CN115424868B - Super capacitor with graphene coated foam nickel/cement structure and preparation and application thereof - Google Patents
Super capacitor with graphene coated foam nickel/cement structure and preparation and application thereof Download PDFInfo
- Publication number
- CN115424868B CN115424868B CN202211058508.8A CN202211058508A CN115424868B CN 115424868 B CN115424868 B CN 115424868B CN 202211058508 A CN202211058508 A CN 202211058508A CN 115424868 B CN115424868 B CN 115424868B
- Authority
- CN
- China
- Prior art keywords
- cement
- foam nickel
- based electrolyte
- structural
- supercapacitor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
-
- 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
- H01G11/56—Solid electrolytes, e.g. gels; Additives therein
-
- 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
-
- 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
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The invention relates to a graphene-coated foam nickel/cement structure super capacitor and preparation and application thereof. The structural supercapacitor (7) comprises structural electrodes (1) on two sides and cement-based electrolyte (6) arranged between the structural electrodes (1), wherein the structural electrodes (1) are composed of reduced graphene oxide (3) and foam nickel (2), and the cement-based electrolyte (6) is solid waste modified cement and is prepared from solid waste, cement, water and a water reducing agent. Compared with the prior art, the reduced graphene oxide coated foam nickel structure electrode provided by the invention has excellent conductivity; the preparation cost of the solid waste modified cement-based electrolyte is low, and the comprehensive utilization of resources and the harmless and recycling treatment of industrial wastes are realized; the structural super capacitor disclosed by the invention not only maintains excellent mechanical properties and higher capacitance, but also is suitable for large-scale application in the field of construction, and is expected to realize structural-functional integration of energy storage of green buildings.
Description
Technical Field
The invention relates to the technical field of structural supercapacitors, in particular to a graphene-coated foam nickel/cement structural supercapacitor and preparation and application thereof.
Background
Carbon dioxide emissions in the construction field have been over 23% of the total global carbon emissions. In order to advance the low carbonization of the construction industry, the concept of "zero energy building" has been proposed. The structural energy storage device is adopted to replace the traditional building component, and the energy storage device can bear external load and has great potential for storing electric energy. Among various types of structural energy storage devices, structural supercapacitors for construction, which are assembled from structural electrodes and solid electrolytes, have been attracting attention due to their satisfactory electrochemical energy storage capacity and mechanical properties.
Electrode materials are one of the key components that determine the performance of structural supercapacitors. Currently, common electrode materials are mainly carbon materials, transition metal oxides, conductive polymers, and the like. In the prior art, the traditional carbon materials such as activated carbon, carbon fiber, carbon aerogel and the like have the defects of complicated preparation, high price and the like, and bring great difficulty to application; whereas transition metal oxides generally have the defects of weak conductivity, poor electrochemical stability and the like; conductive polymers still face challenges such as easy exfoliation, high contact resistance, low energy density, etc. In contrast, carbon-based graphene is attracting attention due to its special two-dimensional honeycomb lattice structure, and its high specific surface area, excellent mechanical properties, and high conductivity make it promising as an ideal electrode material.
The energy storage and mechanical properties of a structural supercapacitor are also largely dependent on the choice of solid electrolyte, since the ionic conductivity of the solid electrolyte affects the capacitance and power density of the capacitor, while the strength of the solid electrolyte determines the mechanical properties of the capacitor. Currently, common solid electrolytes include ceramic-based electrolytes and polymer-based electrolytes. In the prior art, ceramic electrolytes are well suited for high temperature applications, however, at relatively low temperatures, ion conductivity is not ideal; likewise, the ionic conductivity of solid polymer electrolytes is relatively low (-10) at room temperature -6 -10 -4 S/cm) and there is poor contact with the interface of the electrode, which hinders practical application. In recent years, cement-based composite materials have been proposed as solid electrolytes due to their good ionic conductivity and mechanical properties. The invention patent CN107195478A provides a super capacitor with a graphene/magnesium phosphate cement structure and a preparation method thereof, wherein graphene is used as an electrode material, and magnesium phosphate cement is used as a solid electrolyte and mainly comprises heavy magnesium oxide, potassium dihydrogen phosphate, borax and fly ash. Compared with the prior art, the solid electrolyte of the capacitor is simple to prepare, and the early compressive strength is 5-7.5 MPa. However, the structural supercapacitor is provided with magnesium phosphate cementThe working performance is poor, the later strength is difficult to meet the bearing requirement of building components, the price of monopotassium phosphate is high, and the like, and the method is difficult to be applied to the field of building on a large scale.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a graphene-coated foam nickel/cement structure supercapacitor and preparation and application thereof, wherein the solid waste steel slag and waste glass powder are used as auxiliary cementing materials to produce solid electrolyte of the structural supercapacitor for construction, so that the good conductivity of the steel slag can be utilized to improve the conductivity of the electrolyte, the synergistic effect of the steel slag powder and the glass powder can also further improve the mechanical property of the electrolyte, and the method is an effective solid waste recycling way.
The aim of the invention can be achieved by the following technical scheme:
one of the technical schemes of the invention provides a graphene-coated foam nickel/cement structure supercapacitor, which comprises structure electrodes on two sides and cement-based electrolyte arranged between the structure electrodes, wherein the structure electrodes consist of reduced graphene oxide and foam nickel, and the cement-based electrolyte is prepared from solid waste, cement, water and a water reducing agent.
Further, the reduced graphene oxide is coated on the surface of the foam nickel, and the reduced graphene oxide is in direct contact with the cement-based electrolyte, and the area density of the reduced graphene oxide is 1-2 mg/cm 2 Preferably 1 to 1.2mg/cm 2 。
Further, the mass ratio of the solid waste to the cement to the water reducer is (20-50), 50-80, 30-50 and 0.1-0.2.
Further, the solid waste comprises steel slag powder and glass powder, and the mass ratio is (1-3) (0-3).
The specific surface area of the steel slag powder is more than 400m 2 The intensity activity index per kg,28d reaches more than 80%.
The glass powder has specific surface area greater than 400m 2 The intensity activity index per kg,28d reaches more than 80%.
Further, the cement is portland cement.
Further, the water reducer is a polycarboxylic acid high-efficiency water reducer.
The second technical scheme of the invention provides a preparation method of the graphene-coated foam nickel/cement structure supercapacitor, which comprises the following steps:
s1, preparing a structural electrode: coating reduced graphene oxide on the surface of foam nickel, and placing the foam nickel in urea solution to react to obtain a structural electrode;
s2, preparing a cement-based electrolyte: uniformly mixing solid waste and cement, adding deionized water and a water reducing agent, and stirring to obtain a cement-based electrolyte;
and S3, assembling the structural electrode prepared in the step S1 on two sides of the cement-based electrolyte prepared in the step S2 to obtain the structural supercapacitor.
Further, in the step S1, the mass ratio of urea to deionized water in the urea solution is (1-2): (40-80), preferably (1-2): (50-70).
Further, in the step S1, the specific reaction step is that the graphene oxide foam nickel coated is placed in urea solution of a reaction kettle lining to be generated in the reaction kettle lining, and the reaction kettle is placed in an oven to carry out hydrothermal reaction.
The temperature of the oven is 120-180 ℃, and the hydrothermal reaction time is 8-18 h.
Further, in step S1, after the reaction is completed, the obtained reaction product is firstly washed with 98% ethanol, then washed with deionized water, and dried to obtain the structural electrode.
The above further, the washing times of the ethanol and the deionized water are 3-5 times, and the drying temperature is 40-60 ℃.
Further, in step S2, the cement-based electrolyte is in a flowing state.
Further, in step S2, after the assembly is completed, the cement-based electrolyte is compacted by vibration, and the cement-based electrolyte is placed in a curing chamber for curing after demolding.
The temperature of the curing chamber is 19-22 ℃ and the relative humidity is 95-99%.
The third technical scheme of the invention provides application of the graphene-coated foam nickel/cement structure super capacitor, and the structure super capacitor is applied to the field of production construction.
The traditional super capacitor has excellent electrochemical performance, is difficult to bear load, is not suitable for being applied to a building, and has the following advantages and beneficial effects:
1. the reduced graphene oxide electrode material has large specific surface area and good conductivity, and can greatly improve the capacitance of the structural supercapacitor;
2. the solid waste steel slag powder and glass powder are added into the cement-based electrolyte as auxiliary cementing materials, so that the pore volume, the number of ion channels and the concentration of ions in a pore solution are increased, the comprehensive utilization of resources and the harmless and recycling treatment of industrial wastes are realized, and the capacitance of the structural supercapacitor is improved;
3. the super capacitor with the structure is low in preparation cost, environment-friendly, suitable for large-scale application in the field of construction and expected to realize the structural-functional integration of energy storage of green buildings.
Drawings
FIG. 1 is a schematic diagram of a supercapacitor according to the present invention;
FIG. 2 is a cyclic voltammogram of electrodes at different scan rates;
FIG. 3 shows charge and discharge curves of electrodes at different current densities;
FIG. 4 is a cyclic voltammogram of a supercapacitor of example 1 construction;
FIG. 5 is an AC impedance spectrum of the super capacitor of the structure of example 1;
FIG. 6 is a constant current charge-discharge curve of the supercapacitor of example 1;
FIG. 7 is a cyclic voltammogram of a supercapacitor of example 2 construction;
FIG. 8 is an AC impedance spectrum of the super capacitor of the structure of example 2;
FIG. 9 is a constant current charge-discharge curve of the supercapacitor of example 2;
FIG. 10 is a cyclic voltammogram of a supercapacitor of example 3 construction;
FIG. 11 is an AC impedance spectrum of the super capacitor of the structure of example 3;
FIG. 12 is a constant current charge-discharge curve of the supercapacitor of example 3;
FIG. 13 is a cyclic voltammogram of a supercapacitor of example 4 construction;
FIG. 14 is an AC impedance spectrum of the supercapacitor of example 4;
FIG. 15 is a constant current charge-discharge curve of the supercapacitor of example 4;
FIG. 16 is a cyclic voltammogram of a supercapacitor of example 5 construction;
FIG. 17 is an AC impedance spectrum of the super capacitor of the structure of example 5;
FIG. 18 is a constant current charge-discharge curve of the supercapacitor of example 5;
fig. 19 is an SEM image of the surface-reduced graphene oxide of the nickel foam of comparative example 1;
FIG. 20 is an SEM image of the surface reduced graphene oxide of example 1 nickel foam;
fig. 21 is a constant current charge-discharge graph of an electrode.
Reference numerals illustrate: 1 is a structural electrode, 2 is foam nickel, 3 is reduced graphene oxide, 4 is a cation, 5 is an anion, 6 is a cement-based electrolyte, and 7 is a structural supercapacitor.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples. The present embodiment is implemented on the premise of the technical scheme of the present invention, and a detailed implementation manner and a specific operation process are given, but the protection scope of the present invention is not limited to the following examples.
In the following examples, the size of the cement-based electrolyte mold was 40X 40mm in mechanical property test, and the loading speed was 2.4kN/s using a YAW-300E full-automatic pressure tester, and 6 samples were measured for each group, and then the average value was taken. The pore volume of the cement-based electrolyte was measured using a Quantachrome Poremaste 33 mercury porosimeter.
In the electrochemical performance test, the size of the structural super capacitor is 10 multiplied by 5mm, and the Cyclic Voltammetry (CV), constant current charge and Discharge (DC) and the Cyclic Voltammetry (CV), alternating current impedance (EIS) and constant current charge and Discharge (DC) of the structural super capacitor are tested by adopting a CHI 660C electrochemical workstation. The structural supercapacitor was in a saturated water state prior to testing.
The remainder, unless specifically stated, is indicative of a conventional commercial product or conventional processing technique in the art.
Example 1
The preparation method of the graphene-coated foam nickel/cement structure supercapacitor comprises the following specific steps:
weighing 60ml of deionized water and 2g of urea, placing the deionized water and 2g of urea in a liner of a reaction kettle, uniformly mixing to obtain a urea solution, coating reduced graphene oxide 3 on the surface of foam nickel 2 with the thickness of 10 multiplied by 10mm, directly contacting the reduced graphene oxide with a cement-based electrolyte, placing the solution in the urea solution, sealing the reaction kettle, placing the reaction kettle in a baking oven with the temperature of 180 ℃ for hydrothermal reaction for 12 hours, and cooling the reaction kettle to obtain a reduced graphene oxide structural electrode semi-finished product;
washing the semi-finished product of the structural electrode by ethanol for 5 times, washing by deionized water for 5 times, placing the washed foam nickel 2 in a vacuum drying oven at 40 ℃ for drying for 24 hours to obtain the structural electrode 1, wherein the area density of the surface reduced graphene oxide coating of the foam nickel is 1.108mg/cm 2 ；
Weighing 500g of cement, 175g of water and 0.5g of water reducer, putting into a cement paste stirring pot for stirring, adding into a 40X 40mm square mould respectively after fully stirring uniformly, putting into a vibrating table for vibrating to compact a mixture, demoulding after indoor curing for 24 hours, putting into a curing chamber with the temperature of 20 ℃ and the relative humidity of 95%, curing for 28 days, and testing the compressive strength;
adding the obtained stirred material into a 10×10×5mm mold to obtain a flowing cement-based electrolyte 6;
and then respectively assembling the prepared structural electrodes 1 on two sides of the cement-based electrolyte 6, then placing the structural electrodes on a vibrating table for vibrating to compact a mixture, and finally placing the structural electrodes in a curing chamber with the temperature of 20 ℃ and the relative humidity of 95% for curing for 28 days to obtain the structural supercapacitor 7, and testing the electrochemical performance of the structural supercapacitor 7.
The cyclic voltammogram of the electrode of FIG. 2 shows that when the scan rate is increased from 10mV/s to 100mV/s, the cyclic voltammogram remains rectangular in shape without significant deformation, indicating that the electrode conforms to the ideal double layer capacitance behavior and has good reversibility.
As can be seen from the charge-discharge tests under different current densities in FIG. 3, the charge-discharge curves all show symmetrical triangle shapes, and the linear relationship is good, which indicates that the electrode material has good capacitance behavior. When the current density is 1mA/cm, the discharge time is longest, as long as 343.8s. As calculated, the area capacitance of the electrode was 390.7mF/cm 2 . When the current density is increased to 10mA/cm 2 The discharge time was the shortest, 22.8s. Calculated, the area capacitance of the electrode at this time was 253.3mF/cm 2 . The current density is improved ten times, the capacitance retention rate reaches 64.8%, and the electrode has excellent multiplying power performance. The hardened cement paste obtained by the mechanical test has a compressive strength of 49.26MPa for 28 days and a pore volume of 0.1083ml/g.
Fig. 4 is a Cyclic Voltammogram (CV) at a scan rate, which is approximately a rectangular plot, and no pseudocapacitance effect was found throughout the charging process.
Fig. 5 is an alternating current impedance spectrum (EIS) characterizing the internal resistance of a structural supercapacitor, from which an internal resistance of 87.1 Ω can be obtained. FIG. 6 shows a constant current charge-Discharge Curve (DC) which shows an approximately triangular shape with a good linear relationship at a current density of 0.1mA/cm, and the surface capacitance of the structural supercapacitor can be directly calculated to be 11.94mF/cm by the discharge time 2 。
Example 2
The preparation process was essentially the same as in example 1, except that: 400g of cement, 100g of steel slag powder, 175g of water and 0.5g of water reducer are weighed and placed in a cement paste stirring pot for stirring.
The hardened cement paste obtained by the mechanical test has a compressive strength of 44.18MPa for 28 days and a pore volume of 0.1275ml/g. Fig. 7 is a Cyclic Voltammogram (CV) curve at a constant scanning rate, which is a nearly rectangular graph, showing that the current reaches a maximum value at the moment of changing the direction of the voltage, and that the reversibility of charge and discharge is good, and the cyclic voltammogram curve accords with the ideal capacitive behavior. Meanwhile, no pseudocapacitance effect is found in the whole charging process. Fig. 8 is an alternating current impedance spectrum (EIS) characterizing the internal resistance of a structural supercapacitor, from which an internal resistance of 54.4 Ω can be obtained. Fig. 9 is a constant current charge-Discharge Curve (DC), which shows an approximately triangular shape with a relatively good linear relationship at a current density of 0.1mA/cm, indicating that it has a relatively good capacitance characteristic. The surface capacitance of the structural super capacitor can be directly calculated to be 18.68mF/cm through the discharge time 2 。
Example 3
The preparation process was essentially the same as in example 1, except that: 350g of cement, 100g of steel slag powder, 50g of glass powder, 175g of water and 0.5g of water reducer are weighed and placed in a cement paste stirring pot for stirring.
The hardened cement paste obtained by the mechanical test has a compressive strength of 47.19MPa for 28 days and a pore volume of 0.119ml/g. Fig. 10 is a Cyclic Voltammogram (CV) at a constant scanning rate, which is a graph similar to a rectangular graph, showing that the current reaches a maximum value at the moment of changing the direction of the voltage, and that the reversibility of charge and discharge is good, and the cyclic voltammogram corresponds to the ideal capacitive behavior. Meanwhile, no pseudocapacitance effect is found in the whole charging process. Fig. 11 is an alternating current impedance spectrum (EIS) characterizing the internal resistance of a structural supercapacitor, from which an internal resistance of 60.5 Ω can be obtained. Fig. 12 is a constant current charge-Discharge Curve (DC), which shows an approximately triangular shape with a relatively good linear relationship at a current density of 0.1mA/cm, indicating that it has a relatively good capacitance characteristic. The surface capacitance of the structural super capacitor can be directly calculated to be 18.5mF/cm through the discharge time 2 。
Example 4
The preparation process was essentially the same as in example 1, except that: 300g of cement, 100g of steel slag powder, 100g of glass powder, 175g of water and 0.5g of water reducer are weighed and placed in a cement paste stirring pot for stirring.
The hardened cement paste obtained by the mechanical test has a compressive strength of 40.69MPa for 28 days and a pore volume of 0.142ml/g. Fig. 13 is a Cyclic Voltammogram (CV) curve at a constant scanning rate, which is a nearly rectangular graph showing that the current reaches a maximum value at the moment of changing the direction of the voltage, and that the reversibility of charge and discharge is good, and the cyclic voltammogram curve conforms to the ideal capacitive behavior. Meanwhile, no pseudocapacitance effect is found in the whole charging process. Fig. 14 is an alternating current impedance spectrum (EIS) characterizing the internal resistance of a structural supercapacitor, from which an internal resistance of 51.4 Ω can be obtained. FIG. 15 is a constant current charge-Discharge Curve (DC) showing an approximately triangular shape with a good linear relationship at a current density of 0.1 mA/cm. The surface capacitance of the structural super capacitor can be directly calculated to be 20.31mF/cm through the discharge time 2 。
Example 5
The preparation process was essentially the same as in example 1, except that: 250g of cement, 100g of steel slag powder, 150g of glass powder, 175g of water and 0.5g of water reducer are weighed and placed in a cement paste stirring pot for stirring.
The hardened cement paste obtained by the mechanical test has a compressive strength of 33.83MPa for 28 days and a pore volume of 0.1716ml/g. Fig. 16 is a Cyclic Voltammogram (CV) at a constant scanning rate, which is a nearly rectangular graph showing that the current reaches a maximum value at the moment of changing the direction of the voltage, and that the reversibility of charge and discharge is good, and the cyclic voltammogram corresponds to an ideal capacitive behavior. Meanwhile, no pseudocapacitance effect is found in the whole charging process. Fig. 17 is an alternating current impedance spectrum (EIS) characterizing the internal resistance of a structural supercapacitor, from which an internal resistance of 41 Ω can be obtained. Fig. 18 is a constant current charge-Discharge Curve (DC), which shows an approximately triangular shape with a relatively good linear relationship at a current density of 0.1mA/cm, indicating that it has a relatively good capacitance characteristic. The surface capacitance of the structural super capacitor can be directly calculated to be 21.99mF/cm through the discharge time 2 。
Example 6
A preparation method of a graphene coated foam nickel/solid wastewater sludge structure supercapacitor comprises the following steps:
step 1, preparing a structural electrode: weighing 60ml of deionized water and 2g of urea, placing the deionized water and the 2g of urea in a liner of a reaction kettle, uniformly mixing to obtain urea solution, coating reduced graphene oxide 3 on the surface of foam nickel 2 with the size of 10 multiplied by 10mm, and placing the foam nickel coated with the reduced graphene oxide 3 in the urea solution; putting the reaction kettle into a baking oven with the temperature of 180 ℃ for hydrothermal reaction for 12 hours, and cooling the reaction kettle to obtain a semi-finished product of the electrode with the reduced graphene oxide structure; the semi-finished product of the structural electrode is washed for 5 times by ethanol, then washed for 5 times by deionized water, finally dried for 24 hours in a vacuum drying oven at the temperature of 40 ℃ to obtain the structural electrode 1, and the area density of the reduced graphene oxide coating on the surface of the foam nickel is 1.108mg/cm 2 ；
Step 2, preparation of cement-based electrolyte: 100g of steel slag powder, 150g of glass powder and 250g of cement are uniformly mixed, 200g of deionized water and 0.5g of water reducer are added, fully and uniformly stirred, poured into a 10X 5mm die, and vibrated to be compact, so that the flowing cement-based electrolyte 6 is obtained.
(3) And (3) assembling the structural electrode 1 prepared in the step (1) on two sides of the cement-based electrolyte 6 in the flowing state in the step (2), vibrating to compact the cement-based electrolyte, demolding, and then placing the structural electrode in a curing chamber with the temperature of 20 ℃ and the relative humidity of 95% for curing to obtain the structural supercapacitor 7.
Through detection, the prepared graphene-coated foam nickel/solid wastewater sludge structure super capacitor has excellent mechanical properties and good specific capacitance.
Example 7
The preparation process was essentially the same as in example 6, except that: preparation of cement-based electrolyte 6: 100g of steel slag powder, 150g of glass powder and 250g of cement are uniformly mixed, 225g of deionized water and 0.5g of water reducer are added, fully and uniformly stirred, poured into a 10X 5mm die, and vibrated to be compact, so that the flowing cement-based electrolyte is obtained.
Through detection, the prepared graphene coated foam nickel/solid waste modified cement structure supercapacitor has excellent mechanical properties and good specific capacitance.
Comparative example 1: compared with the example 1, the rest conditions are unchanged, but the structural electrode is obtained by directly placing foam nickel in a mixed solution of graphene oxide, deionized water and urea and performing hydrothermal reaction.
Most of them are the same as in example 1, except that the reduced graphene oxide content, the microstructure and the electrochemical properties carried by the nickel foam surface are significantly different. The area densities of the electrode foam nickel surface reduced graphene oxide in comparative example 1 and example 1 were 0.45mg/cm, respectively 2 And 1.2mg/cm 2 . Fig. 19 is an SEM image of the reduced graphene oxide surface of the nickel foam of comparative example 1. As is clear from the figure, the reduced graphene oxide has a pleated sheet shape, and has a large amount of impurities on the surface thereof. The reduced graphene oxide in example 1 was uniformly distributed and contained only a small amount of impurities (fig. 20). Fig. 21 is a constant current charge-discharge graph of the electrodes in comparative example 1 and example 1. At a current density of 0.2mA/cm, the electrode charge-discharge curves in comparative example 1 and example 1 exhibited approximately triangular shapes, and the linear relationship was relatively good, indicating that it had good capacitance characteristics. The area capacitance of the electrodes in comparative example 1 and example 1 was directly calculated to be 60.75mF/cm, respectively, by the discharge time 2 And 105.5mF/cm 2 。
The specific results of examples 1-5 are shown in Table 1.
Table 1 cement-based electrolyte 28 day compressive strength and pore volume
| Examples | Compressive strength (MPa) | Pore volume (ml/g) |
| Example 1 | 49.26 | 0.1083 |
| Example 2 | 44.18 | 0.1275 |
| Example 3 | 47.19 | 0.119 |
| Example 4 | 40.69 | 0.142 |
| Example 5 | 33.83 | 0.1716 |
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The graphene-coated foam nickel/cement structure supercapacitor is characterized in that the structure supercapacitor (7) comprises structure electrodes (1) on two sides and cement-based electrolyte (6) arranged between the structure electrodes (1), wherein the structure electrodes (1) consist of reduced graphene oxide (3) and foam nickel (2), and the cement-based electrolyte (6) is prepared from solid waste, cement, water and a water reducing agent, and the solid waste comprises steel slag powder and glass powder;
the concrete preparation method of the cement-based electrolyte (6) comprises the following steps: and uniformly mixing the solid waste and cement, adding deionized water and a water reducing agent, and stirring to obtain the cement-based electrolyte (6).
2. The graphene-coated foam nickel/cement structure supercapacitor according to claim 1, wherein the reduced graphene oxide (3) is coated on the surface of the foam nickel (2), the reduced graphene oxide (3) is directly contacted with the cement-based electrolyte (6), and the area density of the reduced graphene oxide (3) is 1-1.2 mg/cm 2 。
3. The graphene-coated foam nickel/cement structure supercapacitor according to claim 1 is characterized in that the solid waste comprises steel slag powder and glass powder in a mass ratio of (1-3): (0-3), and the content of the glass powder is not 0.
4. The graphene-coated foam nickel/cement structure supercapacitor according to claim 1 is characterized in that the mass ratio of the solid waste to the cement to the water and the water reducing agent is (20-50): (50-80): (30-50): (0.1-0.2).
5. The super capacitor with the graphene-coated foam nickel/cement structure according to claim 1, wherein the specific surface area of the steel slag powder is more than 400 and 400m 2 The intensity activity index of the powder/kg and 28d reaches more than 80 percent;
the specific surface area of the glass powder is more than 400 and 400m 2 The intensity activity index per kg,28d reaches more than 80%.
6. A method for preparing the graphene-coated foam nickel/cement structure supercapacitor according to any one of claims 1 to 5, comprising the following steps:
s1, preparing a structural electrode: coating reduced graphene oxide (3) on the surface of foam nickel (2), placing the foam nickel in urea solution, and reacting to obtain a structural electrode (1);
s2, preparing a cement-based electrolyte: uniformly mixing solid waste and cement, adding deionized water and a water reducing agent, and stirring to obtain a cement-based electrolyte (6);
s3, assembling the structural electrode (1) prepared in the step S1 on two sides of the cement-based electrolyte (6) prepared in the step S2 to obtain the structural supercapacitor (7).
7. The preparation method of the graphene-coated foam nickel/cement structure supercapacitor according to claim 6, wherein in the step S1, the mass ratio of urea to deionized water in the urea solution is (1-2): (50-70), and/or,
in the step S1, the specific reaction steps are that the foam nickel coated with the reduced graphene oxide (3) is placed in urea solution of a reaction kettle lining, the reaction kettle is placed in an oven for hydrothermal reaction, and/or,
in the step S1, after the reaction is completed, the obtained reaction product is firstly washed by 98% ethanol, then washed by deionized water, and the structural electrode is obtained after drying.
8. The preparation method of the graphene-coated foam nickel/cement structure supercapacitor according to claim 7 is characterized in that the cleaning times of ethanol and deionized water are 3-5 times respectively, and the drying temperature is 40-60 ℃.
9. The method for manufacturing a graphene-coated foam nickel/cement-structured supercapacitor according to claim 6, wherein in step S2, the cement-based electrolyte is in a flowing state, and/or,
in the step S3, after the assembly is completed, the cement-based electrolyte is compacted by vibration, and the cement-based electrolyte is placed in a curing chamber for curing after demolding.
10. Use of a graphene-coated foam nickel/cement structured supercapacitor according to any one of claims 1 to 5, characterized in that it is applied in the field of production of buildings.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211058508.8A CN115424868B (en) | 2022-08-30 | 2022-08-30 | Super capacitor with graphene coated foam nickel/cement structure and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211058508.8A CN115424868B (en) | 2022-08-30 | 2022-08-30 | Super capacitor with graphene coated foam nickel/cement structure and preparation and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115424868A CN115424868A (en) | 2022-12-02 |
| CN115424868B true CN115424868B (en) | 2023-08-29 |
Family
ID=84199611
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211058508.8A Active CN115424868B (en) | 2022-08-30 | 2022-08-30 | Super capacitor with graphene coated foam nickel/cement structure and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115424868B (en) |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001338845A (en) * | 2000-03-22 | 2001-12-07 | Nippon Chemicon Corp | Method and device for manufacturing solid electrolytic capacitor |
| RU2394005C1 (en) * | 2009-06-15 | 2010-07-10 | Александр Макарович Салдаев | Method of making building blocks |
| CN103258656A (en) * | 2013-04-25 | 2013-08-21 | 华中科技大学 | Method for preparing electrodes of super capacitor based on nickel foam and products thereof |
| CN105088274A (en) * | 2015-08-24 | 2015-11-25 | 沈阳北冶冶金科技有限公司 | Device for treating and recycling aluminum electrolysis solid waste |
| CN105428085A (en) * | 2014-09-23 | 2016-03-23 | 中国科学院大连化学物理研究所 | Biomass-based colloidal electrolyte and biomass-based colloidal electrolyte super capacitor |
| CN105731942A (en) * | 2016-01-19 | 2016-07-06 | 中国建筑材料科学研究总院 | Cement-based composite material used for 3D printing as well as preparation method and application thereof |
| KR101775468B1 (en) * | 2016-09-30 | 2017-09-06 | 전북대학교산학협력단 | Electrode for the super capacitor and method of the same |
| CN107195478A (en) * | 2017-04-26 | 2017-09-22 | 同济大学 | A kind of graphene/magnesium phosphate cement structure ultracapacitor |
| CN107481869A (en) * | 2017-08-11 | 2017-12-15 | 北京大学 | A kind of double-network hydrogel electrolyte and its preparation and application |
| CN110627470A (en) * | 2019-11-01 | 2019-12-31 | 新化县天马建筑新材料科技有限公司 | Double-network reinforced composite quick-drying gel cement material and preparation method thereof |
| CN113012947A (en) * | 2021-02-07 | 2021-06-22 | 中国科学院福建物质结构研究所 | Preparation method and application of water-based solid electrolyte |
| CN113321201A (en) * | 2021-06-11 | 2021-08-31 | 同济大学 | Porous carbon material based on waste recovered epoxy resin and preparation method and application thereof |
| CN113436908A (en) * | 2021-06-10 | 2021-09-24 | 同济大学 | Structural super capacitor and preparation method thereof |
| CN114920510A (en) * | 2022-04-26 | 2022-08-19 | 东南大学 | Preparation method and application of cement-based-hydrogel composite electrolyte material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20160045841A1 (en) * | 2013-03-15 | 2016-02-18 | Transtar Group, Ltd. | New and improved system for processing various chemicals and materials |
-
2022
- 2022-08-30 CN CN202211058508.8A patent/CN115424868B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001338845A (en) * | 2000-03-22 | 2001-12-07 | Nippon Chemicon Corp | Method and device for manufacturing solid electrolytic capacitor |
| RU2394005C1 (en) * | 2009-06-15 | 2010-07-10 | Александр Макарович Салдаев | Method of making building blocks |
| CN103258656A (en) * | 2013-04-25 | 2013-08-21 | 华中科技大学 | Method for preparing electrodes of super capacitor based on nickel foam and products thereof |
| CN105428085A (en) * | 2014-09-23 | 2016-03-23 | 中国科学院大连化学物理研究所 | Biomass-based colloidal electrolyte and biomass-based colloidal electrolyte super capacitor |
| CN105088274A (en) * | 2015-08-24 | 2015-11-25 | 沈阳北冶冶金科技有限公司 | Device for treating and recycling aluminum electrolysis solid waste |
| CN105731942A (en) * | 2016-01-19 | 2016-07-06 | 中国建筑材料科学研究总院 | Cement-based composite material used for 3D printing as well as preparation method and application thereof |
| KR101775468B1 (en) * | 2016-09-30 | 2017-09-06 | 전북대학교산학협력단 | Electrode for the super capacitor and method of the same |
| CN107195478A (en) * | 2017-04-26 | 2017-09-22 | 同济大学 | A kind of graphene/magnesium phosphate cement structure ultracapacitor |
| CN107481869A (en) * | 2017-08-11 | 2017-12-15 | 北京大学 | A kind of double-network hydrogel electrolyte and its preparation and application |
| CN110627470A (en) * | 2019-11-01 | 2019-12-31 | 新化县天马建筑新材料科技有限公司 | Double-network reinforced composite quick-drying gel cement material and preparation method thereof |
| CN113012947A (en) * | 2021-02-07 | 2021-06-22 | 中国科学院福建物质结构研究所 | Preparation method and application of water-based solid electrolyte |
| CN113436908A (en) * | 2021-06-10 | 2021-09-24 | 同济大学 | Structural super capacitor and preparation method thereof |
| CN113321201A (en) * | 2021-06-11 | 2021-08-31 | 同济大学 | Porous carbon material based on waste recovered epoxy resin and preparation method and application thereof |
| CN114920510A (en) * | 2022-04-26 | 2022-08-19 | 东南大学 | Preparation method and application of cement-based-hydrogel composite electrolyte material |
Non-Patent Citations (1)
| Title |
|---|
| 氧化石墨烯在水泥基材料中的应用研究综述;何欣 等;粉煤灰综合利用;第34卷(第04期);第55-58页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115424868A (en) | 2022-12-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Fang et al. | A large areal capacitance structural supercapacitor with a 3D rGO@ MnO 2 foam electrode and polyacrylic acid–Portland cement–KOH electrolyte | |
| CN105140466B (en) | A kind of lead carbon battery negative plate | |
| CN105602309B (en) | A kind of sub- coating paste of high resiliency diversion and its lithium ion battery separator preparation method | |
| CN102201575A (en) | Lead sulfate-graphene composite electrode material and lead-acid battery negative electrode lead paste containing same | |
| CN108878835A (en) | A kind of preparation method of lithium sulfur battery anode material | |
| CN110504110B (en) | Method for preparing supercapacitor by using multi-connected pyridyl metal organic framework Ni-MOF | |
| CN110491676B (en) | Method for preparing high-voltage-resistant electrode material by using porous carbon polyaniline | |
| CN105405676A (en) | Novel structured supercapacitor taking graphene and cement as materials and fabrication of supercapacitor | |
| CN107195478B (en) | A kind of graphene/magnesium phosphate cement structure supercapacitor | |
| CN113436908B (en) | Structural super capacitor and preparation method thereof | |
| CN115424868B (en) | Super capacitor with graphene coated foam nickel/cement structure and preparation and application thereof | |
| CN103762388B (en) | A kind of internal formation process of electric motor car valve-regulated lead-acid battery | |
| CN111477818B (en) | Full-ceramic lithium ion battery diaphragm and preparation method thereof | |
| CN107732244A (en) | A kind of rice husk base charcoal based additive for lead carbon battery negative pole | |
| CN108383491A (en) | Kaolinite soil matrix heat accumulation ceramics and preparation method thereof | |
| JP5396216B2 (en) | Lead acid battery | |
| CN102263254A (en) | Method for producing composite anode of lead acid battery | |
| CN112086642A (en) | Graphitized carbon-coated high-specific-surface-area porous carbon sphere and preparation method and application thereof | |
| CN107331866A (en) | A kind of application of expanded graphite in kalium ion battery negative material | |
| CN111934028A (en) | Lead-acid battery manufacturing method based on conductive adhesive and lead sulfate | |
| CN101388446B (en) | Three-dimensional electrode for accummulater and preparing mehtod | |
| Wang et al. | Porous polymer cement composites for quasi-solid graphene supercapacitors | |
| CN108376788B (en) | Zinc-bromine flow battery pole plate | |
| CN109461975B (en) | Graphene lead-carbon power battery and manufacturing method thereof | |
| CN106683895A (en) | Anthraquinone-based modified composite electrode material, preparation method and application thereof, and electronic component containing anthraquinone-based modified composite electrode material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |