CN113772660B - Method for preparing high-volume-ratio-capacitance graphene by using metal cation-assisted heat treatment technology - Google Patents

Method for preparing high-volume-ratio-capacitance graphene by using metal cation-assisted heat treatment technology Download PDF

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CN113772660B
CN113772660B CN202110843041.7A CN202110843041A CN113772660B CN 113772660 B CN113772660 B CN 113772660B CN 202110843041 A CN202110843041 A CN 202110843041A CN 113772660 B CN113772660 B CN 113772660B
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heat treatment
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CN113772660A (en
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王黎东
刘兆远
费维栋
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Harbin Institute of Technology
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/182—Graphene
    • C01B32/184—Preparation
    • 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
    • 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
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    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
    • C01B2204/20—Graphene characterized by its properties
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
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    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2204/00—Structure or properties of graphene
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

Abstract

A kind of rice cakeA method for preparing high-volume-ratio-capacitance graphene by using a metal cation-assisted heat treatment technology belongs to the technical field of super capacitors. The invention aims to solve the technical problems of low bulk density and low volume specific capacitance of the existing graphene material, and the method comprises the following steps: uniformly dispersing graphene oxide in deionized water; then adding metal ion salt, mixing uniformly, then carrying out solid-liquid separation, and drying; then heat treating, washing with water until the ion concentration of the supernatant is less than 10 ‑ 3 molL ‑1 And drying to obtain the high-volume-ratio capacitance graphene. The bulk density of the graphene material prepared by the invention is 0.9-1.7gcm ‑3 Volume specific capacitance of 200-520Fcm ‑3 (ii) a Is suitable for preparing the super capacitor with high volume specific capacitance.

Description

Method for preparing high-volume-ratio-capacitance graphene by using metal cation-assisted heat treatment technology
Technical Field
The invention belongs to the technical field of super capacitors; in particular to a method for preparing high-volume-ratio capacitance graphene by using a metal cation auxiliary heat treatment technology.
Background
As a novel energy storage device, the super capacitor has the advantages of high power density, long cycle life, low maintenance cost, environmental protection and the like, and is a hotspot in the research of the field of new energy. Carbon materials are widely used as electrode materials due to their stable structure, high electrical conductivity, and low production cost. Among many carbon materials, graphene attracts much attention due to its excellent physicochemical properties, such as high specific surface area and good electron mobility. Theoretical calculation shows that the specific surface area of the single-layer graphene can reach 2630m 2 g -1 The theoretical specific capacitance can reach 550 Fg -1 . However, the graphene is inevitably agglomerated in the preparation process, so that the practical electric double layer capacitance of the graphene is generally not higher than 200 Fg -1 Although agglomeration can be avoided by preparing the three-dimensional porous graphene, the volume specific capacitance of the graphene is very low, and the preparation method is not beneficial to practical application.
In order to improve the electrochemical performance of graphene materials, high specific surface area and reasonable adjustment of pore structure distribution are generally required to improve the mass specific capacitance. Kaner et al (science.2012, 335 (6074): 1326-1330.) use a laser to reduce graphene oxide to produce a graphene material with a large number of vermicular macropores, however the bulk density of the material is only 0.048g cm -3 The specific capacitance in the aqueous electrolyte is only 9.7F cm -3 . Xu et al(Nature communications.2014, 54554) the pore-forming is carried out by etching hydrogen peroxide on the three-dimensional graphene frame, so that the channel for transporting electrolyte ions is increased, and the specific surface area of the material reaches 1560m due to the increase of the nano pores 2 g -1 Then mechanically compressing the mixture to obtain an electrode material with a bulk density of 0.71g cm -3 The volume specific capacity in the organic electrolyte is 212F cm -3 . The graphene prepared above results in a relatively low bulk density (in general) due to porosity<0.75g cm -3 ) The volume specific capacity still does not meet the requirement of practical application.
Many efforts have been made to increase the bulk density of graphene materials. Yang et al (science.2013, 341 (6145): 534-537) use liquid as medium and utilize capillary condensation effect to make the density of graphene film from 0.76g cm -3 Increased to 1.33g cm -3 In the aqueous electrolyte, the specific volume capacity reaches 255.5F cm -3 (ii) a Yue et al (Electrochimica acta. 2017, 254181-190) heat-treat graphene oxide by using polyethyleneimine as a medium, and realize that the bulk density of nitrogen-doped graphene is from 0.9 to 1.2g cm -3 The specific volume capacity reaches 317.3F cm -3 . These methods still have the density of the electrode material much less than the true density of graphite (2.26 g cm) because the material itself still has a high specific surface area and a high void structure -3 ) The volume specific capacitance still does not meet the requirement of practical application.
In one of the patents previously disclosed by us (CN 201810601338.0), a method of heat-treating graphene oxide with phosphoric acid has been prepared with high bulk density (1.55 g cm) -3 ) The volume specific capacitance of the graphene material can reach 483F cm -3 Has the advantages of short preparation time, mild conditions, simple operation and the like. However, concentrated phosphoric acid has a strong corrosive effect, a large amount of acid mist can be evaporated in the preparation process, a certain corrosive effect can be generated on the prepared equipment, a large amount of water can be consumed in the subsequent water washing process, and the recovery process of waste acid is relatively complex in price.
In summary, the problem to be solved in the art is to provide a more environmentally friendly strategy for preparing a graphene electrode material with high volume ratio capacitance.
Disclosure of Invention
The invention aims to solve the technical problems of low bulk density and low volume specific capacitance of the existing graphene material, and provides an environment-friendly method for preparing graphene with high volume specific capacitance.
According to the invention, the Graphene Oxide (GO) is subjected to heat treatment assisted by metal cations to obtain a graphene material with extremely high stacking density, the surface of the graphene has a high content of oxygen-containing groups with electrochemical activity to provide a pseudo capacitor, and the graphene material has high mass specific capacity and can also obtain excellent volume specific capacitance.
Compared with the existing preparation method, the preparation method has the advantages of low cost, simple equipment, wide raw material source, excellent performance of the prepared graphene material and the like.
In order to solve the technical problem, the method for preparing the graphene with high volume-specific capacitance by using the metal cation-assisted heat treatment technology is carried out according to the following steps:
step one, uniformly dispersing graphene oxide in deionized water to obtain a graphene oxide dispersion liquid;
step two, adding a metal ion salt into the graphene oxide dispersion liquid obtained in the step one, uniformly mixing, performing solid-liquid separation, and drying;
step three, carrying out heat treatment on the dried product obtained in the step two, and then washing with water until the ion concentration of the supernatant is less than 10 - 3 mol L -1 And drying to obtain the high-volume-ratio capacitance graphene.
Further limiting, in the first step, the weight ratio of the graphene oxide to the deionized water is 1: (1-1000).
Further limiting, the weight ratio of the graphene oxide to the metal ion salt in the second step is 1 (0.1-400).
Further defining that the weight ratio of the graphene oxide to the metal ion salt in the second step is 1.
Further limiting, step two, the metal ionsThe salt being Li + 、Na + 、K + 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Ba 2+ 、Cr 3+ 、 Mn 2 + 、Fe 2+ 、Fe 3+ 、Co 2+ 、Ni 2+ 、Cu 2+ 、Zn 2+ 、Al 3+ 、Sn 4+ One or more of halogen salt, nitrate, sulfate, etc. in an arbitrary ratio, and the solubility of the above metal ion salt is 1g/100g water or more.
Further, in the second step, the metal ion salt is anhydrous lithium chloride.
Further limited, the drying in the second step is vacuum drying at 50-200 ℃ or conventional drying for 2-24 h.
Further limit, the heat treatment temperature in the third step is 150-450 ℃, and the heat treatment time is 10-90 min.
Further limited, the drying in the third step is freeze drying at-70 ℃ to-50 ℃ for 12h to 24h, or vacuum drying at 50 ℃ to 200 ℃ or conventional drying for 2h to 24h.
According to the graphene material prepared by the metal cations, the graphene is assembled under the action of the cations-pi and the cations-oxygen-containing functional groups, the metal cations are beneficial to the conversion of the oxygen-containing functional groups in the graphene to C-OH and C = O groups in the heat treatment process, and the graphene material has the advantages of more oxygen-containing groups with electrochemical activity on the surface, high stacking density, large volume specific capacitance, excellent rate capability, good circulation stability and the like. The bulk density of the graphene material prepared by the invention is 0.9-1.7g cm -3 The volume specific capacitance is 200-520F cm -3 。
Compared with the traditional graphene chemical reduction, toxic reducing reagents such as hydrazine hydrate and the like are not needed, so that the method is green and environment-friendly;
the surface of the reduced graphene oxide prepared by the method has rich oxygen-containing groups with electrochemical activity, so that the problem of low pseudo capacitance in the graphene material is solved;
the graphene prepared by the method has extremely low pore volume, so that the graphene has high bulk density and high volume specific capacitance, and is suitable for preparing a super capacitor with high volume specific capacitance.
Drawings
Fig. 1 is a morphology photograph of the graphene powder prepared by the method of example 1, which is observed under a scanning electron microscope;
fig. 2 is an x-ray photoelectron spectrum of the graphene powder prepared by the method of example 1;
FIG. 3 is an IR spectrum of graphene powder prepared by the method of example 1;
fig. 4 is a raman spectrum of the graphene powder prepared by the method of example 1;
FIG. 5 is an x-ray diffraction pattern of the graphene powder prepared by the method of example 1;
FIG. 6 is a charging and discharging curve of the graphene powder prepared by the method of example 1 under different current densities when the graphene powder is used as an active material of a super capacitor;
FIG. 7 is a plot of volumetric capacitance and mass capacitance at different current densities when the graphene powder prepared by the method of example 1 is used as an active material of a supercapacitor;
fig. 8 shows the cycling stability of graphene prepared by the method of example 1 as an electrode material.
Detailed Description
Example 1: the implementation mode is realized by the following steps:
step one, according to the weight ratio of graphene oxide to deionized water of 1: uniformly dispersing graphene oxide in deionized water according to the proportion of 500;
secondly, adding anhydrous LiCl according to the weight ratio of the graphene oxide to the LiCl of 1 -1 Carrying out centrifugal solid-liquid separation, and vacuum drying at 100 ℃ for 12h;
step three, putting the mixture into a tube furnace, carrying out heat treatment for 60min at 400 ℃, washing for 4 times, and enabling the ion concentration of the supernatant to be less than 10 -3 mol L -1 And then vacuum drying for 4 hours at 80 ℃ to obtain graphene powder.
The morphology photograph of the graphene powder prepared by the method of the present embodiment observed under a scanning electron microscope is shown in fig. 1, and it can be seen from fig. 1 that graphene sheets prepared by the method of the present embodiment 1 are well stacked and assembled together, and the size of the particle is about 80 μm.
An x-ray photoelectron spectrum of the graphene powder prepared by the method of the present embodiment is shown in fig. 2, and it can be seen from the XPS total spectrum of fig. 2 that the prepared sample only contains two elements, i.e., carbon and oxygen, the atomic ratio O/C of the oxygen-carbon content is 0.13, and the oxygen content in the sample is 11.5%, which indicates that a part of oxygen-containing functional groups remains.
The infrared spectrum of the graphene powder prepared by the method of the present embodiment is shown in fig. 3; as can be seen from fig. 3, the sample prepared by the present method contains oxygen-containing functional groups such as carboxyl, hydroxyl, epoxy, and carbonyl groups.
The Raman spectrum of the graphene powder prepared by the method of the embodiment is shown in FIG. 4, 1340cm -1 And 1586cm -1 The peak of (A) is a defect peak and a benzene ring stretching vibration peak of the graphene respectively, and the D peak is stronger, which indicates that the number of defects is more;
an x-ray diffraction pattern of the graphene powder prepared by the method of the embodiment is shown in fig. 5; it can be seen from FIG. 5 that there is a diffraction peak at a position around 25.6, corresponding to an interplanar spacing of 0.347nm.
The charging and discharging curves of the graphene powder prepared by the method of the embodiment under different current densities when the graphene powder is used as an active material of a supercapacitor are shown in fig. 6; the sweeping speed is 5mV s -1 A very pronounced redox peak exists around 0.45V, which is caused by the inter-transformation between the quinones C = O and C-OH in graphene, indicating the presence of redox pseudocapacitance in the sample.
When the graphene powder prepared by the method of the embodiment is used as an active substance of a supercapacitor, volume specific capacitance and mass specific capacitance curves at different current densities are shown in fig. 7; the maximum value of the mass specific capacitance is 307 Fg -1 The corresponding volume specific capacitance is 512F cm -3 。
The cycle stability of the graphene prepared by the method of this example as an electrode material is shown in fig. 8, which shows that the graphene is 5Ag -1 After 10,000 cycles, the capacitance value is the original one103%, which shows that the electrode material has extremely high cycling stability.
Example 2: the implementation mode is realized by the following steps:
step one, according to the weight ratio of graphene oxide to deionized water of 1: uniformly dispersing graphene oxide in deionized water according to the proportion of 500;
and step two, adding anhydrous LiCl according to the weight ratio of the graphene oxide to the LiCl of 1 -1 Performing centrifugal solid-liquid separation, and performing vacuum drying at 100 ℃ for 12 hours;
step three, placing the mixture into a tube furnace, carrying out heat treatment for 60min at 400 ℃, washing for 4 times, and enabling the ion concentration of the supernatant to be less than 10 -3 mol L -1 And then vacuum drying for 4 hours at 80 ℃ to obtain graphene powder.
Example 3: the implementation mode is realized by the following steps:
step one, according to the weight ratio of graphene oxide to deionized water of 1: uniformly dispersing graphene oxide in deionized water according to the proportion of 500;
secondly, adding anhydrous LiCl according to the weight ratio of the graphene oxide to the LiCl of 1 -1 Carrying out centrifugal solid-liquid separation, and vacuum drying at 100 ℃ for 12h;
step three, placing the mixture into a tube furnace, carrying out heat treatment for 60min at 400 ℃, washing for 4 times, and enabling the ion concentration of the supernatant to be less than 10 -3 mol L -1 And then vacuum drying for 4 hours at 80 ℃ to obtain graphene powder.
Example 4: the implementation mode is realized by the following steps:
step one, according to the weight ratio of graphene oxide to deionized water of 1: uniformly dispersing graphene oxide in deionized water according to the proportion of 500;
and step two, adding anhydrous LiCl according to the weight ratio of the graphene oxide to the LiCl of 1 -1 Performing centrifugal solid-liquid separation, and performing vacuum drying at 100 ℃ for 12 hours;
step three, then putting the tube into the tubeHeat treating in a furnace at 200 deg.C for 60min, washing with water for 4 times, and collecting supernatant with ion concentration less than 10 -3 mol L -1 And then vacuum drying is carried out for 4 hours at the temperature of 80 ℃ to obtain the graphene powder.
Example 5: the implementation mode is realized by the following steps:
step one, according to the weight ratio of graphene oxide to deionized water of 1: uniformly dispersing graphene oxide in deionized water according to the proportion of 500;
step two, adding anhydrous KCl according to the weight ratio of the graphene oxide to the KCl being 1 -1 Carrying out centrifugal solid-liquid separation, and vacuum drying at 100 ℃ for 12h;
step three, placing the mixture into a tube furnace, carrying out heat treatment for 60min at the temperature of 200 ℃, washing for 4 times, and enabling the ion concentration of the supernatant to be less than 10 -3 mol L -1 And then vacuum drying for 4 hours at 80 ℃ to obtain graphene powder.

Claims (6)

1. A method for preparing high-volume-ratio-capacitance graphene by using a metal cation-assisted heat treatment technology is characterized by comprising the following steps of:
step one, uniformly dispersing graphene oxide in deionized water to obtain a graphene oxide dispersion liquid;
step two, adding metal ion salts into the graphene oxide dispersion liquid obtained in the step one, uniformly mixing, carrying out solid-liquid separation, and drying;
step three, putting the dried product in the step two into a tube furnace for heat treatment, and then washing with water until the ion concentration of the supernatant is less than 10 -3 mol L -1 Drying to obtain the high-volume-ratio capacitance graphene;
wherein the metal ion salt is Li + 、Na + 、K + 、Mg 2+ 、Ca 2+ 、Sr 2+ 、Ba 2+ 、Cr 3+ 、Mn 2+ 、Fe 2+ 、Fe 3+ 、Co 2+ 、Ni 2+ 、Cu 2 + 、Zn 2+ 、Al 3+ 、Sn 4+ Halogen salt of (2), nitreOne or more of acid salt and sulfate, and the solubility of the metal ion salt is more than or equal to 1g/100g water; the heat treatment temperature in the third step is 150-450 ℃, and the heat treatment time is 10-90 min.
2. The method of claim 1, wherein in the first step, the weight ratio of graphene oxide to deionized water is 1: (1-1000).
3. The method of claim 1, wherein the weight ratio of the graphene oxide to the metal ion salt in the second step is 1 (0.1-400).
4. The method according to claim 1, wherein the weight ratio of the graphene oxide to the metal ion salt in the second step is 1.
5. The method of claim 1, wherein the drying in the second step is vacuum drying at 50-200 ℃ or conventional drying for 2h to 24h.
6. The method according to claim 1, wherein the drying in the third step is carried out at-70 ℃ to-50 ℃ for 12h to 24h, or at 50 ℃ to 200 ℃ for vacuum drying or conventional drying for 2h to 24h.
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