CN110571065B - Graphene composite hydrogel and preparation and application thereof - Google Patents

Graphene composite hydrogel and preparation and application thereof Download PDF

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CN110571065B
CN110571065B CN201910848218.5A CN201910848218A CN110571065B CN 110571065 B CN110571065 B CN 110571065B CN 201910848218 A CN201910848218 A CN 201910848218A CN 110571065 B CN110571065 B CN 110571065B
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composite hydrogel
graphene
mesoporous carbon
carbon nanospheres
nanospheres
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CN110571065A (en
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王�义
赵明宇
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Donghua University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • 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
    • H01G11/26—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 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
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • 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 composite hydrogel and preparation and application thereof. The composite hydrogel comprises graphene and mesoporous carbon nanospheres. The preparation method comprises the following steps: dispersing graphene oxide and mesoporous carbon nanospheres in water, performing ultrasonic treatment by using a probe until the graphene oxide and the mesoporous carbon nanospheres are uniformly dispersed to obtain a dispersion liquid, and adding a weak reducing agent for hydrothermal reaction. The all-solid-state supercapacitor assembled by the composite hydrogel has high specific capacitance, high volume energy density and good flexibility, and the capacitance performance of the all-solid-state supercapacitor can be obviously improved under the irradiation of sunlight.

Description

Graphene composite hydrogel and preparation and application thereof
Technical Field
The invention belongs to the field of supercapacitor electrodes and preparation and application thereof, and particularly relates to graphene composite hydrogel and preparation and application thereof.
Background
The rapid development of technologies for wearable devices, electronic textiles, mobile devices, and implanted electronics has enabled the electronics field to be in the era of a diverse array of smart devices, which require separate energy storage and power supply systems, and which require good mechanical stability. Therefore, the development of multifunctional self-powered flexible wearable intelligent devices is of great significance. Currently, flexible self-powered devices comprise: flexible lithium ion batteries, fuel cells, supercapacitors, and the like. Among them, supercapacitors are becoming an important energy storage system due to their fast charge and discharge, high power density, and long cycle life. Flexible flexible supercapacitor pairing toolMiniaturized devices with low power requirements provide energy. Key to the development of flexible capacitors: (1) preparing an electrode material having high capacity and stability; (2) has good flexibility and operability. In order to solve the problems, the current electrochemical capacitor generally adopts a porous activated carbon electrode structure, the mass specific capacitance is generally about 80-120F/g, the mass energy density is about 4-5Wh/kg, the requirement of practical application is not met, and a pure activated carbon electrode has no flexible operability. Recent research shows that graphene has a theoretical surface area of about 2630m due to high internal conductivity, excellent flexibility and ultrahigh theoretical surface area2And/g, the theoretical mass specific capacitance is about 550F/g. Meanwhile, graphene can form a mechanically stable flexible film, and is an ideal material for developing flexible capacitors.
However, there are strong pi-pi interactions between graphene sheets, they are prone to stacking to form aggregates with reduced specific surface area, which severely reduces their adsorption and diffusion of ions, resulting in lower specific capacitance (typically <180F/g in organic electrolytes) and relatively lower charge/discharge rates. In comparison, the mesoporous carbon nanospheres can be used as a carbon material with high energy storage efficiency due to the characteristics of small size, large specific surface area, uniform pore size distribution and the like, but the nanospheres are zero-dimensional materials, so that the stacking of the spheres leads to large internal resistance of the whole electrode and slow electron transmission speed, thereby reducing the performance of the electrode in electrochemical energy storage. Therefore, there is a great challenge to produce flexible energy storage devices with high energy density and maintaining good mechanical properties.
In addition, one of the big problems to be solved for flexible wearable energy storage devices, especially in all-solid-state ultracapacitors, is the diminished energy storage capacity of the ultracapacitors at low temperatures or in extreme environments (cold climates). It is important to develop a green sustainable strategy to enhance the performance of capacitors in low temperature environments. As is well known, solar energy is an inexhaustible natural resource and has attracted worldwide attention. Under the irradiation of sunlight, a plurality of photo-thermal materials can realize the conversion between light energy and heat energy, and realize photo-thermal heating to improve the temperature. However, it is only rarely reported that the capacitor with high light-heat conversion capability is prepared, and the capacitance performance of the capacitor under low temperature environment, especially the capacitance performance of the flexible capacitor, is improved by using sunlight. (YI F, REN H, DAI K, et al. solar thermal-drive characterization of supercapacitors [ J ]. Energy & Environmental Science,2018,11(8):2016-24.)
Disclosure of Invention
The invention aims to solve the technical problem of providing graphene composite hydrogel and preparation and application thereof, so as to overcome the defects that an all-solid-state supercapacitor in the prior art is not enough in flexibility and the energy storage capacity is weakened in a low-temperature or extreme environment.
The invention provides graphene composite hydrogel which comprises graphene and mesoporous carbon nanospheres in a mass ratio of 1-4: 1.
The mesoporous carbon nanospheres are nitrogen-doped mesoporous carbon nanospheres and are obtained by co-calcining phenolic resin prepolymer nanospheres and melamine.
The diameter of the mesoporous carbon nanosphere is 50-100nm, and the aperture is 2-5 nm.
The composite hydrogel has a three-dimensional structure with hierarchical pores, wherein the hierarchical pores are micropores, mesopores and macropores.
The composite hydrogel can be prepared into any shape according to a mould.
The invention also provides a preparation method of the graphene composite hydrogel, which comprises the following steps:
(1) dispersing graphene oxide and mesoporous carbon nanospheres in water according to a mass ratio of 1-4:1, stirring, and performing ultrasonic treatment by using a probe until the graphene oxide and the mesoporous carbon nanospheres are uniformly dispersed to obtain a dispersion liquid, wherein the concentration of the graphene oxide in the dispersion liquid is 1-3 mg/mL;
(2) and (3) adding a weak reducing agent into the dispersion liquid obtained in the step (1), and carrying out hydrothermal reaction to obtain the graphene composite hydrogel, wherein the mass ratio of the weak reducing agent to the graphene oxide obtained in the step (1) is 2-5: 1.
The stirring time in the step (1) is 0.5-2 h; the ultrasonic time is 2-4 h.
The weak reducing agent in the step (2) has the characteristics of being easily soluble in water and the like, and comprises ascorbic acid, sodium ascorbate, cysteine or sodium borohydride.
The hydrothermal reaction temperature in the step (2) is 80-100 ℃, and the hydrothermal reaction time is 2-6 h.
The invention also provides application of the graphene composite hydrogel in an all-solid-state supercapacitor.
The invention also provides an all-solid-state supercapacitor, the composite hydrogel is prepared into any shape through a die, after washing, the composite hydrogel is directly pressed on a stainless steel net to prepare an electrode, the pressed electrode is coated with a polymer electrolyte, and the all-solid-state supercapacitor is assembled after drying.
The pressing pressure is 1-10 MPa.
The mesh number of the stainless steel net is 400-800 meshes.
The polymer electrolyte is PVA/H2SO4The sulfuric acid concentration was 1M and the PVA concentration was 10 wt%.
The mesoporous carbon nanospheres can be inserted between graphene sheet layers to prevent the graphene sheet layers from being stacked, meanwhile, the graphene can be lapped with the mesoporous carbon nanospheres to realize electron transmission, and the ion capacity and the conductivity of the electrode can be improved under the synergistic effect of the graphene sheet layers and the mesoporous carbon nanospheres.
The all-solid-state supercapacitor is an all-solid-state flexible solar photo-thermal supercapacitor, and the specific capacitance value is 8.1F cm-3(ii) a The internal resistance is low, the CV curve is similar to a rectangle, and the GCD charge-discharge curve is a symmetrical triangle; under the irradiation of sunlight, the capacitance performance of the solar cell can be improved.
The invention utilizes graphene (high conductivity and easy formation of flexible aerogel) and nitrogen-doped mesoporous carbon nanospheres (huge charge storage and improved electrolyte wettability) and simultaneously utilizes the strong photo-thermal conversion capability of the graphene and the nitrogen-doped mesoporous carbon nanospheres to construct the solar enhanced flexible all-solid-state supercapacitor. The supercapacitor is composed of a three-dimensional graphene hydrogel (N-MCN @ GH) composite electrode film of a nitrogen-doped mesoporous carbon sphere intercalation, and due to the synergistic effect of the carbon nanospheres and graphene, the composite has a layered porous structure and a large contactable surface area, and can realize rapid applicationElectron transport and ion transport with high energy density (1.1 mWh/cm)3) And a power density of (13.3 mW/cm)3) And has good cycling stability (80% retained at 5A/g after 10000 cycles). More importantly, the photo-thermal type super capacitor can be irradiated by solar energy (0.36W/cm)2) The rapid recovery of the capacitance to 1.7 times of the initial value under the low-temperature environment (5 ℃) is realized. The method provides a new idea for the design of the flexible all-solid-state super photo-thermal capacitor and provides an innovative strategy for improving the performance in a low-temperature environment.
The all-solid-state flexible solar photo-thermal supercapacitor is prepared by simply pressing mesoporous carbon sphere intercalated graphene composite hydrogel serving as an electrode material, has good flexibility and mechanical stability and high capacity, and can enhance the capacitance performance by utilizing solar illumination.
Advantageous effects
The preparation method is simple and strong in operability, and the obtained N-MCN @ GH all-solid-state supercapacitor is high in specific capacitance, high in volume energy density and good in flexibility, and the visible light absorption of the capacitor is higher than that of a pure graphene-based (GH) capacitor, so that the capacitance performance of the capacitor can be remarkably improved under the irradiation of sunlight, and the capacitance attenuated at low temperature can be recovered.
Drawings
FIG. 1 is a simplified flow diagram (a) of a process for making an N-MCN @ GH flexible capacitor electrode of the present invention; SEM pictures (b-c), photomicrographs (d), TEM (e-f), XRD (g) (where the inset is Raman), STEM (h), HRTEM (i), EDS Mapping (j) for N-MCN @ GH in example 1.
FIG. 2 is XPS (a-c) and nitrogen desorption curves (d) for the N-MCN @ GH and GH hydrogels of example 2 (where the inset is the pore size distribution plot).
FIG. 3 is a comparison of CV (a), GCD (b), mass specific capacitance (c) and EIS (d) for the N-MCN @ GH supercapacitor and GH supercapacitor of example 3.
FIG. 4 is a graph of CV (a), GCD (b), volumetric, area specific capacitance (c), Ragon (d), and charge-discharge cycle life for the N-MCN @ GH supercapacitor of example 3.
Fig. 5 is a graph of cv (a), gcd (b), series lit LED lamps (c), different degrees of bending cv (d) (where the inset is a digital photograph of the capacitor in the bent state), bend life test (e) (where the inset is a bend life test of the capacitor in a universal tensile tester), and fold life test (f) (where the inset is a digital photograph of the capacitor in the folded state) for the N-MCN @ GH supercapacitors of example 4, in series and parallel.
Fig. 6 shows the uv absorption plots (a), the photothermal efficiency (b), the gcd (c) under different temperature conditions, the EIS (d) (where the inset is an enlarged view of the EIS) and the change in capacitance (e) under different conditions for the GH electrode and the N-MCN @ GH electrode in example 3.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) 1.8g of phenol was dissolved in 45mL of an aqueous sodium hydroxide solution (1M) and mixed with 6.3mL of a formaldehyde solution (37 wt%), and 45mL of a 64mg/mL F127 solution was added thereto, heated to 66 ℃ and stirred for 2 hours, followed by addition of 150mL of water and continued reaction for 18 hours. After the reaction is completed, the solution is diluted by 3 times and is put into a hydrothermal kettle for hydrothermal reaction at a high temperature of 130 ℃ for 24 hours to obtain phenolic resin prepolymer nanospheres, and the nanospheres are washed, dried and calcined with melamine at a temperature of 900 ℃ for 2 hours to obtain the nitrogen-doped mesoporous carbon nanospheres.
(2) 1mg of the mesoporous carbon nanospheres are added into 1mL of graphene oxide solution containing 2mg/mL, and the solution is subjected to ultrasonic treatment for 1 hour by a probe to obtain uniform dispersion liquid.
(3) And (3) adding a sodium ascorbate solution (50 mu L, the concentration of 1M) into the dispersion liquid obtained in the step (2), and carrying out hydrothermal reaction at 100 ℃ for 2 hours to obtain the graphene composite hydrogel.
FIGS. 1b-c, e-i and j show that the mesoporous carbon nanospheres are embedded in the graphene sheet layer to form a three-dimensional network structure, and FIG. (d) shows that the hydrogel can be made into any shape.
Example 2
According to the example 1, the mass of the mesoporous carbon nanoball in the step (2) is modified to 2mg, and the rest is the same as the example 1, so that the graphene composite (N-MCN @ GH) hydrogel is obtained.
The pure Graphene (GH) hydrogel was the same as in example 1 except that no mesoporous carbon nanospheres were added.
FIGS. 2a-c show nitrogen element peaks, which prove that the nitrogen-doped mesoporous carbon nanospheres are embedded into the graphene network, and FIG. 2d shows that the specific surface area of N-MCN @ GH is 742m2G, GH specific surface area of 125m2And/g, the addition of the mesoporous carbon nanospheres is proved to effectively improve the specific surface area of the compound, thereby being beneficial to the immersion of the electrolyte.
Example 3
The graphene composite hydrogel in example 2 was directly pressed on a current collector stainless steel mesh (500 mesh) under a pressure of 10MPa, and a polymer electrolyte PVA/H was used2SO4(the concentration of PVA is 10 wt%, the concentration of sulfuric acid is 1M), the electrolyte is coated on the electrodes, and after drying, the two electrodes are oppositely overlapped to assemble the flexible all-solid-state supercapacitor.
The pure Graphene (GH) hydrogel of example 2 was assembled into GH supercapacitors according to the method described above.
The capacitor was placed under a solar simulator (0.36W/cm)2) And simulating a low-temperature environment by a constant-temperature water bath under the capacitor, and testing the electrochemical performance of the capacitor under the illumination condition, as shown in fig. 6, the N-MCN @ GH electrode has stronger absorption capacity to light, because the mesoporous carbon nanospheres are embedded and can improve the absorption to light through multiple reflection, and the carbon material is a negative temperature coefficient material, so that the resistance is reduced at the increased temperature, and further, the low-temperature illumination test of the capacitor shows that the performance of the capacitor is sharply reduced to 50% at the low temperature (5 ℃), and the performance of the capacitor is sharply reduced to 50% at the low temperature (0.36W/cm)2The solar illumination of (2) causes the capacitor performance to recover and rise to 1.7 times before.
Fig. 3 shows that the N-MCN @ GH capacitance performance 160F/g is better than GH 90F/g, because the addition of N-MCN effectively prevents stacking between graphene sheets, and simultaneously graphene forms a lap joint with carbon nanospheres, and the two synergistically provide a higher specific surface area and ordered pore channels, further improving the overall capacitance performance.
FIG. 4 shows that the N-MCN @ GH supercapacitor has higher volume specific capacity (8.1F/cm)3) And energy density (1.1 mWh/cm)3) And the capacitance can still maintain 80% after 10000 times of charge and discharge cycles.
Example 4
According to example 1, 2mg of mesoporous carbon nanoball was added to 2mL of deionized water containing 4mg of graphene oxide, and the rest was the same as example 1, to obtain graphene composite hydrogel, which was directly pressed on a current collector stainless steel mesh (500 mesh) under 10MPa pressure, and using polymer electrolyte PVA/H2SO4(the concentration of PVA is 10 wt%, the concentration of sulfuric acid is 1M), coating electrolyte on the electrodes, assembling two electrodes into a flexible all-solid-state supercapacitor after drying, connecting the same capacitors in series and parallel, and testing the series and parallel electrochemical performance of the capacitors.
Fig. 5 shows that N-MCN @ GH capacitors can provide different voltage outputs through series connection and parallel connection, and the capacitors have better mechanical properties, and CV tests can be performed under different degrees of bending to show that the capacitors are stable. The capacitance of 90% and 95% can be respectively maintained after 1000 times of bending or 100 times of folding.
Example 5
According to the embodiment 1, 2mg of mesoporous carbon nanospheres are added into 2mL of deionized water containing 4mg of graphene oxide, the rest is the same as that in the embodiment 1, graphene composite hydrogel is obtained, the hydrogel is soaked in 1M sulfuric acid for 24 hours, and the graphene composite hydrogel is packaged and tested according to the conditions in the embodiment 4, wherein the cyclic voltammetry curve (voltage window is 0V to 1V, scanning rate is 5-100 mV/s) and the charge-discharge curve (current density is 0.5-20A/g) of the graphene composite hydrogel are tested, and the specific mass capacity of the graphene composite hydrogel is 160F/g.

Claims (7)

1. The graphene composite hydrogel is characterized by comprising graphene and mesoporous carbon nanospheres in a mass ratio of 1-4: 1;
the mesoporous carbon nanospheres are nitrogen-doped mesoporous carbon nanospheres and are obtained by co-calcining phenolic resin prepolymer nanospheres and melamine;
the preparation method of the phenolic resin prepolymer nanosphere comprises the following steps: dissolving 1.8g of phenol, mixing with 6.3mL of 37 wt% formaldehyde solution, and adding 45mL of 64mg/mL F127 solution for hydrothermal reaction to obtain phenolic resin prepolymer nanospheres;
the composite hydrogel has a three-dimensional structure with hierarchical pores, wherein the hierarchical pores are micropores, mesopores and macropores;
the graphene composite hydrogel is prepared into an all-solid-state supercapacitor which is a photo-thermal supercapacitor, and the capacitance of the supercapacitor can be quickly recovered to 1.7 times of the initial value by sunlight irradiation at the low temperature of 5 ℃.
2. The hydrogel of claim 1, wherein the composite hydrogel can be formed into any shape according to a mold.
3. A method for preparing the graphene composite hydrogel according to claim 1, comprising:
(1) dispersing graphene oxide and mesoporous carbon nanospheres in water according to a mass ratio of 1-4:1, stirring, and performing ultrasonic treatment by using a probe until the graphene oxide and the mesoporous carbon nanospheres are uniformly dispersed to obtain a dispersion liquid, wherein the concentration of the graphene oxide in the dispersion liquid is 1-3 mg/mL;
(2) and (3) adding a weak reducing agent into the dispersion liquid obtained in the step (1), and carrying out hydrothermal reaction to obtain the graphene composite hydrogel, wherein the mass ratio of the weak reducing agent to the graphene oxide obtained in the step (1) is 2-5: 1.
4. The method according to claim 3, wherein the stirring time in the step (1) is 0.5-2 h; the ultrasonic time is 2-4 h.
5. The method according to claim 3, wherein the weak reducing agent in step (2) comprises ascorbic acid, sodium ascorbate, cysteine or sodium borohydride.
6. The method according to claim 3, wherein the hydrothermal reaction temperature in the step (2) is 80-100 ℃ and the hydrothermal reaction time is 2-6 h.
7. An all-solid-state supercapacitor, characterized in that the composite hydrogel according to claim 1 is prepared into any shape by a mold, after washing, the composite hydrogel is directly pressed on a stainless steel net to prepare an electrode, the pressed electrode is coated with a polymer electrolyte, and the electrode is assembled after drying.
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