CN105702473A - Carbon-based electrode material having super high specific capacitance and combined electrode material thereof - Google Patents
Carbon-based electrode material having super high specific capacitance and combined electrode material thereof Download PDFInfo
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- CN105702473A CN105702473A CN201410697163.XA CN201410697163A CN105702473A CN 105702473 A CN105702473 A CN 105702473A CN 201410697163 A CN201410697163 A CN 201410697163A CN 105702473 A CN105702473 A CN 105702473A
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- carbon
- electrode material
- based electrode
- graphene
- doping
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Classifications
-
- 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
Landscapes
- Electric Double-Layer Capacitors Or The Like (AREA)
- Carbon And Carbon Compounds (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a carbon-based electrode material having super high specific capacitance and a combined electrode material thereof. Capacitance of the carbon-based electrode material comprises two parts, including double-electric-layer capacitance and Faradaic pseudo capacitance, the double-electric-layer capacitance is 20-60% of the capacitance of the carbon-based electrode material, the specific capacitance of the carbon-based electrode material under the 1A/g current density is more than 400, the volume specific capacitance is more than 300 F/ml, the energy density of a symmetric device of a water-based electrolyte is more than 20 Wh/kg, and the volume energy density is more than 15Wh/kg.
Description
Technical Field
The invention relates to a carbon-based electrode material with ultrahigh specific capacitance and a composite electrode material thereof, belonging to the technical field of materials and electrochemistry.
Background
The super capacitor has the characteristics of high power density, long cycle life, safety, reliability and the like, and can be widely applied to hybrid electric vehicles, high-power output equipment and the like. Super capacitors have now formed a very considerable market size worldwide, with values of $ 4.7 billion in 2010, maintaining nearly a 20% growth rate in recent years. Although the industry prospect of the super capacitor is outstanding, the energy density is limited to be too low (mass specific capacitance of the conventional activated carbon super capacitor)<200F/g, volume specific capacitance<200F/mL, energy density<10Wh/kg), much lower than that of lithium batteries (>100Wh/kg), which makes large-scale application impossible. The reason that the energy density of the activated carbon electrode is low is that a large number of microporous structures are not beneficial to effective migration of charges, so that energy storage of a large number of active sites is invalid, and meanwhile, the stability of the activated carbon electrode is poor due to high structural defects, so that the improvement of the energy density is limited. Another important reason is that the porous carbon material has sp-rich carbon atoms3Mainly hybridized, sp2Low proportion of hybridized atoms and poor conductivity (typical of<100S/cm). To obtain a carbon material having high conductivity, sp of carbon atom must be increased2The hybridization ratio. Although at presentHave reported to have a high sp2The hybrid carbon material has sp2 hybridization with locality, the local conductivity is good, but the overall conductivity still can not meet the requirement of capacitor electrode. High sp2The hybridized graphene can have high specific surface area (2,620 m)2The conductive carbon material has the advantages of/g), high conductivity and high structural stability, and can overcome the performance bottleneck of the active carbon electrode material. However, the specific capacity of the carbon electrode is still far below the theoretical value (550F/g) at present, mainly due to the fact that the actual specific surface area is below 1000m2(ii)/g; in addition, the low bulk density of graphene also reduces the volumetric energy density of the device.
In order to obtain higher specific capacitance, it has been reported in literature that a doping element, such as nitrogen, oxygen, sulfur, boron, etc., is introduced into porous carbon or graphene to generate faraday capacitance by oxidation-reduction reaction. However, there are two fatal problems with this type of material reported in the literature: firstly, the introduced doping elements can obviously reduce the conductivity of the material; secondly, the doping element produces a very low faraday capacitance fraction (typically below 10%), mainly due to the inefficient use of the large number of doping active centers.
Furthermore, high sp2The hybrid carbon material can also be used as a carrier with high specific surface area and high conductivity to load other active materials with high specific capacity, so that the specific energy density of the electrode material is further improved. Although the faraday capacitor (such as polymer, transition metal oxide and the like) can obtain higher specific capacitance through oxidation-reduction reaction in the charging and discharging processes, the practical application of the faraday capacitor is limited because the faraday capacitor has poor stability (the capacitance retention ratio is less than 50% after five thousand cycles), and the power density is lower (less than 1 kilowatt per kilogram). In addition, after the electrode material having the faraday capacitance is manufactured into the supercapacitor device, the oxidation-reduction potential cannot be simultaneously reached due to the difference in the voltages of the positive and negative electrodes, and the energy storage characteristics of the supercapacitor material cannot be completely expressed. At present, the specific capacitance of the capacitor device based on the surface oxidation-reduction reaction of metal compounds or conductive polymers is lost by more than 15%.
Therefore, how to provide a carbon-based composite material, which integrates the advantages of the carbon material with high specific surface area, the carbon material with high conductivity and the Faraday capacitance, and gets rid of the respective disadvantages, so as to obtain the super capacitor material with ultrahigh specific capacitance and energy density is one of the research hotspots in the field.
Disclosure of Invention
The invention aims to overcome the defects of the existing carbon-based composite material, and provides a carbon-based electrode material with ultrahigh specific capacitance, a composite electrode material and a preparation method thereof.
The invention provides a carbon-based electrode material with ultrahigh specific capacitance, which is characterized in that the capacitance of the carbon-based electrode material consists of two parts, namely an electric double layer capacitance and a Faraday pseudocapacitance, the electric double layer capacitance accounts for 20-60% of the capacitance of the carbon-based electrode material, the specific capacity of the carbon-based electrode material is more than 400 under the current density of 1A/g, the volume specific capacity is more than 300 farads per milliliter, the energy density of a symmetrical device of a water-based electrolyte is more than 20 watt-hour per kilogram, and the volume energy density is more than 15-watt-hour per liter.
The basic idea of the invention is as follows: active sites are introduced into a carbon material with high conductivity and high specific surface area through element doping to generate a Faraday pseudo-capacitance, the doping elements are one or the combination of two of nitrogen, boron, phosphorus and sulfur, and the atomic concentration of the doping elements is 0.5-20%. After doping, the conductivity of the carbon-based material is not obviously reduced, the dispersibility of the carbon-based material in water is obviously improved, and the zeta potential is less than-15 mV;
besides the characteristics of ultrahigh specific capacitance and energy density, the carbon material provided by the invention has another important advantage that the oxidation-reduction potential of the electrode material can be adjusted by controlling the content of the doped element and the doped structure, so that different Faraday capacitances can be realized. Taking the nitrogen-doped mesoporous graphene obtained by the invention as an example, the bonding modes between nitrogen and carbon include pyridine type, pyrrole type andthe graphene is characterized by comprising three graphite types, wherein pyridine-type and pyrrole-type nitrogen atoms can perform reversible oxidation-reduction reaction with hydrogen ions and are effective doping active sites, and the oxidation-reduction reaction potential is influenced by the ratio of the pyridine-type and pyrrole-type nitrogen atoms, namely the oxidation-reduction potential of the nitrogen-doped mesoporous graphene can be regulated and controlled by regulating the ratio of the pyridine-type and pyrrole-type nitrogen atoms. According to the series connection principle of two electrode capacitors, the total capacitance C of the device is equal to C1C2/(C1+C2) After the doped carbon-based electrode materials with different oxidation-reduction potentials are compounded, the anode and the cathode can simultaneously reach the oxidation-reduction potentials under a plurality of voltages, and the maximum Faraday capacitance, namely C1-C2, can be obtained at the same time. The specific capacitance of the device thus obtained is less than or equal to 5% compared with the specific capacitance of the material itself. After a single material with Faraday capacitance is made into a device, the capacitance loss is more than 15%.
Preferably, sp of carbon atoms in the carbon-based electrode material2The hybridization ratio is more than 60%, and the conductivity of the carbon-based electrode material is more than 200 Siemens per centimeter.
Preferably, the specific surface area of the carbon-based electrode material is more than 1200 square meters per gram.
Preferably, the zeta potential of the carbon-based electrode material in water is less than-15 mV.
The carbon-based electrode material mainly comprises sp2 hybridized carbon atoms, has a structure with high specific surface area and contains defects, and the specific surface area is more than 1200 square meters per gram; from a chemical composition, a dopant atom other than carbon atoms; the carbon-based electrode material is less than-15 mV in terms of zeta potential in water.
Preferably, the carbon-based electrode material faraday pseudocapacitance is generated by introducing doping elements into active sites, wherein the doping elements are at least one of nitrogen, boron, phosphorus and sulfur, and the doping amount of the doping elements is 0.5-20%.
Preferably, redox reaction occurs to introduce the active sites by the doping element binding to charged ions.
Preferably, the combination of the doping elements and the carbon atoms includes intra-ring doping, boundary doping and high defect site doping.
Preferably, the doping element is nitrogen, and the combination mode of nitrogen and carbon in the carbon-based electrode material comprises pyridine type, pyrrole type and graphite type, wherein the pyridine type and the pyrrole type account for more than 70%.
Preferably, the carbon-based electrode material is mesoporous graphene doped with the doping element and having a high specific surface area, and sp of carbon atoms in the mesoporous graphene having the high specific surface area2The hybridization proportion is more than 80%, the specific surface area is more than 1500 square meters per gram, the conductivity is more than 400 Siemens per centimeter, and the number of layers of the graphene is 3-5.
Preferably, the doped high specific surface area three-dimensional graphene has a three-dimensionally connected conductive network, the conductivity of the conductive network is more than 300 Siemens per centimeter, the specific surface area is more than 2000 square meters per gram, and the density of the conductive network is less than 0.1 gram per cubic centimeter.
Preferably, one of the preferable carbon-based electrode materials comprises a mesoporous structure and a microporous structure, wherein the pore diameter of the micropores ranges from 0.5 nm to 2 nm, and the pore diameter of the mesopores ranges from 2 nm to 20 nm.
In addition, the invention also provides a composite electrode material comprising the carbon-based electrode material, wherein the composite material is formed by compounding the carbon-based electrode materials with different oxidation-reduction potentials or is formed by compounding the carbon-based electrode material with a metal compound and/or a conductive polymer.
Preferably, the metal compound includes at least one of manganese oxide, nickel oxide, cobalt oxide, niobium oxide, tantalum oxide, ruthenium oxide, titanium sulfide, molybdenum sulfide, vanadium sulfide, tantalum sulfide, vanadium selenide, and tantalum selenide, and the conductive polymer includes polyaniline, polypyrrole, and/or polythiophene.
In the following disclosure, the preparation method is described by taking the carbon-based electrode material as graphene doped with at least one of nitrogen, boron, phosphorus and sulfur.
In the preparation of the carbon-based electrode material, in a doping source, a nitrogen source comprises at least one of melamine, aminoguanidine, ammonia gas, amino acid and ethylenediamine, a boron source comprises at least one of boron tribromide, boron trifluoride, boric acid and elemental boron, a phosphorus source comprises at least one of trioctylphosphine, triphenylphosphine and phosphorus pentoxide, and a sulfur source comprises at least one of thiourea, thiophene and dibenzyl disulfide;
the carbon source comprises methane, ethylene, acetylene, methanol and/or ethanol;
the metal template or metal catalyst comprises Ni, Cu, Co and/or Fe;
in the metal source, the Ni source comprises at least one of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate; the Cu source comprises at least one of copper nitrate, copper acetate, copper chloride and copper sulfate; the Co source comprises at least one of cobalt nitrate, cobalt acetate, cobalt chloride and cobalt sulfate; the Fe source comprises at least one of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate.
The present invention also provides a first method of preparing an exemplary carbon-based electrode material, the method comprising:
firstly, dispersing a metal template with a three-dimensional continuous pore structure, an organic carbon source and a doping source in a solvent, ultrasonically dispersing to prepare a metal template/organic carbon source/doping source xerogel with the organic carbon source and the doping source filled in the metal template, and then sequentially carrying out chemical vapor deposition and impurity removal on the metal template/organic carbon source/doping source xerogel to prepare the carbon-based electrode material;
or,
firstly, mixing porous oxide or porous ceramic with a three-dimensional continuous pore structure with a metal source solution, stirring, ultrasonically dispersing, vacuumizing, and volatilizing or drying the solution to obtain porous oxide or porous ceramic sol filled with a metal source; then the porous oxide or the porous ceramic sol filled with the metal source is subjected to heat preservation in a protective atmosphere at 300-500 ℃ to obtain the porous oxide or the porous ceramic filled with the metal catalyst, wherein the porous oxide or the porous ceramic comprises but is not limited to porous oxides including silicon dioxide, magnesium oxide, titanium dioxide, strontium titanate, barium titanate, sodium silicate, calcium silicate, magnesium silicate and the like,
secondly, dispersing the porous oxide or porous ceramic filled with the metal catalyst, the organic carbon source and the doping source in a solvent, and performing ultrasonic dispersion and drying to obtain the organic carbon source, the porous oxide filled with the doping source in the porous oxide or porous ceramic, or porous ceramic/metal catalyst/organic carbon source/doping source xerogel;
thirdly, sequentially carrying out chemical vapor deposition on porous oxide or porous ceramic/metal catalyst/organic carbon source/doping source xerogel to remove impurities, and preparing the carbon-based electrode material;
wherein the temperature of the chemical vapor deposition method is 600-1100 ℃, and the gas used for the chemical vapor deposition comprises hydrogen and a gaseous carbon source.
The basic idea for preparing the mesoporous graphene is as follows: mesoporous graphene is grown along the wall of the mesoporous silica by a chemical vapor deposition method under the catalysis of metal in a pore channel by taking the mesoporous silica as a template and taking one or more of polyfurfuryl alcohol, sucrose, glucose, phenolic resin, polymethyl methacrylate and polystyrene as a carbon source. The metal catalyst is one or the combination of more of Ni, Cu, Co and Fe. The Ni source is one or a combination of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate; the Cu source is one or a combination of more of copper nitrate, copper acetate, copper chloride and copper sulfate; the Co source is one or a combination of more of cobalt nitrate, cobalt acetate, cobalt chloride and cobalt sulfate; the Fe source is one or a combination of several of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate. The mass ratio of the metal source to the silicon dioxide is 0.25-2.5. The carrier gas used in the chemical vapor deposition method is nitrogen or argon, the reducing gas is hydrogen, and the gas carbon source is one or a combination of several of methane, ethylene, acetylene, methanol, ethanol and the like; the growth temperature of the graphene is 800-.
Preferably, the organic carbon source comprises at least one of polyfurfuryl alcohol, sucrose, glucose, phenolic resin, polymethyl methacrylate and polystyrene.
Preferably, the pore size of the metal template, porous oxide and/or porous ceramic is 2 to 20 nanometers.
Preferably, the concentration of the metal source in the metal source solution is 0.1-2.0mol/L, the mass ratio of the metal source to the porous oxide or the porous ceramic is 0.25-2.5, and the mass ratio of the doping source to the carbon source is (0.1-2): 1, preferably (0.5-1): 1, the mass ratio of the porous oxide or the porous ceramic to the carbon source is (0.2-2): 1.
preferably, the porous oxide or porous ceramic filled with the metal catalyst is prepared with a holding time of 2-5 hours and a protective atmosphere of an inert gas doped with 1-20% hydrogen.
Preferably, the filling means comprises a vacuum infusion method, the infusion pressure being 1-100 Pa.
Preferably, the chemical vapor deposition temperature is 800-: the flow rate of nitrogen or argon is 50-400 sccm, the flow rate of hydrogen is 5-100 sccm, the flow rate of gaseous carbon source is 1-20 sccm, the flow rate of ammonia is 0.5-20 sccm, the flow rate of water vapor is 0.5-10 sccm, and the flow rate of carbon dioxide is 0.5-10 sccm.
The invention provides a preparation method of another exemplary carbon-based electrode material, which comprises the following steps:
1) adding an activating agent, a doping source and a metal source into graphite, heating for 0.5-10 hours in gas containing a gaseous carbon source and hydrogen at the temperature of 600-1000 ℃ after ball milling, then cooling and removing impurities to obtain the carbon-based electrode material, wherein the activating agent is at least one of potassium hydroxide, sodium hydroxide and zinc chloride, and the mass ratio of the graphite, the activating agent, the doping source and the metal source is 1: (0.5-2): (0.01-1): (0.5-2); or,
a) firstly, adding an activating agent into graphene, and then heating and reacting for 0.5-10 hours at the temperature of 500-1000 ℃ under the atmosphere of argon or nitrogen to prepare defective graphene, wherein the mass ratio of the activating agent to the graphene is (0.5-4): 1, the activating agent is at least one of potassium hydroxide, sodium hydroxide and zinc chloride;
b) ball-milling and mixing the defective graphene prepared in the step a), the doping source and the metal source, placing the mixture in a chemical vapor deposition furnace, heating the mixture to 800-1100 ℃ in argon or nitrogen, introducing gas including hydrogen and a gaseous carbon source, preserving the heat for 10-30 minutes, cooling the mixture, and removing impurities to obtain the carbon-based electrode material, wherein the mass ratio of the defective graphene, the doping source and the metal source is 1: (0.01-1): (0.5-2).
Preferably, in step 1) or step a), the reaction atmosphere is heated at 600-: the flow rate of the gaseous carbon source is 2-20 sccm, the flow rate of the hydrogen gas is 5-20 sccm, the flow rate of the ammonia gas is 10-20 sccm, the flow rate of the nitrogen gas is 200-300 sccm, the flow rate of the steam is 5-20 sccm, and the flow rate of the carbon dioxide is 5-20 sccm.
Preferably, in step b), the gas flow rate is 50-500 sccm, and comprises: the flow rate of hydrogen is 5 to 50sccm, the flow rate of the gaseous carbon source is 2 to 10sccm, the flow rate of ammonia or borane is 1 to 20sccm, the flow rate of nitrogen is 50 to 450sccm, the flow rate of steam is 2 to 20sccm, and the flow rate of carbon dioxide is 2 to 20 sccm.
In addition to the above preparation method, the present invention also provides a preparation method of another exemplary carbon-based electrode material, the method comprising:
firstly, dispersing graphene oxide, a doping source and a metal source in an ethanol solvent with nano polymer spheres, and freeze-drying to obtain a three-dimensional porous precursor, wherein the mass ratio of the graphene oxide to the doping source to the metal source is 1: (0.01-1): (0.5-2), or dispersing graphene oxide, a doping source, nano silicon dioxide and a metal source in an aqueous solution containing a high molecular binder, heating to prepare gel, and heating the gel at 250-350 ℃ for 5-10 hours to remove water to obtain the carbonized material, wherein the mass ratio of the graphene oxide to the doping source to the nano silicon dioxide to the metal source is 1: (0.01-1): (0.5-2): (0.5-2);
and then, placing the prepared three-dimensional porous precursor or the ball-milled carbonized material in a chemical vapor deposition furnace, heating to 800-.
Preferably, the concentration of the nanometer polymer ball in the ethanol solvent is 0.1-5 g/mL, and the nanometer polymer ball comprises nanometer polystyrene ball, polymethyl methacrylate and polyethylene.
Preferably, the freeze-drying process comprises: the temperature is-50 to-80, and the time is 5 to 20 hours.
Preferably, the concentration of the macromolecular binder in the aqueous solution of the macromolecular binder is 0.05-0.5 g/mL, and the macromolecular binder comprises starch, polyacrylamide, polyacrylic acid, polyvinylpyrrolidone, polyvinyl alcohol, polymaleic anhydride, polyquaternary ammonium salt and polyethylene glycol.
Preferably, the gas flow rate is 300-500 sccm, including: the flow rate of nitrogen is 250-450 sccm, the flow rate of hydrogen is 20-50 sccm, the flow rate of gaseous carbon source is 5-10 sccm, the flow rate of ammonia is 5-10 sccm, the flow rate of steam is 2-5 sccm, and the flow rate of carbon dioxide is 2-5 sccm.
Preferably, impurities including the template, and/or the metal source, and/or the metal catalyst are removed by hydrochloric acid, hydrofluoric acid leaching, and washing with water, ethanol.
The invention has the beneficial effects that:
the carbon-based electrode material and the composite electrode material thereof provided by the invention integrate the advantages of the carbon material with high specific surface area, the carbon material with high conductivity and the Faraday capacitance, and get rid of the respective disadvantages, thereby obtaining the super capacitor material with ultrahigh specific capacitance and energy density;
compared with commercial porous carbon materials, the doped mesoporous graphene has better conductivity and provides a rapid channel for charge transmission; compared with the traditional graphene, the graphene obtained by the invention has a developed ordered mesoporous and microporous structure, and provides more channels for the interaction of the graphene and an electrolyte. The doping element enables the electrode material obtained by the invention to generate oxidation-reduction reaction in the charging and discharging process to generate Faraday capacitance, thereby obtaining higher specific capacitance and energy density. Compared with traditional Faraday capacitance electrode materials such as transition metal oxides (such as nickel oxide, manganese oxide and the like), polymers (such as polyaniline, polypyrrole and the like), the mesoporous nitrogen-doped graphene obtained by the method has similar specific capacitance and energy density, but has a faster response rate, a higher power density and better charge-discharge cycle stability.
Drawings
Fig. 1 shows a schematic diagram of the combination of doping atoms and carbon atoms of a doped carbon-based electrode material prepared in the present invention, taking nitrogen doping as an example;
FIG. 2 shows a Raman spectrum of a carbon-based electrode material prepared in one embodiment of the present invention;
FIG. 3 shows a small angle X-ray diffraction pattern of a carbon-based electrode material prepared in one embodiment of the present invention;
FIG. 4 shows a pore size distribution plot for a carbon-based electrode material prepared in one embodiment of the present invention;
FIG. 5 shows a narrow spectral scan of XPSN1s (using nitrogen doping as an example) of a carbon-based electrode material prepared in one embodiment of the present invention;
FIG. 6 shows the results of cyclic voltammetry (scan rate 2mV/s) for a nitrogen-doped carbon-based electrode material prepared in one embodiment of the present invention in a three-electrode system (a), and its charge-discharge curve (b);
FIG. 7 shows the results of cyclic voltammetry (scan rate 2mV/s) for a nitrogen-doped carbon-based electrode material prepared in one embodiment of the present invention in a symmetric electrode system (a), and its charge-discharge curve (b);
FIG. 8 shows the results of cyclic voltammetry (scan rate of 2mV/s) for three nitrogen-doped carbon-based electrodes of different redox potentials prepared in the present invention in a three-electrode system (a), and the results of cyclic voltammetry for a new composite electrode material obtained after compositing the three carbon-based electrodes (scan rate of 2mV/s) in a three-electrode system (b).
Detailed Description
The present invention is further described below in conjunction with the following embodiments and the accompanying drawings, it being understood that the drawings and the following embodiments are illustrative of the invention only and are not limiting.
The invention aims to provide a carbon-based electrode material for a high-performance super capacitor and a composite electrode material thereof, which have the following electrochemical characteristics: the capacitor consists of two parts, namely an electric double layer capacitor and a Faraday pseudo capacitor, and the specific capacity is more than 400 farads per gram or more than 300 farads per milliliter; the proportion of the double electric layer capacitor is 20-60%; or a symmetrical device with water-based electrolyte having an energy density greater than 20 watt-hours per kilogram, or a volumetric energy density greater than 15 watt-hours per liter. Having such excellent electrochemical propertiesThe carbon-based electrode material is structurally characterized in that carbon atoms pass through sp2Hybridization, the proportion of which is more than 60 percent; the conductive performance is very high, and the conductivity is more than 200 Siemens per centimeter; has very high specific surface area, which is more than 1200 square meters per gram.
The basic idea of the invention is as follows: active sites are introduced into a carbon material with high conductivity and high specific surface area through element doping to generate a Faraday pseudo-capacitance, the doping elements are one or the combination of two of nitrogen, boron, phosphorus and sulfur, and the atomic concentration of the doping elements is 0.5-20%. After doping, the conductivity of the carbon-based material is not obviously reduced, the dispersibility of the carbon-based material in water is obviously improved, and the zeta potential is less than-15 mV. Preferably, the nitrogen-doped mesoporous graphene is characterized by sp2The hybridized carbon atom proportion is more than 80%, the conductivity is more than 400 Siemens per centimeter, and the specific surface area is more than 1500 square meters per gram. The nitrogen-doped carbon-based electrode material has good dispersibility in water, the zeta potential is less than-15 mV, the combination mode of nitrogen and carbon in the nitrogen-doped carbon-based electrode material comprises pyridine type, pyrrole type and graphite type, wherein the proportion of the pyridine type and the pyrrole type is more than 70%.
Besides the characteristics of ultrahigh specific capacitance and energy density, the carbon material provided by the invention has another important advantage that the oxidation-reduction potential of the electrode material can be adjusted by controlling the content of the doped element and the doped structure, so that different Faraday capacitances can be realized. The combination mode between the doping element and the carbon comprises one or the combination of intra-ring doping, boundary doping and high-defect position doping. The active doping elements in the carbon-based electrode material are combined with charged ions to generate oxidation-reduction reaction. Taking the nitrogen-doped mesoporous graphene obtained by the invention as an example, the combination mode of nitrogen and carbon includes pyridine type, pyrrole type and graphite type, wherein the ratio of the pyridine type to the pyrrole type is more than 70%, as shown in fig. 1, wherein pyridine type and pyrrole type nitrogen atoms can perform reversible redox reaction with hydrogen ions, and are effective doping active sites, the redox reaction potential is influenced by the ratio of the pyridine type to the pyrrole type nitrogen atoms, that is, the ratio of the pyridine type to the pyrrole type nitrogen atoms can be adjusted to adjustAnd controlling the oxidation-reduction potential of the nitrogen-doped mesoporous graphene. According to the series connection principle of two electrode capacitors, the total capacitance C of the device is equal to C1C2/(C1+C2) After the doped carbon-based electrode materials with different oxidation-reduction potentials are compounded, the anode and the cathode can simultaneously reach the oxidation-reduction potentials under a plurality of voltages, and simultaneously the maximum Faraday capacitance, namely C, can be obtained1＝C2At this time, the maximum specific capacitance can be obtained. The specific capacitance of the device thus obtained is less than or equal to 5% compared with the specific capacitance of the material itself. After a single material with Faraday capacitance is made into a device, the capacitance loss is more than 15%.
The doped high specific surface area graphene is characterized by sp2The hybridized carbon atom proportion is more than 80%, the conductivity is more than 400 Siemens per centimeter, and the specific surface area is more than 1500 square meters per gram.
The high specific surface area doped graphene is preferably a high specific surface area doped mesoporous graphene, and has two pore channel structures of a mesopore and a micropore, wherein the pore diameter range of the micropore is 0.52 nm, and the pore diameter range of the mesopore is 220 nm.
The high-performance carbon-based electrode material provided by the invention can also be used as an additive to be compounded with a conventional supercapacitor material, so that the performance of the capacitor is improved. These materials include conventional carbon materials such as mesoporous carbon, activated carbon, graphene, carbon nanotubes, and the like; one or more metal compounds selected from manganese oxide, nickel oxide, cobalt oxide, niobium oxide, tantalum oxide, ruthenium oxide, titanium sulfide, molybdenum sulfide, vanadium sulfide, tantalum sulfide, vanadium selenide, tantalum selenide, and the like; or compounding one or more conductive polymers selected from polyaniline, polypyrrole, polythiophene, etc. Wherein, the specific capacitance is improved by more than 15 percent after the composite material is compounded with the conventional carbon material and the metal compound; the cycle life is improved by more than 40 percent after the conductive polymer is compounded.
Preferably, the basic idea of preparing the mesoporous graphene of the invention is as follows: filling a metal catalyst, a carbon source and a doping source in the pore canal of the silicon dioxide by taking mesoporous silicon dioxide as a template, and preparing the doped mesoporous graphene by a chemical vapor deposition method.
Mesoporous graphene is grown along the wall of the mesoporous silica by a chemical vapor deposition method under the catalysis of metal in a pore channel by taking the mesoporous silica as a template and taking one or more of polyfurfuryl alcohol, sucrose, glucose, phenolic resin, polymethyl methacrylate and polystyrene as a carbon source. The metal catalyst is one or the combination of more of Ni, Cu, Co and Fe. The Ni source is one or a combination of nickel nitrate, nickel acetate, nickel chloride and nickel sulfate; the Cu source is one or a combination of more of copper nitrate, copper acetate, copper chloride and copper sulfate; the Co source is one or a combination of more of cobalt nitrate, cobalt acetate, cobalt chloride and cobalt sulfate; the Fe source is one or a combination of several of ferric nitrate, ferric acetate, ferric chloride and ferric sulfate. The mass ratio of the metal source to the silicon dioxide is 0.25-2.5. The carrier gas used in the chemical vapor deposition method is nitrogen or argon, the reducing gas is hydrogen, and the gas carbon source is one or a combination of several of methane, ethylene, acetylene, methanol, ethanol and the like; the growth temperature of the graphene is 800-.
The method for filling the metal catalyst into the mesoporous silicon dioxide or porous ceramic pore channel is a vacuum infusion method, and the infusion pressure is 1-100 Pa.
When nitrogen, boron, phosphorus and sulfur sources are added into the pore channel, the doped mesoporous graphene can be obtained. The concentration of the doping element can be adjusted by the adding amount of the doping source, and when the mass ratio of the doping source to the carbon source is 0.01-0.5, the obtained atomic concentration is 0.5-15%. The nitrogen source comprises one or a combination of more of melamine, aminoguanidine, ammonia gas, amino acid and ethylenediamine; the boron source comprises one or a combination of more of boron tribromide, boron trifluoride, boric acid and elemental boron; the phosphorus source is one or a combination of more of trioctylphosphine, triphenylphosphine and phosphorus pentoxide; the sulfur source comprises one or more of thiourea, thiophene and dibenzyl disulfide. The doping source co-doped with the two elements can be one of the nitrogen source, the boron source, the phosphorus source and the sulfur source.
Compared with commercial porous carbon materials, the doped mesoporous graphene has better conductivity and provides a rapid channel for charge transmission; compared with the traditional graphene, the graphene obtained by the invention has a developed ordered mesoporous and microporous structure, and provides more channels for the interaction of the graphene and an electrolyte. The doping element enables the electrode material obtained by the invention to generate oxidation-reduction reaction in the charging and discharging process to generate Faraday capacitance, thereby obtaining higher specific capacitance and energy density. Compared with traditional Faraday capacitance electrode materials such as transition metal oxides (such as nickel oxide, manganese oxide and the like), polymers (such as polyaniline, polypyrrole and the like), the mesoporous nitrogen-doped graphene obtained by the method has similar specific capacitance and energy density, but has a faster response rate, a higher power density and better charge-discharge cycle stability.
Preferably, the high specific surface area doped graphene can be obtained by doping and activating graphene, and the activating agent is one or a combination of more than one of potassium hydroxide, sodium hydroxide, ammonia gas, zinc chloride, water vapor, carbon dioxide and the like; the ratio of the activating agent to the graphene is 0.5-4; the activation temperature is 500-1000 ℃; the activation time is 0.5-8 hours.
Preferably, the high specific surface area doped graphene can be a doped high specific surface area three-dimensional graphene with a three-dimensional connected pore channel structure, has good electric and heat conducting channels, has the electric conductivity of more than 300 siemens per centimeter, has the specific surface area of more than 2000 square meters per gram, and has the density of less than 0.1 gram per cubic centimeter. The preparation method comprises the steps of filling a carbon source and a doping source in a metal template with a three-dimensional continuous pore structure serving as a catalyst, and preparing the doped high-specific-surface-area three-dimensional graphene by a chemical vapor deposition method; or filling a metal catalyst, a carbon source and a doping source in the pore channel by taking one of porous ceramic or porous silicon dioxide with a three-dimensional continuous pore structure as a template, and preparing the doped high-specific-surface-area three-dimensional graphene by a chemical vapor deposition method. The temperature of the chemical vapor deposition method is 600-1000 ℃, the reaction time is 5-60 minutes, the gases are inert gases, carbon sources, hydrogen and activating gases, and the gas flow is 1-500 sccm. The activating gas is one or more of water vapor, ammonia gas and carbon dioxide.
The other method for preparing the doped high-specific-surface-area three-dimensional graphene is to disperse the graphene, a doping source and a metal source in an ethanol solvent with nano polymer spheres, and freeze-drying to obtain a three-dimensional porous precursor. Placing the sample in a chemical vapor deposition furnace, heating to 800-1100 ℃ in argon or nitrogen, introducing hydrogen, ammonia and a gas carbon source, preserving the temperature for 10-30 minutes, cooling to room temperature, and taking out the sample. The product is removed with impurities such as nickel and the like by nitric acid, and the specific surface area of the product is more than 1200-2000m2Doped graphene per gram.
The two or more doped carbon-based electrode materials with different oxidation-reduction potentials are compounded; the specific capacity of the device of the symmetrical supercapacitor made of the electrode composite material is less than 5% of the specific capacity of the material.
The preparation and characterization processes of three (but not limited to) carbon-based electrode materials with ultrahigh specific capacitance and a composite electrode material thereof are described in detail below.
1. The preparation method comprises the steps of filling a carbon source and a doping source in a metal template with a three-dimensional continuous pore structure serving as a catalyst, and preparing the doped high-specific-surface-area three-dimensional graphene by a chemical vapor deposition method; or filling a metal catalyst, a carbon source and a doping source in the pore channel by taking one of porous ceramic or porous silicon dioxide with a three-dimensional continuous pore structure as a template, and preparing the doped high-specific-surface-area three-dimensional graphene by a chemical vapor deposition method. The temperature of the chemical vapor deposition method is 600-1000 ℃, the reaction time is 5-60 minutes, the gases are inert gases, carbon sources, hydrogen and activating gases, and the gas flow is 1-500 sccm. The activating gas is one or more of water vapor, ammonia gas and carbon dioxide.
The method specifically comprises the following steps:
doped mesoporous doped graphene
1) The metal catalyst is filled into the mesoporous silicon dioxide pore canal
Preparing an aqueous solution of a metal source with the concentration of 0.1-2.0mol/L, and mixing the aqueous solution with commercial mesoporous silica according to the mass ratio of metal to silica of 0.25-2.5. Stirring, ultrasonic dispersing, vacuumizing to 1-100Pa, and volatilizing to obtain sol. Heating to 450 ℃ in an argon atmosphere containing 5% of hydrogen, and preserving the heat for 2-5 hours to obtain mesoporous silica (silicon dioxide/metal) filled with a metal catalyst;
2) filling a carbon source and a doping source into the mesoporous silica pore channel
Dissolving a carbon source and one or two doping sources in water, ethanol and other suitable solutions, adding the silicon dioxide/metal obtained in the step 1), and performing ultrasonic dispersion and drying to obtain the silicon dioxide/metal/carbon source/doping source. The proportion of the doping source to the carbon source is adjusted according to the doping concentration, and is generally 0.01-0.5;
3) chemical vapor deposition method for growing graphene
Placing the silicon dioxide/metal/carbon source/doping source obtained in the step 2) into an atmosphere furnace, heating to 800-1100 ℃ in argon or nitrogen, introducing hydrogen, ammonia and a gas carbon source, and preserving the temperature for 10-30 minutes. Cooled to room temperature and the sample was taken out. The reaction temperature and time are determined according to the kinds of the carbon source and the metal catalyst;
4) template etching and sample purification
Soaking the sample obtained in the step 3) in a mixed solution of hydrochloric acid and hydrofluoric acid, filtering after 24 hours, and washing with a large amount of deionized water and ethanol. Drying to obtain mesoporous doped graphene;
5) morphology and structure characterization of mesoporous doped graphene
The morphology of the graphene sample obtained by the invention is observed by a transmission electron microscope (JEM 2010). The structure of graphene was characterized by Raman spectroscopy (RenishawinviaRamamane Microscope, excitation wavelength 514.5 nm). The relative content ratio of each element on the surface of the sample and the chemical combination state thereof are analyzed by X-ray photoelectron spectroscopy (XPS, PHI5000 CESCASCASSYSTEM). The conductivity of graphene was determined by the four-probe VanDerPauw method (AccentHL 5500). And (3) representing the mesoporous structure of the graphene by using a nitrogen adsorption/desorption experiment. Representing the dispersibility of the mesoporous doped graphene in water by zeta potential;
6) performance characterization of mesoporous graphene-doped supercapacitor
Taking 50 mg of a mesoporous doped graphene sample, dispersing in 5 ml of N-methyl pyrrolidone (NMP), and uniformly stirring. And slowly injecting the mixture into the three-dimensional graphene foam, drying and pressing the mixture into an electrode plate. The density of the electrode slice is 0.7-0.85 g per cubic centimeter. 0.5mol/L lithium sulfate is used as electrolyte to prepare a symmetrical electrochemical capacitor for testing.
2. The element-doped graphene with the ultrahigh specific surface area can be obtained by two methods:
1) one or a combination of potassium hydroxide, sodium hydroxide and zinc chloride is added into commercially available graphite to serve as an activating agent, and the ratio of the activating agent to the graphene is 0.5-4. Adding a doping source and a metal source, and ball-milling for 2-8 hours. The mixture is placed in a furnace containing methane, hydrogen, argon or nitrogen (when nitrogen is doped, ammonia can be introduced) at 600-1000 ℃ for heating reaction for 0.5-10 hours. The product is subjected to acid removal of impurities such as catalyst and the like to prepare the product with the specific surface area of more than 1500-2Doped graphene per gram. The method has controllable content of doping elements, low material preparation cost and simple and easy operation;
2) doping elements can also be accomplished by a two-step process: (a) one or a combination of potassium hydroxide, sodium hydroxide and zinc chloride is added into commercially available graphite to serve as an activating agent, and the ratio of the activating agent to the graphene is 0.5-4. Then placing the mixture in a furnace protected by argon or nitrogen at the temperature of 600-2Per g of defective graphene. (b) Mixing the defective graphene with the doping source and the metal source with high specific surface area by ball milling for 0.5-4 hours, and thenThen placing the mixture in a chemical vapor deposition furnace, heating the mixture to 800-1100 ℃ in argon or nitrogen, introducing hydrogen, ammonia (or borane) and a gaseous carbon source, and preserving the heat for 10-30 minutes. Cooled to room temperature and the sample was taken out. The reaction temperature and time depend on the kind of the carbon source and the metal catalyst. The product is subjected to acid removal of impurities such as catalyst and the like to prepare the product with the specific surface area of more than 1500-2Doped graphene per gram. Compared with a one-step method, the method can obtain products with better performance.
3. The ultrahigh specific surface doped three-dimensional graphene can be obtained by two methods:
1) and dispersing the graphene oxide, the doping source and the metal source in an ethanol solvent with nano polymer spheres, and freeze-drying to obtain a three-dimensional porous precursor. Placing the sample in a chemical vapor deposition furnace, heating to 800-1100 ℃ in argon or nitrogen, introducing hydrogen, ammonia and a gas carbon source, preserving the temperature for 10-30 minutes, cooling to room temperature, and taking out the sample. The product is removed with impurities such as nickel and the like by nitric acid, and the specific surface area of the product is more than 1200-2000m2Doped graphene per gram;
2) dispersing graphene oxide, a doping source, nano silicon dioxide and a metal source in an aqueous solution containing a high-molecular adhesive, and heating to prepare a uniformly mixed high-viscosity colloid; after the gel is obtained by continuous heating, the gel is heated in a muffle furnace at the temperature of 250-350 ℃ for 5-10 hours, and the water is slowly removed. The obtained carbonized material is put in a chemical vapor deposition furnace after simple ball milling, the temperature is raised to 800-1100 ℃ in argon or nitrogen, hydrogen, ammonia and a gas carbon source are introduced, the temperature is kept for 10 to 30 minutes, the sample is cooled to room temperature, and the sample is taken out. The product is subjected to acid removal of impurities such as catalyst, silicon dioxide and the like to prepare the product with the specific surface area of more than 1200-2000m2Doped graphene per gram.
FIG. 1 is a schematic diagram of the combination of doping atoms and carbon atoms of the doped carbon-based electrode material obtained by the present invention, taking nitrogen doping as an example;
FIG. 2 is a Raman spectrum of a carbon-based electrode material obtained by the present invention, which shows that the carbon-based electrode material obtained by the present invention has a high degree of purityThe quality of (c). From the figure, it can be seen that the 2D peak is positioned 2685cm-1And has good symmetry, the intensity ratio of the 2D peak to the G peak is I2D/IGThe half-peak width of the 2D peak was 55cm ═ 0.5-1This indicates that the graphene obtained by the present invention has 3 to 5 layers; g peak is obviously stronger than D peak, and the ratio of intensity IG/ID2.5, the defects of the graphene obtained by the invention are few;
FIG. 3 is a small-angle X-ray diffraction diagram, which shows that the graphene obtained by the invention has a hexagonal ordered mesoporous structure, and the corresponding space group is p6 mm;
figure 4 pore size distribution diagram. The pore size distribution is obtained through an adsorption/desorption experiment of nitrogen, and the graphene obtained by the method disclosed by the invention contains two pore channel structures of mesopores (4-6 nanometers) and micropores (0.5-2.0 nanometers);
FIG. 5XPSN1s narrow spectral scan. Indicating that the obtained mesoporous graphene sample contains nitrogen (taking nitrogen doping as an example);
FIG. 6a shows the result of cyclic voltammetry for nitrogen-doped mesoporous graphene in a three-electrode system, wherein the scanning rate is 2 mV/s. It is evident from the figure that the redox peaks are very symmetrical and differ in peak position by 59 mV. The electrochemical reaction rate of the doped graphene obtained by the invention is fast. FIG. 6b is a charge-discharge curve;
FIG. 7a shows the result of cyclic voltammetry for device testing of a symmetrical supercapacitor, taking nitrogen-doped mesoporous graphene as an example, with a scan rate of 2 mV/s; FIG. 7b is a charge-discharge curve;
in the figure 8, after three nitrogen-doped graphene with different oxidation-reduction potentials are compounded, the specific capacity is obviously improved.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like of the following examples are also only one example of suitable ranges, i.e., those skilled in the art can select the appropriate ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1 mesoporous nitrogen-doped carbon-based Material
Preparing an aqueous solution of nickel nitrate with the concentration of 0.1mol/L, and mixing the aqueous solution with commercial mesoporous silica SBA-15 according to the mass ratio of nickel to silica of 1: 2. Stirring, ultrasonic dispersing, vacuumizing to 20Pa, and volatilizing to obtain sol. Heating to 450 ℃ in an argon atmosphere containing 5% of hydrogen, and preserving heat for 2 hours to obtain mesoporous silica (SBA-15/Ni) filled with metallic nickel;
dissolving carbon source polyfurfuryl alcohol and aminoguanidine into ethanol according to the proportion of 5:1, adding SBA-15/Ni, carrying out ultrasonic dispersion for 30 minutes, and drying at 100 ℃ for 10 hours to obtain dry gel of SBA-15/Ni/polyfurfuryl alcohol/aminoguanidine;
50 g of the sample is placed in an atmosphere furnace, the temperature is raised to 900 ℃ in argon or nitrogen, hydrogen, ammonia and methane are introduced according to the proportion of 20:15:10sccm, and the temperature is kept for 10-30 minutes. Cooling to room temperature, and taking out a sample;
and soaking the obtained sample in a mixed solution of hydrochloric acid and hydrofluoric acid, filtering after 24 hours, and washing with a large amount of deionized water and ethanol. Drying the obtained nitrogen-doped mesoporous doped graphene;
the morphology of the sample was observed by transmission electron microscopy (JEM 2010). The structure of graphene was characterized by Raman spectroscopy (RenishawinviaRamamane Microscope, excitation wavelength 514.5 nm). The relative content ratio of each element on the surface of the sample and the chemical combination state thereof are analyzed by X-ray photoelectron spectroscopy (XPS, PHI5000 CESCASCASSYSTEM). The conductivity of graphene was determined by the four-probe VanDerPauw method (AccentHL 5500). And (3) representing the mesoporous structure of the graphene by using a nitrogen adsorption/desorption experiment. Representing the dispersibility of the mesoporous doped graphene in water by zeta potential;
taking 50 mg of a mesoporous nitrogen-doped graphene sample, dispersing in 5 ml of N-methyl pyrrolidone (NMP), and uniformly stirring. And slowly injecting the mixture into the three-dimensional graphene foam, drying and pressing the mixture into an electrode plate. The density of the electrode sheet was 0.75 grams per cubic centimeter. 0.5mol/L lithium sulfate is taken as electrolyte to prepare a symmetrical electrochemical capacitor for testing;
the specific capacity of the obtained sample under the current density of 1A/g is 650F/g, and the volume specific capacity is 480F/cm3The retention ratio of the current after 1 ten thousand full charges was 92.5%, the energy density was 58Wh/kg, and the power density was 45 kW/kg.
In the carbon-based electrode material prepared in this example, the atomic concentration of the doping element is 7.8%, and sp of the carbon atom is2The hybridization proportion is 98%, the pyridine type and pyrrole type combination mode between nitrogen and carbon accounts for 82% of all nitrogen elements, 82% of the nitrogen elements are active sites, Faraday pseudo-capacitance is generated, and the specific surface area of the carbon-based composite electrode material is 1852 square meters per gram;
fig. 1 shows a bonding manner between nitrogen and carbon of the nitrogen-doped graphene obtained in this embodiment. In the figure, N-5 represents pyrrole type nitrogen, N-6 represents pyridine type nitrogen, and N-Q represents graphite type nitrogen. Where N-5 and N-6 may create Faraday pseudocapacitance.
Fig. 2 is a raman spectrum of the carbon-based electrode material obtained in the present embodiment, which shows that the carbon-based electrode material obtained in the present invention has high quality. From the figure, it can be seen that the 2D peak is positioned 2685cm-1And has good symmetry, the intensity ratio of the 2D peak to the G peak is I2D/IGThe half-peak width of the 2D peak was 55cm ═ 0.5-1This indicates that the graphene obtained by the present invention has 3 to 5 layers; g peak is obviously stronger than D peak, and the ratio of intensity IG/IDAnd 2.5, the defect of the graphene obtained by the invention is less.
Fig. 3 is a small-angle X-ray diffraction pattern of the carbon-based electrode material prepared in the example, which shows that the graphene obtained by the invention has a hexagonal ordered mesoporous structure, and the corresponding space group is p6 mm.
Fig. 4 is a pore size distribution diagram of the carbon-based electrode material prepared in the present example. The pore size distribution is obtained through an adsorption/desorption experiment of nitrogen, and the graphene obtained by the method disclosed by the invention contains two pore channel structures of mesopores (4-6 nanometers) and micropores (0.5-2.0 nanometers).
Fig. 5 is a narrow spectrum scan of XPSN1s of a carbon-based electrode material prepared in this example. It is shown that the obtained mesoporous graphene sample contains nitrogen (nitrogen doping is taken as an example).
FIG. 6a shows the result of cyclic voltammetry for the nitrogen-doped mesoporous graphene prepared in this example in a three-electrode system, wherein the scan rate is 2 mV/s. It is evident from the figure that the redox peaks are very symmetrical and differ in peak position by 59 mV. The electrochemical reaction rate of the doped graphene obtained by the invention is fast. Fig. 6b is a charge-discharge curve at a current density of 0.5A/g, from which it can be seen that the charge time is 1350 seconds, the discharge time is 1420 seconds, the specific capacitance is 675 farads per gram, and the coulombic efficiency is greater than 95%.
FIG. 7a shows the result of cyclic voltammetry for device testing of a symmetrical supercapacitor, taking nitrogen-doped mesoporous graphene as an example, with a scan rate of 2 mV/s; FIG. 7b is a charge and discharge curve at a current density of 0.5A/g. It can be seen that the charging and discharging time is similar and presents a straight line, which shows that the charging and discharging rate and the coulombic efficiency are good.
Comparative example 1 mesoporous nitrogen doped amorphous carbon
Dissolving carbon source polyfurfuryl alcohol and aminoguanidine into ethanol according to the proportion of 5:1, adding mesoporous silicon dioxide SBA-15, performing ultrasonic dispersion for 30 minutes, and drying at 100 ℃ for 10 hours to obtain dry gel of SBA-15/polyfurfuryl alcohol/aminoguanidine;
50 g of the sample is placed in an atmosphere furnace, heated to 900 ℃ in argon or nitrogen, and kept for 1030 minutes. Cooling to room temperature, and taking out a sample;
and soaking the obtained sample in a mixed solution of hydrofluoric acid for 24 hours, filtering, and washing with a large amount of deionized water and ethanol. Drying the obtained nitrogen-doped amorphous carbon;
the preparation and characterization method of the supercapacitor electrode is the same as that of the embodiment 1;
the specific capacity of the obtained sample under the current density of 1A/g is 185F/g, and the volume specific capacity is 75F/cm3The retention rate of current after 1 ten thousand full charges was 83%, the energy density was 8Wh/kg, and the power density was 0.92 kW/kg.
Example 2 mesoporous nitrogen doped graphene with different redox potentials
The preparation method of the mesoporous silica (SBA-15/Ni) filled with the metal nickel is completely the same as that of the embodiment 1;
respectively dissolving carbon source polyfurfuryl alcohol and aminoguanidine into ethanol according to the proportion of 5:1 (namely embodiment 1), 2:1 and 1:1, adding SBA-15/Ni, carrying out ultrasonic dispersion for 30 minutes, and drying for 10 hours at 100 ℃ to obtain xerogels of three groups of SBA-15/Ni/polyfurfuryl alcohol/aminoguanidine;
50 g of each sample is taken and respectively placed in an atmosphere furnace, the temperature is raised to 900 ℃ in argon or nitrogen, hydrogen, ammonia and methane are introduced, the ratio is 20:15:10sccm, and the temperature is kept for 10-30 minutes. Cooling to room temperature, and taking out a sample;
and soaking the obtained sample in a mixed solution of hydrochloric acid and hydrofluoric acid, filtering after 24 hours, and washing with a large amount of deionized water and ethanol. Drying to obtain three kinds of nitrogen-doped mesoporous doped graphene;
the three samples with different nitrogen contents are taken, 50 mg of each sample is taken, and the samples are dispersed in 15 ml of N-methyl pyrrolidone (NMP) and stirred uniformly. And slowly injecting the mixture into the three-dimensional graphene foam, drying and pressing the mixture into an electrode plate. The density of the electrode sheet was 0.75 grams per cubic centimeter. 0.5mol/L lithium sulfate is taken as electrolyte, the working voltage is 0-1.6V, and a symmetrical electrochemical capacitor is made for testing;
the specific capacity of the obtained electrode under the current density of 1A/g is 820F/g, and the volume specific capacity is 630F/cm3The retention rate of current after 1 ten thousand times of full electricity is 93%, the energy density is 71Wh/kg, and the power density is 85 kW/kg;
in the carbon-based composite electrode material prepared by compositing the doped carbon-based materials with different redox potentials in the embodiment, the atomic concentration of the doping element is 8.2%, and sp of carbon atoms2The hybridization proportion is 97.5 percent, the pyridine type and pyrrole type combination mode between nitrogen and carbon accounts for 88 percent of all nitrogen elements, 88 percent of the nitrogen elements are active sites, the Faraday pseudo-capacitance is generated, and the specific surface area of the carbon-based composite electrode material is 2100 square meters per gram.
As shown in FIG. 8, the doped carbon-based material with different redox potentials of example 2 exhibited a 26% increase in specific capacitance from 650F/g to 820F/g after recombination, as compared to the single doped material of example 1; the energy density is improved from 58 to 71Wh/kg, and is improved by 22 percent.
Example 3 mesoporous boron doped carbon-based material
Mesoporous silica (SBA-15/Ni) filled with metallic nickel was prepared as in example 1;
taking carbon sources of polyfurfuryl alcohol (PFA) and boron tribromide (BBr)3) Dissolving in ethanol at a ratio of 5:2, adding SBA-15/Ni, ultrasonically dispersing for 30 min, and drying at 100 deg.C for 10 hr to obtain SBA-15/Ni/PFA/BBr3The xerogel of (a);
50 g of the sample is placed in an atmosphere furnace, the temperature is raised to 800 ℃ in argon or nitrogen, hydrogen and methane are introduced, the ratio is 20:10sccm, and the temperature is kept for 10-30 minutes. Cooling to room temperature, and taking out a sample;
and soaking the obtained sample in a mixed solution of hydrochloric acid and hydrofluoric acid, filtering after 24 hours, and washing with a large amount of deionized water and ethanol. Drying the obtained boron-doped mesoporous doped graphene;
the characterization and electrochemical test of the mesoporous boron doped graphene are the same as those of the embodiment 1;
the specific capacity of the obtained mesoporous boron doped graphene sample under the current density of 1A/g is 520F/g, and the volume specific capacity is 370F/cm3The retention rate of current after 1 ten thousand times of full electricity is 90.5%, the energy density is 46Wh/kg, and the power density is 32 kW/kg;
in the carbon-based electrode material prepared in this example, the atomic concentration of the doping element is 6.1%, and sp of the carbon atom is2The hybridization proportion is 98.2%, the combination mode of boron and carbon atoms in graphene comprises intra-ring doping, boundary doping and high defect site doping, and the specific surface area of the carbon-based electrode material is 2450 square meters per gram.
Example 4 mesoporous phosphorus doped carbon-based Material
Mesoporous silica (SBA-15/Ni) filled with metallic nickel was prepared as in example 1;
dissolving carbon source phenolic resin and triphenylphosphine in ethanol according to the ratio of 6:1, adding SBA-15/Ni, performing ultrasonic dispersion for 40 minutes, and drying at 100 ℃ for 10 hours to obtain dry gel of SBA-15/Ni/phenolic resin/triphenylphosphine;
50 g of the sample is placed in an atmosphere furnace, the temperature is raised to 800 ℃ in argon or nitrogen, hydrogen and methane are introduced, the ratio is 20:10sccm, and the temperature is kept for 10-30 minutes. Cooling to room temperature, and taking out a sample;
and soaking the obtained sample in a mixed solution of hydrochloric acid and hydrofluoric acid, filtering after 24 hours, and washing with a large amount of deionized water and ethanol. Drying the obtained phosphorus-doped mesoporous doped graphene;
the characterization and electrochemical test of the mesoporous phosphorus-doped graphene are the same as those in example 1;
the specific capacity of the obtained mesoporous boron doped graphene sample under the current density of 1A/g is 420F/g,the specific volumetric capacity is 330F/cm3The retention rate of current after 1 ten thousand times of full electricity is 90.0 percent, the energy density is 37Wh/kg, and the power density is 28 kW/kg;
in the carbon-based electrode material prepared in this example, the atomic concentration of the doping element is 3.9%, and sp of the carbon atom is2The hybridization proportion is 92%, the combination mode of phosphorus and carbon atoms in the graphene comprises intra-ring doping, boundary doping and high-defect-level doping, and the specific surface area of the carbon-based electrode material is 1720 square meters per gram.
Example 5 mesoporous sulfur doped carbon-based materials
Mesoporous silica (SBA-15/Co) filled with metallic cobalt was prepared as in example 1, except that nickel nitrate was substituted for cobalt nitrate;
dissolving carbon source glucose and thiourea in ethanol according to a ratio of 4:1, adding SBA-15/Co, performing ultrasonic dispersion for 60 minutes, and drying at 100 ℃ for 10 hours to obtain dry gel of SBA-15/Co/glucose/thiourea phenolic resin;
50 g of the sample is placed in an atmosphere furnace, the temperature is raised to 800 ℃ in argon or nitrogen, hydrogen and methane are introduced, the ratio is 20:10sccm, and the temperature is kept for 10-30 minutes. Cooling to room temperature, and taking out a sample;
and soaking the obtained sample in a mixed solution of hydrochloric acid and hydrofluoric acid, filtering after 24 hours, and washing with a large amount of deionized water and ethanol. Drying to obtain sulfur-doped mesoporous doped graphene;
the characterization and electrochemical test of the mesoporous phosphorus-doped graphene are the same as those in example 1;
the specific capacity of the obtained mesoporous phosphorus doped graphene sample under the current density of 1A/g is 580F/g, and the volume specific capacity is 440F/cm3The retention rate of current after 1 ten thousand times of full electricity is 93.0 percent, the energy density is 52Wh/kg, and the power density is 46 kW/kg;
in the carbon-based electrode material prepared in this example, the atomic concentration of the doping element is 5.7%, and sp of the carbon atom is2The hybridization proportion is 90.8%, the combination mode between the sulfur element and the carbon atoms in the graphene comprises boundary doping and high defect site doping, and the proportion of each type of combination mode is as follows: the doped sulfur at the boundary accounts for 82 percent, 65 percent of sulfur elements are active sites, the Faraday pseudo-capacitance is generated, and the specific surface area of the carbon-based electrode material is 2150 square meters per gram.
Example 6 composite of mesoporous doped carbon-based Material with conductive Polymer
The feasibility of the invention is illustrated by the example of compounding polyaniline with a mesoporous nitrogen-doped carbon-based material;
the preparation of the mesoporous nitrogen-doped carbon-based material is completely the same as that of the embodiment 1;
in an ice-water bath, 0.05 g of the mesoporous nitrogen-doped carbon-based material prepared in example (1) was added to 100 ml of an aqueous aniline hydrochloride solution having a concentration of 1mol per liter. After stirring and mixing evenly, slowly dropping 50 ml of ammonium persulfate solution with the concentration of 0.2 mol per liter, and stirring for 6 hours. Filtering, washing with deionized water, and drying to obtain the mesoporous nitrogen doped carbon-based material/polyaniline composite material;
50 mg of the composite material is taken and dispersed in 5 ml of N-methyl pyrrolidone (NMP) and stirred uniformly. And slowly injecting the mixture into the three-dimensional graphene foam, drying and pressing the mixture into an electrode plate. 0.5mol/L sulfuric acid is used as electrolyte to prepare a symmetrical electrochemical capacitor for testing;
the specific capacity of the obtained sample compounded by the mesoporous doped carbon-based material and the conductive polymer at the current density of 1A/g is 1080F/g, the retention rate of the current after 1 ten thousand times of full electricity is 76.0%, the energy density is 92Wh/kg, and the power density is 26 kW/kg.
Comparative example 2 conventional conductive Polymer
Similar to example 6, except that the carbon-based material was not added during the polymerization of aniline;
in an ice-water bath, 100 ml of aqueous aniline hydrochloride solution having a concentration of 1mol per liter. After stirring and mixing evenly, slowly dropping 50 ml of ammonium persulfate solution with the concentration of 0.2 mol per liter, and stirring for 6 hours. Filtering, washing with deionized water, and drying to obtain the polyaniline composite material;
50 mg of the composite material is taken and dispersed in 5 ml of N-methyl pyrrolidone (NMP) and stirred uniformly. And slowly injecting the mixture into the three-dimensional graphene foam, drying and pressing the mixture into an electrode plate. 0.5mol/L sulfuric acid is used as electrolyte to prepare a symmetrical electrochemical capacitor for testing;
the specific capacity of the obtained conductive polymer composite sample at the current density of 1A/g is 920F/g, the retention rate of the current after 1 ten thousand times of full electricity is 48.0%, the energy density is 83Wh/kg, and the power density is 0.45 kW/kg.
Compared with pure polyaniline, the carbon/polyaniline-doped composite material provided by the invention has the advantages that the cycle life is prolonged by 58%, and the power density is increased by more than 50 times.
Example 7 ultra high surface area nitrogen doped graphene, carried out by method 2.1
To 10 g of commercially available graphite, 5g of potassium hydroxide was added as an activator, 5g of aminoguanidine was added as a nitrogen source, and 5g of nickel acetate was added as a catalyst, and ball-milled for 2 hours. Placing the mixture in a tubular furnace, heating to 1000 ℃, introducing methane, hydrogen, argon and nitrogen in a ratio of 20:50:300:20sccm, and heating for reaction for 0.5 hour. Removing impurities such as metallic nickel catalyst and the like from the product by hydrochloric acid to prepare the product with the specific surface area exceeding 2500m2Doped graphene per gram;
the characterization and the electrochemical test of the doped graphene with the ultrahigh specific surface area are the same as those of the embodiment 1;
the nitrogen content of the obtained sample was 5% at 1A/gThe specific capacity under the current density is 620F/g, and the volumetric specific capacity is 460F/cm3The retention rate of current after 1 ten thousand times of full electricity is 92.5 percent, the energy density is 42Wh/kg, and the power density is 31 kW/kg;
in the carbon-based electrode material prepared in this example, the atomic concentration of the doping element is 5%, and sp of the carbon atom is2The hybridization proportion is 89%, the proportion of pyridine type and pyrrole type combination mode between nitrogen and carbon is 72%, 72% of nitrogen elements are active sites, Faraday pseudo-capacitance is generated, and the specific surface area of the carbon-based electrode material is 2750 square meters per gram.
Example 8 ultra high surface area boron doped high specific area graphene, performed by method 2.2
To 10 g of graphene, 5g of potassium hydroxide was added as an activator, and ball-milled for 10 hours. Placing the mixture in a tubular furnace, introducing nitrogen as protective gas, heating to 900 ℃, reacting for 2 hours to prepare the mixture with the specific surface area of 2000m2(ii) defective graphene/g;
and ball-milling and mixing the defective graphene with high specific surface area, 20 g of boric acid as a doping source and a catalyst cobalt nitrate for 4 hours, then placing the mixture in a chemical vapor deposition furnace, heating the mixture to 800 ℃ in argon or nitrogen, introducing argon, hydrogen and methane, and keeping the temperature for 30 minutes. Cooled to room temperature and the sample was taken out. The product is subjected to acid removal of impurities such as catalyst and the like to prepare the product with the specific surface area of more than 2200m2Doped graphene per gram;
the characterization and the electrochemical test of the doped graphene with the ultrahigh specific surface area are the same as those of the embodiment 1;
the boron content of the obtained sample is 8 percent, the specific capacity under the current density of 1A/g is 680F/g, and the volume specific capacity is 490F/cm3The retention rate of current after 1 ten thousand times of full electricity is 91.2 percent, the energy density is 46Wh/kg, and the power density is 37 kW/kg;
carbon-based electrode material prepared in this exampleSp of middle, carbon atom2The hybridization proportion is 85%, the combination mode of boron and carbon atoms in the graphene comprises intra-ring doping, boundary doping and high-defect-level doping, and the specific surface area of the carbon-based electrode material is 1890 square meters per gram.
Example 9 ultra-high specific surface area nitrogen-doped three-dimensional graphene
Filling a metal catalyst, a carbon source and a doping source into a pore channel by taking one of porous silicon dioxide with a three-dimensional continuous pore structure as a template, and preparing the nitrogen-doped high-specific-surface-area three-dimensional graphene by a chemical vapor deposition method. The method comprises the following specific steps:
preparing an aqueous solution of nickel nitrate with the concentration of 0.1mol/L, and mixing the aqueous solution with the three-dimensional porous silica according to the mass ratio of nickel to silica of 1: 1. Stirring, ultrasonically dispersing, vacuumizing until the pressure is 10Pa, and volatilizing the solution. Heating to 400 ℃ in an argon atmosphere containing 5% of hydrogen, and preserving the heat for 2 hours to obtain the three-dimensional porous silicon dioxide (SiO) filled with metallic nickel2/Ni)；
Dissolving carbon source polyfurfuryl alcohol and aminoguanidine in ethanol according to the proportion of 4:1, adding SiO2Ni, ultrasonic dispersing for 30 minutes, drying for 10 hours at 100 ℃ to obtain SiO2A Ni/polyfurfuryl alcohol/aminoguanidine precursor;
heating the sample to 900 ℃ in argon or nitrogen, introducing hydrogen, ammonia gas, methane and water vapor in a ratio of 20:15:10:5sccm, and keeping the temperature for 30 minutes. Cooling to room temperature, and taking out a sample;
and soaking the obtained sample in a mixed solution of hydrochloric acid and hydrofluoric acid, filtering after 24 hours, and washing with a large amount of deionized water and ethanol. Drying the obtained nitrogen-doped three-dimensional graphene with high specific surface area;
the characterization and electrochemical test of the nitrogen-doped three-dimensional graphene with the ultrahigh specific surface area are the same as those of the embodiment 1;
the obtained sample had a nitrogen content of 14% and a specific surface area of 2400m2(ii)/g, the specific capacity under the current density of 1A/g is 460F/g, and the volume specific capacity is 320F/cm3The retention rate of current after 1 ten thousand times of full electricity is 90.6 percent, the energy density is 32Wh/kg, and the power density is 21 kW/kg;
in the carbon-based electrode material prepared in this example, sp of carbon atom2The hybridization proportion is 78%, the pyridine type and pyrrole type combination mode proportion between nitrogen and carbon is 67%, 67% of nitrogen elements are active sites, the Faraday pseudo-capacitance is generated, and the specific surface area of the carbon-based electrode material is 2220 square meters per gram.
Example 11 ultra-high specific surface Nitrogen-doped three-dimensional graphene
2 g of graphene oxide, 1 g of glycine and 1.5 g of ferric nitrate are dispersed in an ethanol solvent (100 ml) with nano polystyrene spheres, and a three-dimensional porous precursor is obtained by freeze drying. Placing the sample in a chemical vapor deposition furnace, heating to 800 ℃ in argon, introducing hydrogen, ammonia gas and a gas carbon source in a ratio of 20:15:10sccm, preserving the temperature for 30 minutes, cooling to room temperature, and taking out the sample. Removing iron and other impurities from the product by nitric acid to prepare the product with the specific surface area over 2000m2Doped graphene per gram;
the characterization and electrochemical test of the nitrogen-doped three-dimensional graphene with the ultrahigh specific surface area are the same as those of the embodiment 1;
the obtained sample has nitrogen content of 3.6%, specific capacity of 410F/g under current density of 1A/g, and volume specific capacity of 270F/cm3The retention rate of current after 1 ten thousand times of full electricity is 92.8 percent, the energy density is 21Wh/kg, and the power density is 14 kW/kg;
in the carbon-based electrode material prepared in this example, sp of carbon atom289% of hybridization, 76% of pyridine type and pyrrole type combination mode between nitrogen and carbon, 76% of nitrogen element as active site, generating Faraday pseudo-capacitance, and specific surface of carbon-based electrode materialThe product is 2450 square meters per gram.
Example 12 ultra-high specific surface area nitrogen-doped three-dimensional graphene
2 g of graphene oxide, 1 g of glycine and 3 g of cobalt nitrate are dispersed in an aqueous solution containing a high-molecular adhesive PEG, the aqueous solution is heated to 60 ℃, and the mixture is stirred for 2 hours to prepare a uniformly mixed high-viscosity colloid. The colloid was heated in a muffle furnace at 350 ℃ for 5 hours, and water was slowly removed. The obtained carbonized material is put into a chemical vapor deposition furnace after simple ball milling, the temperature is raised to 1100 ℃ in argon or nitrogen, hydrogen, ammonia gas, methane and ammonia gas are introduced at the ratio of 20:15:10:10sccm, the temperature is kept for 30 minutes, the sample is cooled to room temperature, and then the sample is taken out. The product is subjected to acid to remove impurities such as catalyst, silicon dioxide and the like, and the specific surface area is 2000m2Doped graphene per gram;
in the carbon-based electrode material prepared in this example, the atomic concentration of the doping element is 10.8%, and sp of the carbon atom is2The hybridization proportion is 76%, the pyridine type and pyrrole type combination mode proportion between nitrogen and carbon is 66%, 66% of nitrogen elements are active sites, the Faraday pseudo-capacitance is generated, and the specific surface area of the carbon-based electrode material is 2840 square meters per gram.
Claims (13)
1. The carbon-based electrode material with the ultrahigh specific capacitance is characterized in that the capacitance of the carbon-based electrode material is composed of two parts, namely an electric double layer capacitance and a Faraday pseudocapacitance, the electric double layer capacitance accounts for 20-60% of the capacitance of the carbon-based electrode material, the specific capacity of the carbon-based electrode material is more than 400 under the current density of 1A/g, the volume specific capacity is more than 300 farads per milliliter, the energy density of a symmetrical device of a water-based electrolyte is more than 20 watt-hour per kilogram, and the volume energy density is more than 15 watt-hour per liter.
2. Carbon-based electrode material with ultra-high specific capacitance according to claim 1, characterized in that the carbon atoms in the carbon-based electrode material aresp 2The hybridization ratio is more than 60%, and the conductivity of the carbon-based electrode material is more than 200 Siemens per centimeter.
3. Carbon-based electrode material with ultra-high specific capacitance according to claim 1 or 2, characterized in that the specific surface area of the carbon-based electrode material is above 1200 square meters per gram.
4. Carbon-based electrode material with ultra-high specific capacitance according to claim 1 or 2, characterized in that the zeta potential of the carbon-based electrode material in water is less than-15 mV.
5. The carbon-based electrode material with ultrahigh specific capacitance according to any one of claims 1-4, wherein the faradaic pseudocapacitance of the carbon-based electrode material is generated by introducing a doping element into an active site, wherein the doping element is at least one of nitrogen, boron, phosphorus and sulfur, and the doping amount of the doping element is 0.5% -20%.
6. The carbon-based electrode material with ultra-high specific capacitance according to claim 5, wherein the doping element is combined with charged ions to cause redox reaction to introduce the active sites.
7. Carbon-based electrode material with ultra-high specific capacitance according to claim 5 or 6, characterized in that the bonding means between the doping elements and the carbon atoms comprise intra-ring doping, boundary doping and high defect site doping.
8. The carbon-based electrode material according to any one of claims 5 to 7, wherein the doping element is nitrogen, and the bonding manner of nitrogen and carbon in the carbon-based electrode material includes pyridine type, pyrrole type, and graphite type, wherein the pyridine type and the pyrrole type account for more than 70%.
9. The carbon-based electrode material according to any one of claims 5 to 8, wherein the carbon-based electrode material is mesoporous graphene doped with the doping element at a high specific surface area, and carbon atoms in the mesoporous graphene doped with the doping element at the high specific surface areasp 2The hybridization proportion is more than 80%, the specific surface area is more than 1500 square meters per gram, the conductivity is more than 400 Siemens per centimeter, and the number of layers of the graphene is 3-5.
10. The carbon-based electrode material according to claim 9, wherein the high specific surface area doped three-dimensional graphene has a three-dimensionally interconnected conductive network with a conductivity greater than 300 siemens per centimeter, a specific surface area greater than 2000 square meters per gram and a density of less than 0.1 grams per cubic centimeter.
11. The carbon-based electrode material according to any one of claims 1 to 10, wherein the carbon-based electrode material comprises both mesoporous and microporous pore structures, the pore size of the micropores is in the range of 0.5 to 2 nm, and the pore size of the mesopores is in the range of 2 to 20 nm.
12. A composite electrode material comprising a carbon-based electrode material according to any one of claims 1 to 11, wherein the composite material is formed by compounding the carbon-based electrode material having different redox potentials or by compounding the carbon-based electrode material with a metal compound and/or a conductive polymer.
13. The composite electrode material of claim 12, wherein the metal compound comprises at least one of manganese oxide, nickel oxide, cobalt oxide, niobium oxide, tantalum oxide, ruthenium oxide, titanium sulfide, molybdenum sulfide, vanadium sulfide, tantalum sulfide, vanadium selenide, tantalum selenide, and the conductive polymer comprises polyaniline, polypyrrole, and/or polythiophene.
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