conductivity and surface interface characteristics, and further has high specific capacitance; the specific capacitance of the manganese hydroxy silicate M 2-xS/Mx O@FA electrode material synthesized by taking the fly ash as a substrate is obviously higher than that of the Mn (OH) 2/Mn3O4 material synthesized by taking the fly ash as a non-substrate, because the fly ash substrate provides a high specific surface area for the material, the material is uniformly dispersed, and the problem of low utilization rate of active sites caused by agglomeration is avoided.
Application example: the asymmetric supercapacitor was prepared and the assembly conditions were as follows:
(1) Uniformly mixing 16mg of M 2-xS/Mx O@FA electrode material, 2mg of acetylene black and 2mg of polytetrafluoroethylene, adding 2mL of ethanol to prepare slurry, and uniformly coating on foam nickel to obtain a positive electrode material;
(2) Uniformly mixing 64mg of active carbon, 8mg of acetylene black and 8mg of polytetrafluoroethylene, adding 8mL of ethanol to prepare slurry, and uniformly coating to obtain a negative electrode material;
(3) 3.04g of polyvinyl alcohol (PVA) is dissolved in 30mL of deionized water and stirred uniformly, and 4.26g of KOH is added while stirring, so as to obtain an electrolyte;
(4) The device is assembled by using M 2-xS/Mx O@FA electrode material and active carbon electrode material as an anode and a cathode, a piece of cellulose paper as a diaphragm and PVA/KOH electrolyte, a flexible plastic PET film is used for packaging the device, and two copper chips are connected to the edge of each electrode.
Detection example 2: the electrochemical properties of the asymmetric supercapacitor were tested under the following conditions: a Cyclic Voltammetry (CV) test with a scanning speed of 5mV/s to 20mV/s, a constant current charge-discharge (GCD) test with a current density of 0.5A/g to 8A/g, and a cyclic charge-discharge test with a current density of 5A/g.
The cyclic voltammogram of the asymmetric supercapacitor is shown in fig. 16, the constant current charge-discharge curve is shown in fig. 17, the cyclic stability curve is shown in fig. 18, and the Ragone curve is shown in fig. 19; the energy density of the asymmetric supercapacitor can reach 144Wh/kg, the power density can reach 375W/kg, the asymmetric supercapacitor has excellent cycling stability, and the capacity of the asymmetric supercapacitor can still be kept 100% for 10000 times under the current density of 5A/g.
In the foregoing, the present invention is merely preferred embodiments, which are based on different implementations of the overall concept of the invention, and the protection scope of the invention is not limited thereto, and any changes or substitutions easily come within the technical scope of the present invention as those skilled in the art should not fall within the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.
Claims (8)
1. A method for preparing an electrode material based on solid waste containing SiO 2, which is characterized by comprising the following steps:
S1: mixing solid waste containing SiO 2 with Na 2CO3、CaCO3、Al2O3、B2O3, grinding, and calcining at high temperature to obtain an Al/B doped silicate material; the high-temperature calcination process converts SiO 2 in the solid waste into water-insoluble silicate, al 2O3 and CaCO 3 convert SiO 2 into NaAlSiO 4 and CaSiO 4, and simultaneously realizes co-doping of hetero-atom Al element and B element;
S2: carrying out ion exchange on an Al/B doped silicate material, (CHCOO) 2Mn·4H2O、NH4Cl、NH4·H2 O and deionized water through hydrothermal reaction, and drying after the reaction is finished to obtain Al/B doped manganese hydroxysilicate Mn 2(SiO3)(OH)2(H2 O), wherein the silicate is converted into manganese hydroxysilicate with electrochemical energy storage activity in the ion exchange process, and simultaneously heteroatom Al element and B element are reserved and doped into the manganese hydroxysilicate;
S3: immersing Al/B doped manganese hydroxy silicate Mn 2(SiO3)(OH)2(H2 O) in Na 2S2O8 solution, drying to obtain Al/B doped Mn 2(SiO3)(OH)2(H2O)/Mn3O4 electrode material with heterostructure and manganese vacancy, oxidizing partial positive divalent manganese ions in Al/B doped manganese hydroxy silicate Mn 2(SiO3)(OH)2(H2 O) to higher valence state to form manganese vacancy and depositing in situ in Mn 3O4 form, forming heterostructure by the two materials, and forming manganese vacancy at oxidized manganese ion position.
2. The method of claim 1, wherein the solid waste containing SiO 2 in S1 comprises fly ash, biomass ash, coal gangue, red mud, gasification ash, blast furnace slag.
3. The method according to claim 1, wherein the mass ratio of the solid waste containing SiO 2 to Na 2CO3、CaCO3、Al2O3、B2O3 in S1 is (1-10): (1-10): (0.5-2.5): (0-2.5): (0-0.5), the high-temperature calcination temperature is 700-900 ℃ and the time is 2-3h.
4. The method according to claim 1, wherein the mass ratio of Al/B doped silicate material in S2, (CHCOO) 2Mn·4H2O、NH4Cl、NH4·H2 O and deionized water is (0.5-1): (2-6): (1.2-3): (20-50): (400-800), the hydrothermal reaction temperature is 120-180 ℃ and the time is 20-24h.
5. The method of claim 1, wherein the concentration of Na 2S2O8 solution in S3 is 0.5-4wt.%, soaking for 2-5h.
6. Use of an electrode material prepared by the method of any one of claims 1-5 in a supercapacitor.
7. An asymmetric supercapacitor with high energy density, wherein the asymmetric supercapacitor uses an Al/B doped Mn 2(SiO3)(OH)2(H2O)/Mn3O4 electrode material with heterostructures and manganese vacancies prepared by the method of any one of claims 1-5 as a positive electrode and a carbon material as a negative electrode.
8. The use of the high energy density asymmetric supercapacitor of claim 7 in large hybrid power devices and electric vehicles.
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| EP1134826A1 (en) * | 1999-05-10 | 2001-09-19 | Hydro-Quebec | New lithium insertion electrode materials based on orthosilicate derivatives |
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| 二氧化硅/硅酸锰核壳微球的可控制备;王玲燕;王春利;杜芳林;;中国科技论文;20120915(第09期);全文 * |
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