CN114334469A - Two-dimensional graphitized nano carbon material and preparation method and electrochemical application thereof - Google Patents
Two-dimensional graphitized nano carbon material and preparation method and electrochemical application thereof Download PDFInfo
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- 238000003763 carbonization Methods 0.000 claims abstract description 10
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- 239000007772 electrode material Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 10
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- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 4
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
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- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 claims description 3
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Abstract
The invention relates to a two-dimensional graphitized nano carbon material, a preparation method and electrochemical application thereof. According to the invention, biomass fish scales are used as raw materials, after acid-base pretreatment, liquefaction is carried out by a biological enzymolysis method to obtain a uniform liquid-phase carbon source, a catalyst is introduced, high-temperature carbonization is carried out, and a graphitized nano carbon material is obtained after post-treatment. The preparation method comprises the following steps: coordination compounding of a carbon source and metal ions; obtaining a metal-carbon source precursor through curing treatment; carbonizing at different temperatures; finally, the graphitized nano carbon materials with different morphologies can be obtained by activation treatment. The results of the examples show that the biomass carbon material modified foam nickel electrode provided by the invention is 1A g‑1The optimal specific capacitance at current density was 448F g‑1The capacity retention of the electrode after 5000 cycles was 98.46%.
Description
Technical Field
The invention belongs to the technical field of electrode materials, and relates to a two-dimensional graphitized nano carbon material, a preparation method thereof and electrochemical application thereof.
Background
In recent decades, the conversion of low value biomass into high quality, high energy density, clean, zero carbon dioxide emission, commercially valuable materials has been a research hotspot. As a natural organic high molecular substance, the biomass has high carbon element content, wide availability, low cost, renewable resources and wide development prospect. Therefore, the carbon precursor is often used as a carbon precursor to construct a biological carbon material, and has wide application in the fields of supercapacitors, electrocatalysis, electrochemical sensors, lithium/sodium ion batteries and the like. In recent years, extensive research has been conducted on the conversion of natural biomass into various functional carbon materials. Heteroatoms and large surface area in the carbon skeleton facilitate ion diffusion and accelerate electron transfer reactions, which are important factors affecting their application in energy storage and conversion. Despite the broad development prospects of biomass carbon material electrodes, the rational and efficient construction of carbon material electrodes meeting the requirements of energy storage and conversion is still a great challenge so far.
Disclosure of Invention
In view of the above, the invention provides a two-dimensional graphitized nano carbon material, and a preparation method and application thereof.
The invention provides a graphitized nano carbon material, which has a porous structure; the graphitized nano carbon material has a lamellar structure.
Preferably, the specific surface area of the graphitized nano carbon is 900-1300 m2 g-1。
Preferably, the graphitized nanocarbon has a thin flat lamellar structure.
The invention provides a preparation method of the graphitized nano carbon material in the technical scheme, which comprises the following steps: (1) soaking biomass fish scales in strong acid and strong base solutions in sequence, then cleaning with ultrapure water, draining, adding quantitative biological enzyme and ultrapure water, stirring and reacting for 24 hours, and filtering to obtain a liquid solution; (2) catalyzing the solution prepared in step 1 with a certain amount of metalUniformly mixing and stirring the agents at 40-50 ℃, and then drying in vacuum for 2-24 hours to obtain solid substances; (3) at 4-12 ℃ for min-1The temperature is increased to 800-1000 ℃ at the speed, and the air flow is 80-120 ml min-1Under the condition, carrying out carbonization treatment on the solid obtained in the step 2 for 2-8 h; (4) performing acid treatment on the product obtained in the step 3 to remove metal substances in the product to obtain a black solid; (5) and (4) carrying out chemical alkali activation treatment on the product obtained in the step (4) to obtain the graphitized nano carbon material.
Preferably, the molar concentration of the strong alkali solution is preferably 1-20 mol L-1The strong alkali solution is a potassium hydroxide solution and/or a sodium hydroxide solution; the concentration of the strong acid is 10-40%, and the strong acid is concentrated hydrochloric acid; the mass concentration of the enzyme is 10-40%, and the enzyme is alkaline protease.
Preferably, the mass ratio of the catalyst to the biomass precursor is 1: (1-3); the catalyst is potassium ferricyanide, potassium ferrocyanide, ferric chloride, ferric nitrate or ferric sulfate.
Preferably, the carbonization temperature is 800-1000 ℃, the time is 2-4 h, and the temperature rise rate of raising the temperature to the carbonization temperature is 4-12 ℃ min-1。
The invention provides an application of the two-dimensional graphitized nano carbon material in the technical scheme or the two-dimensional graphitized nano carbon material obtained by the preparation method in the technical scheme in a super capacitor electrode material.
The graphitized nano carbon material provided by the invention is of a porous sheet layered structure, is composed of a porous two-dimensional carbon film, has a large specific surface area and a high graphitization degree, is doped with nitrogen, and is beneficial to improving the specific capacitance of the material in actual use. The results of the examples show that the foamed nickel electrode modified by the graphitized nano carbon material provided by the invention is 1A g-1The optimal specific capacitance at current density was 448F g-1。1A g-1The capacity retention rate of the electrode after 5000 cycles under the current density is 94.92-98.46%, and the alternating current impedance test result shows that the charge transfer resistance is 0.15-0.34 omega.
Drawings
Fig. 1 is a transmission electron microscope image of the graphitized nanocarbon material prepared in example 1.
Fig. 2 is an X-ray diffraction spectrum diagram of the graphitized nanocarbon material prepared in example 1.
Fig. 3 is an X-ray photoelectron spectrum of the graphitized nanocarbon material prepared in example 1.
Fig. 4 is a core level region XPS spectrum of C1s in the graphitized nanocarbon material prepared in example 1.
Fig. 5 is a core level region XPS spectrum of O1s in the graphitized nanocarbon material prepared in example 1.
Fig. 6 is a core level region XPS spectrum of N1s in the graphitized nanocarbon material prepared in example 1.
Fig. 7 is an adsorption isotherm curve of the graphitized nanocarbon material of application example 1.
Fig. 8 is a pore size distribution curve of the graphitized nanocarbon material of application example 1.
Fig. 9 is a cyclic voltammogram scanned with the graphitized nanocarbon material/foamed nickel supercapacitor electrode of application example 1 as a working electrode.
Fig. 10 is a constant current charge and discharge graph scanned using the graphitized nanocarbon material/foamed nickel supercapacitor electrode of example 1 as a working electrode.
Fig. 11 is a Nyquist plot of the graphitized nanocarbon material/foamed nickel supercapacitor electrode of application example 1 as a working electrode.
Fig. 12 is a cycle stability test chart of an electrode of an application example 1 graphitized nano carbon material/foamed nickel supercapacitor.
Fig. 13 is a cyclic voltammogram scanned using the graphitized nanocarbon material/foamed nickel supercapacitor electrode of example 2 as the working electrode.
Fig. 14 is a constant current charge and discharge curve diagram of the graphitized nano carbon material/foamed nickel supercapacitor electrode as a working electrode in application example 2.
Fig. 15 is a Nyquist plot of the graphitized nanocarbon material/foamed nickel supercapacitor electrode of application example 2 as a working electrode.
Detailed Description
The invention provides a two-dimensional graphitized nano carbon material, a preparation method and electrochemical application thereof.
The specific surface area of the graphitized nano carbon provided by the invention is 900-1300 m2 g-1。
Preferably, the graphitized nanocarbon has a thin lamellar structure.
In the present invention, the method for preparing the graphitized nanocarbon material preferably comprises the steps of: firstly, the biomass raw material is sequentially treated by acid and alkali, and then the liquefied biomass is obtained by enzymolysis.
In the invention, the biomass raw material is preferably fish scales; in the present invention, the biomass raw material is preferably subjected to a pretreatment, and in the present invention, the pretreatment preferably includes: the biomass raw material is sequentially washed, dried, acid treated, alkali treated and enzymolyzed, wherein the washing is preferably water washing, and the specific implementation process of the drying has no special requirement.
In the invention, the alkali treatment is preferably potassium hydroxide solution and/or sodium hydroxide solution, and the molar concentration of the strong alkali solution is preferably 1-20 mol L-1More preferably 5 to 10% mol L-1。
In the invention, the strong acid solution is preferably concentrated hydrochloric acid, and the mass concentration of the strong acid is preferably 10-40%, and more preferably 20-30%.
In the invention, the volume ratio of the wet weight of the biomass raw material to the strong alkali solution or the strong acid solution is preferably (40-50) g: (240-300) mL.
In the invention, the biological enzyme is preferably an alkaline protease solution, and the mass concentration is preferably 10-40%, more preferably 25-35%.
The method has no special requirement on the specific implementation process of mixing the biomass raw material and the strong base or strong acid solution, the time of acid treatment and alkali treatment is preferably 12-24 h, and the temperature of acid treatment and alkali treatment is preferably room temperature.
In the invention, the enzymolysis time is preferably 24 hours, and the enzymolysis temperature is preferably 50-80 ℃, and more preferably 65-75 ℃.
In the present invention, it is preferable to perform post-treatment on the system obtained by enzymatic hydrolysis to obtain an enzymatic biomass, and in the present invention, the post-treatment preferably includes: solid-liquid separation and concentration refrigeration are sequentially carried out, in the invention, the solid-liquid separation is preferably filtration, and in the invention, the solid product after the solid-liquid separation is preferably concentrated and refrigerated for later use; in the invention, the concentration is preferably evaporation concentration, and the concentration temperature is preferably 50-60 ℃; the invention has no special requirement on the evaporation time so as to realize the concentration of the liquid to 30 percent of the original volume; in the invention, the refrigeration is performed by a household refrigerator, no special requirement is imposed on the refrigeration time, and the refrigeration temperature is preferably 1-4 ℃.
After the enzymolysis biomass is obtained, adding a metal catalyst into the enzymolysis biomass under a protective atmosphere, and carrying out high-temperature carbonization to obtain a black solid substance; and then grinding the obtained solid matter, treating the solid matter with strong acid, washing the solid matter with ultrapure water and ethanol, and drying the solid matter to obtain the graphitized nano carbon material, so that the porous two-dimensional carbon material with the characteristics of large specific surface area and high graphitization degree is obtained.
In the invention, the metal catalyst comprises potassium ferricyanide, potassium ferrocyanide, ferric chloride, ferric nitrate or ferric sulfate, the carbonization temperature is preferably 800-1000 ℃, the carbonization time is 2-4 h, and the temperature rise speed when the temperature rises to the carbonization temperature is preferably 4-12 ℃/min, and more preferably 8-10 ℃/min; in the present invention, the protective gas is preferably any one of nitrogen and argon, and more preferably nitrogen. The flow rate of the protective atmosphere is preferably 80-120 mL/min, and more preferably 100-115 mL/min.
In the invention, the post-treatment is preferably carried out on the solid product obtained after carbonization, and in the invention, the post-treatment preferably comprises strong acid treatment, the strong acid is preferably concentrated hydrochloric acid, and the concentration of the concentrated hydrochloric acid is preferably 10-40%, and more preferably 20-30%; the washing is preferably water washing, and the invention has no special requirement on the washing times so as to wash the solid product to be neutral.
In the invention, the supercapacitor electrode material preferably comprises the following components in parts by mass:
70-90 parts of graphitized nano carbon material; 5-20 parts of a conductive agent; 5-15 parts of a binder;
the supercapacitor electrode material provided by the invention comprises 70-90 parts by mass of graphitized nano carbon material, preferably 85 parts by mass of graphitized nano carbon material, and in the invention, the graphitized nano carbon material is the [ ryy1] graphitized nano carbon material in the technical scheme.
Based on the graphitized nano carbon material, the electrode material of the supercapacitor provided by the invention comprises 5-20 parts of a conductive agent, preferably 10 parts. In the present invention, the conductive agent preferably includes acetylene black and/or carbon black Super-p.
Based on the graphitized nano carbon material, the electrode material of the supercapacitor provided by the invention comprises 5-20 parts of a binder, preferably 5 parts. In the present invention, the binder is preferably polyvinylidene fluoride and/or polytetrafluoroethylene.
The invention provides a preparation method for preparing a supercapacitor electrode by using the supercapacitor electrode material in the technical scheme, which comprises the following steps.
Mixing the graphitized nano carbon material, a conductive agent, a bonding agent and a polar organic solvent to obtain electrode slurry; and (3) coating the electrode slurry on a conductive substrate by scraping, drying and tabletting to obtain the supercapacitor electrode.
In the invention, the polar organic solvent is preferably N-methyl-2-pyrrolidone, and the dosage of the polar organic solvent is not particularly required; the invention has no special requirements on the specific implementation process of mixing so as to realize uniform mixing of the materials.
After obtaining the electrode slurry, the invention preferably performs scraping coating on the surface of the conductive substrate with the electrode slurry, drying and tabletting to obtain the supercapacitor electrode. In the present invention, the conductive substrate is preferably foamed nickel, and the size of the conductive substrate is preferably 1cm × 1 cm; the invention has no special requirements on the thickness of the blade coating and the specific implementation process of the coating, and the conventional blade coating thickness and operation which are well known to the technical personnel in the field can be adopted; in the invention, the drying temperature is preferably 50-90 ℃, and more preferably 60-75 ℃; the drying time is preferably 12-24 h, and more preferably 12 h; in the present invention, the pressure of the tablet is preferably 10 MPa; the invention has no special requirements on the specific implementation process of the stamping.
In order to further illustrate the present invention, the following embodiments are described in detail, but they should not be construed as limiting the scope of the present invention.
Example 1
Firstly, fish scales are decomposed to extract hydrolysate. The method comprises the following specific steps: firstly, fish scales are treated by 30 percent concentrated hydrochloric acid and 10 mol L-1And sequentially and respectively soaking the materials in NaOH for 24 hours, washing the materials to be neutral, and naturally draining the water. Then, 12.5 g of pretreated fish scales were weighed out accurately, and 250 ml of alkaline protease solution was added. Stirring the mixture at 75 deg.C for 12 h until fish scales are completely decomposed, and sequentially filtering with filter membrane with pore size of 0.45 μm and 0.22 μm. The filtrate was heated and stirred at 75 ℃ for 4 h to obtain a uniformly concentrated carbon precursor solution, which was stored in a refrigerator at 4 ℃ for further use. Taking 30ml of precursor solution, adding 0.02 moL of potassium ferricyanide into the precursor solution, and stirring for 1 hour to form an orange transparent solution; transferring the solution into a corundum boat, drying at 80 ℃ to obtain a green solid substance, putting the green solid substance into a tube furnace, heating to 900 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours to obtain a black solid substance. Grinding the black solid matter, adding a proper amount of concentrated hydrochloric acid to soak for 12 h, then washing the black solid matter with ethanol and water to be neutral, centrifuging, and drying at 80 ℃ to obtain the graphitized nano carbon material.
Fig. 1 is a transmission electron microscope representation of the prepared graphitized carbon material, wherein (a) in fig. 1 is a transmission electron microscope photograph at a scale of 1 μm, and (b) in fig. 1 is a transmission electron microscope photograph at a scale of 100 nm; as can be seen from fig. 1, the graphitized carbon material prepared in this example has a flat sheet-like structure.
Fig. 2 is an X-ray diffraction spectrum diagram of the prepared graphitized nanocarbon material, and it is apparent from fig. 2 that peaks at 26.4 °, 42.2 °, 44.5 °, 54.5 °, 59.7 ° and 77.4 ° are diffraction peaks ascribed to (002), (100), (101), (004), (103) and (110) crystal planes of graphitized carbon. Fig. 3 is an X-ray photoelectron spectrum of the prepared graphitized nanocarbon material, and it can be determined from fig. 3 that the main constituent elements of the material are carbon, nitrogen and oxygen.
FIG. 4 is a core level region XPS spectrum of C1s in the prepared graphitized nanocarbon material, and from FIG. 4, it is shown that four splitting peaks are at 284.7 eV to 285.6 eV, 288.7 eV and 289.6 eV, respectively, corresponding to the binding energies of sp 2C and sp 3C, C-N bond and C = O bond.
Fig. 5 is a core level region XPS spectrum of O1s in the prepared graphitized nanocarbon material, which is divided into three peaks at 530.9 eV, 532.6 eV and 533.3 eV, respectively, from fig. 5, indicating the presence of C = O and C-OH and O = C-O.
Fig. 6 is a XPS spectrum of the core level region of N1s in the prepared graphitized nanocarbon material, which is divided into three peaks at 398.4 eV, 399.9 eV and 401.4 eV, respectively, from fig. 6, showing pyridine nitrogen and pyrrole nitrogen graphitized nitrogen.
Fig. 7 is an isothermal adsorption curve of the prepared graphitized nanocarbon material, and as can be seen from fig. 7, the adsorption curve is of type iv and has an obvious HII hysteresis loop, indicating that the material has a mesoporous structure.
Fig. 8 is a pore size distribution curve in the prepared graphitized nanocarbon material, and two peaks located around 2 nm and around 5 nm can be clearly seen, indicating that the material has pores of two different sizes.
Application example 1
The graphitized carbon nanomaterial prepared in example 1 is mixed with acetylene black and polytetrafluoroethylene according to the mass ratio of 85:10:5, the mixture is mixed, N-methyl-2-pyrrolidone is used for preparing slurry, and the slurry is coated on a substrate with the area size of 1 x 1cm2The foam nickel substrate coated with the slurry is dried for 24 hours at the constant temperature of 60 ℃, then is placed on a tablet press, and is pressed under the pressure of 10 MPa to prepare the graphitized nano carbon material/foam nickel supercapacitor electrode.
Test example 1
The graphitized nano carbon material/foam nickel super capacitor electrode prepared in application example 1 is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, and the three electrodes are placed in 6 mol L-1And performing electrochemical performance tests such as cyclic voltammetry, constant current charging and discharging, electrode cyclic stability, alternating current impedance and the like in the KOH solution.
FIG. 9 shows that the graphitized carbon nanomaterial/nickel foam supercapacitor electrode in application example 1 is used as a working electrode, and the scanning rate is 10 mV s within an electrochemical window of-1.0-0V-1、20 mV s-1、30 mV s-110 50 mV s-1、10 mV s-1 And 100 mV s-1The cyclic voltammetry curve of the time can be obtained from fig. 8, the graphitized nanocarbon material/foamed nickel supercapacitor electrode prepared in application example 1 has a rectangular-like shape on the cyclic voltammetry curve at different sweep rates, and the peak area increases with the increase of the sweep rate.
FIG. 10 shows that the current density of the graphitized nano carbon material/foamed nickel supercapacitor electrode in application example 1 as a working electrode is 1.0A g within an electrochemical window of-1V to 0V-1Fig. 10 shows the linear constant current discharge curve of the graphitized nanocarbon material/nickel foam supercapacitor electrode prepared in application example 1, which shows the capacitance performance of the material double layer. The invention provides a foam nickel electrode modified by graphitized nano carbon material, which is 1A g-1Specific capacitance at current density of 448F g-1。
FIG. 11 is a graph showing the results of AC impedance detection of the electrode using the graphitized nano-carbon material/foamed nickel supercapacitor electrode of application example 1 as the working electrode, and it can be seen from FIG. 11 that the graphitized nano-carbon material/foamed nickel supercapacitor electrode prepared in application example 1 is 10-2~105The straight line of a Nyquist curve in the frequency range of HZ in the low-frequency region is almost perpendicular to the horizontal axis, good material transmission capacity is shown, the intersection value of the curve and the real part Z' is 0.17 omega, and the fact that the ohmic internal resistance of the prepared electrode material is small is proved.
FIG. 12 shows application example 1Fig. 11 shows a graph of electrode stability performance test results of the graphitized nanocarbon material/nickel foam supercapacitor electrode as a working electrode, where the graphitized nanocarbon material/nickel foam supercapacitor electrode prepared in application example 1 has a current density of 1A g-1The capacity retention ratio after 5000 cycles under the current density of (1) is 98.46%, and the stability is high.
Example 2
Firstly, fish scales are decomposed to extract hydrolysate. The method comprises the following specific steps. Firstly, 36 percent concentrated hydrochloric acid and 10 mol L of fish scales are used-1And sequentially and respectively soaking the materials in NaOH for 24 hours, washing the materials to be neutral, and naturally draining the water. Then, 12.5 g of pretreated fish scales were weighed out accurately, and 250 ml of alkaline protease solution was added. Stirring the mixture at 75 deg.C for 12 h until fish scales are completely decomposed, and sequentially filtering with filter membrane with pore size of 0.45 μm and 0.22 μm. The filtrate was heated and stirred at 75 ℃ for 4 h to obtain a uniformly concentrated carbon precursor solution. Taking 30ml of precursor solution, adding 0.02 moL of ferric chloride into the precursor solution, and stirring for 1 hour to form an orange transparent solution; transferring the solution into a corundum boat, drying at 80 ℃ to obtain a green solid substance, putting the green solid substance into a tube furnace, heating to 1000 ℃ at the heating rate of 5 ℃/min, and carbonizing for 3 hours to obtain a black solid substance. Grinding the black solid matter, adding a proper amount of concentrated hydrochloric acid to soak for 12 h, then washing the black solid matter with ethanol and water to be neutral, centrifuging, and drying at 80 ℃ to obtain the graphitized nano carbon material.
Application example 2
The graphitized carbon nanomaterial prepared in example 2 is mixed with acetylene black and polytetrafluoroethylene according to the mass ratio of 85:10:5, the mixture is mixed and then mixed with N-methyl-2-pyrrolidone to form slurry, and the slurry is coated on a substrate with the area size of 1 x 1cm2The foam nickel substrate coated with the slurry is dried for 24 hours at the constant temperature of 60 ℃, then is placed on a tablet press, and is pressed under the pressure of 10 MPa to prepare the graphitized nano carbon material/foam nickel supercapacitor electrode.
Test example 2
The graphitized nano carbon material/foam nickel super capacitor electrode prepared in application example 2 is used as a working electrode, a saturated calomel electrode is used as a reference electrode, a platinum wire is used as a counter electrode, andthe electrode was placed at 6 mol L-1And performing electrochemical performance tests such as cyclic voltammetry, constant current charging and discharging, electrode cyclic stability, alternating current impedance and the like in the KOH solution.
FIG. 13 shows that the graphitized nano carbon material/foamed nickel supercapacitor electrode in application example 2 is used as a working electrode, and the scanning rate is 10 mV s within an electrochemical window of-1.0-0V-1、20 mV s-1、30 mV s-110 50 mV s-1、10 mV s-1 And 100 mV s-1As can be seen from fig. 12, the graphitized nanocarbon material/foamed nickel supercapacitor electrode prepared in application example 1 has a rectangular-like shape on the cyclic voltammetry curves at different sweep rates, and the peak area increases with the increase of the sweep rate.
FIG. 14 shows that the graphitized nano carbon material/foamed nickel supercapacitor electrode in application example 2 has a current density of 1.0A g within an electrochemical window of-1.0-0V as a working electrode-1The constant current charging and discharging curve of the time can be obtained from fig. 14, and the graphitized nanocarbon material/foamed nickel supercapacitor electrode prepared in application example 2 presents an approximately linear constant current discharging curve, and embodies the capacitance performance of the material double electric layers. The foam nickel electrode modified by the graphitized nano carbon material provided by the invention is 1.0A g-1Specific capacitance at current density of 387F g-1。
FIG. 15 is a graph of the results of AC impedance detection of the electrode using the graphitized nano-carbon material/foamed nickel supercapacitor electrode of application example 2 as the working electrode, and it can be seen from FIG. 15 that the graphitized nano-carbon material/foamed nickel supercapacitor electrode prepared in application example 2 is 10-2~105The slope of the Nyquist curve in the frequency range of HZ in the low frequency region is small because the porous structure is very favorable for the transmission of the electrolyte, and the intersection value of the curve and the real part Z' is 0.11 Ω, which proves that the ohmic internal resistance of the prepared electrode material is small.
Although the above embodiments have been described in detail, they are only a part of the embodiments of the present invention, not all of the embodiments, and other embodiments can be obtained without inventive step according to the embodiments, and all of the embodiments belong to the protection scope of the present invention.
Claims (10)
1. A two-dimensional graphitized nano carbon material and a preparation method and application thereof are characterized by comprising the following steps: (1) soaking biomass fish scales with strong acid and strong base solutions in sequence, then cleaning with ultrapure water, draining, adding quantitative biological enzyme and ultrapure water, stirring and reacting for 24 hours, and filtering to obtain a liquid solution; (2) mixing and stirring the solution prepared in the step 1 and a certain amount of metal catalyst uniformly at 40-50 ℃, and then drying in vacuum for 2-24 hours to obtain a solid substance; (3) heating to 800-1000 ℃ at a rate of 4-12 ℃/min, and controlling the air flow rate to be 80-120 mL min-1Under the condition, carrying out carbonization treatment on the solid obtained in the step 2 for 2-8 h; (4) performing acid treatment on the product obtained in the step 3 to remove metal substances in the product to obtain a black solid; (5) performing chemical alkali activation treatment on the product obtained in the step 4 to obtain a graphitized nano carbon material; (6) mixing the material obtained in the step (5) with a certain amount of adhesive and conductive agent to form slurry, and blade-coating the slurry on the processed foam nickel (NF, with the size of 1 multiplied by 1 cm) to prepare foam nickel electrolysis; (7) and (4) constructing a three-electrode system, and carrying out electrochemical test on the electrode obtained in the step (6).
2. The graphitized nanocarbon material according to claim 1, wherein the HCl concentration used in the step 1 is 10 to 40%, and the NaOH concentration is 1 to 20 mol L-1(ii) a The mass volume ratio of fish scales to HCl/NaOH is (30-50) g: (200-300) mL.
3. The preparation and use of graphitized nanocarbons according to claims 1 and 2, characterized in that the metal catalysts used comprise: potassium ferricyanide, potassium ferrocyanide, ferric chloride, ferric nitrate or ferric sulfate.
4. The graphitized nanocarbon material according to claim 1, 2 or 3, characterized in that the gas used in step (3) is nitrogen, argon or a mixed gas of both.
5. The graphitized nanocarbon material according to claim 1, 2, 3 or 4, characterized in that the acid used in step 4 comprises concentrated hydrochloric acid, concentrated sulfuric acid or concentrated nitric acid.
6. The graphitized nanocarbon material according to claim 1, 2, 3, 4 or 5, characterized in that the chemical activation treatment performed in step 5 is: adding KOH or NaOH into the black substance prepared in the step 4, wherein the mass ratio of the black substance to the alkali is 1: (5-10), carrying out reflux treatment at 80-130 ℃ for 3-6 hours, evaporating the solvent to dryness, heating the obtained solid to 800 ℃ at the speed of 5-20 ℃/min, and treating for 2 hours under the condition that the gas flow is 80-120 ml/min.
7. The graphitized nanocarbon material according to claim 1, wherein the graphitized nanocarbon material has a specific surface area of 900 to 1300m2 g-1。
8. Use of the graphitized nanocarbon material according to any one of claims 1 to 7 in an electrode material.
9. Use of the graphitized nanocarbon material according to claim 1 or 8 in an electrode material, characterized in that the mass ratio of the materials used is: adhesive: conductive agent = (70-90): 5-15): 5-20), binder is polyvinylidene fluoride or polytetrafluoroethylene, and conductive agent is acetylene black or Super-p.
10. Use of the graphitized nanocarbon material according to claim 1, 8, 9 or 10 in an electrode material, characterized in that the electrolyte solution is 6.0 mol L-1KOH solution.
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