CN115893384B - Synthesis method of porous graphene-like nanosheets with biomass as raw material - Google Patents
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Classifications
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- 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
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Abstract
The invention discloses a method for synthesizing porous graphene-like nanosheets by taking biomass as a raw material, which uses biomass and derivatives thereof as raw materials and Zn 2+ Ions as cross-linker and KHCO 3 As an activator, self-assembly is induced by classical solvent evaporation. The invention can selectively add different metal ions for modification for different applications, such as Zn selection in super capacitor applications 2+ Ions are used as pore-forming agents; the corresponding metal ions, such as Fe, are also selected for catalytic conversion applications 3+ 、Ru 3+ And preparing the functionalized graphene-like material. Absolute ethanol is used as a solvent, is volatile at room temperature, is used for starting the self-assembly process, and avoids the use of toxic reagents. The process has simple and safe synthesis process, is expandable and green. The ultrathin graphene-like carbon nano sheet prepared by the method has a high specific surface area, a large pore volume and a hierarchical porous structure, has good conductivity and has a very wide application prospect.
Description
Technical Field
The invention belongs to the technical field of environment-friendly materials, and particularly relates to a synthesis method of a porous graphene-like nanosheet taking biomass as a raw material.
Background
Since the advent of graphene, this has a high specific surface area (-2630 m) 2 g -1 ) High carrier mobility (-10000 cm) 2 V -1 s -1 ) High heat conductivity (5000W MK) -1 ) Has been attracting attention. These superior properties are exploited in many fields including sensors, supercapacitors, catalytic conversion, etc. However, the conventional preparation method is not only a graphite stripping method from top to bottom, but also a vapor deposition CVD, PVD and other methods from bottom to top, which have the pain points of high cost and insufficient yield. Thus in recent yearsThe preparation of graphene-like materials by pyrolysis and carbonization has attracted great attention by using widely available and renewable biomass as a raw material.
From a sustainability perspective, renewable carbon sources and simple synthetic methods that can be extended to industrial quantities are critical to the development of graphene and graphene-like materials in energy applications. Among the many raw materials that are intended for the preparation of graphene, biomass-derived compounds are considered as excellent candidates due to their renewable nature, potential sustainability, and generally low cost. Typically biomass pyrolysis results in a material that is predominantly amorphous carbon, so driving conversion of biomass sp 3C-X bonds to aromatic sp2 c=c bonds requires further exploration. Graphene materials prepared from biomass exhibit most of the characteristics of graphene, but also typically contain disordered layers and defects, have abundant vacancies, doped heteroatoms, etc., and these materials can be defined as graphene-like materials. The preparation of graphene-like materials from biomass typically involves corrosive agents such as strong bases, hydrogen peroxide, and the like; the complexity of the process involves waste of hydrothermally assisted or secondary carbonization energy and also limited versatility for precursor selection, e.g. focusing on sugars or specific raw biomass; modification of the prepared graphene-like material is limited, and effects are difficult to ensure by means of post-loading, soaking and the like. Therefore, efficient and environmentally friendly preparation of multifunctional graphene-like materials remains a challenge.
Disclosure of Invention
Based on the above reasons, the invention aims to overcome the defects of the prior art and provide a method for synthesizing porous graphene-like nano sheets by taking biomass as a raw material, wherein the method is a method for preparing ultrathin N-doped graphene-like porous carbon (GPC) nano sheets by a one-pot method. The method uses lignin as a carbon and nitrogen precursor, zn 2+ Ions as cross-linker and KHCO 3 As an activator, self-assembly is induced by classical solvent evaporation. Due to the complex natural properties of the components of the biomass precursor, doping of heteroatoms can be introduced into the graphene-like structure in the preparation process, so that performances such as conductivity and wettability are improved. Different metal ions can be selectively added for modification for different applications,selecting Zn as in supercapacitor applications 2+ Ions are used as pore-forming agents; the corresponding metal ions, such as Fe, are also selected for catalytic conversion applications 3+ 、Ru 3+ And preparing the functionalized graphene-like material. Absolute ethanol is used as a solvent, is volatile at room temperature, is used for starting the self-assembly process, and avoids the use of toxic reagents. The process has simple and safe synthesis process, is expandable and green. The ultrathin graphene-like carbon nano sheet prepared by the method has a high specific surface area, a large pore volume and a hierarchical porous structure, has good conductivity and has a very wide application prospect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a synthesis method of porous graphene-like nano sheets by taking biomass as a raw material comprises the following steps:
1) Dissolving 0.5 g-1 g of precursor in a solvent, and mixing to obtain a precursor solution;
2) 1g of nonionic surfactant block copolymer F127 is dissolved in 30mL of solvent in an ultrasonic-assisted manner to prepare F127 solution, and the precursor solution is dropwise added into the F127 solution and magnetically stirred in the whole process;
3) Dissolving 0.5-1.0g of metal salt in 5-10mL of solvent, and slowly adding the solution into the precursor solution obtained in the step 1; after stirring for 30 minutes, pouring the obtained solution onto a polytetrafluoroethylene plate, evaporating for 6-12 hours at room temperature in a fume hood, crosslinking by heating for 12-24 hours at 100-160 ℃, and self-assembling to form a composite film;
4) Uniformly mixing the crosslinked film material with an activator to form powder: cutting the obtained film into small pieces, thoroughly grinding with an agate mortar by using an activating agent or mixing into powder by adopting a ball milling mode, wherein the mass ratio of the activating agent to the precursor is 8:1-1:1;
5) Calcining the mixture of step 4) at a heating rate of 1 ℃/min under nitrogen atmosphere for 2 hours at 600 ℃ -1000 ℃, washing the sample with 2M HCl, repeatedly washing with ultrapure water until a neutral pH is obtained, and then drying at 80 ℃ for 12 hours, the resulting sample being denoted GPC-T, wherein T is the calcination temperature, t=600, 750, 900, 1000.
Further, the precursor in step 1) is plant polyphenol or lignin and derivatives thereof. A preferred precursor is lignin.
Further, the metal salt in the step 3) can be Zn 2+ 、Fe 3+ 、Mg 2+ 、Ce 2+ 、Ni 2+ 、Ru 3+ Metal salts, or complexes thereof.
Further, the solvent in the steps 1) to 3) can be selected from absolute ethyl alcohol, acetone and tetrahydrofuran.
Further, the activator in step 4) may be KHCO 3 、KOH、K 2 CO 3 、NaOH、NaHCO 3 。
Further, the precursor addition amount in step 1) was 0.5g and the solvent volume was 50mL.
Further, the mass ratio of activator to precursor in step 4) is 3:1.
The invention has the technical effects that: the invention provides a preparation method for preparing a graphene carbon nano sheet with a hierarchical pore, and the graphene carbon nano sheet is applied to be used as a supercapacitor electrode. The invention takes aromatic biomass such as lignin or polyphenol as a precursor, and couples KHCO through evaporation induced self-assembly (EISA) 3 And chemically activating to obtain the reusable ultrathin highly-wrinkled graphene-like nano sheet. At the same time, zn (NO) is added in the preparation process 3 ) 2 As a cross-linking agent and a pore-forming agent, the ultra-thin hierarchical pore graphene-like carbon nano sheet (GPC) is formed after high-temperature carbonization. The synthesized graphene-like nano sheet material has ultra-high specific surface area, which can reach 3300m at most 2 g -1 The specific pore volume can reach 2.34cm at most 3 g -1 The abundant pore structure is beneficial to electron transport. The electrode of the best material prepared by the invention is prepared in 0.2A g in 6M KOH aqueous solution -1 Obtained 388F g at current density -1 Specific capacitance of (C) at 40Ag -1 The specific capacitance under the condition is 269F g -1 The retention was 69.3%, and excellent in rate performance. At 10A g -1 After the lower 3000 times of circulation, the capacitance retention rate is more than 98%, the material structure is stable, and the material has good electrochemical performance. The stone prepared by the inventionThe graphene is formed by bending and folding ultrathin multi-defect 2D nano sheets to form a 3D network structure, has a rich hierarchical pore structure, has certain value in the aspects of super capacitors, energy storage and catalytic conversion application, and realizes the resource utilization of biomass.
Drawings
Topographical features of gpc-900 material: (a) SEM images of microstructures, (b) TEM images, (c) HR-TEM images, (d) SEAD images.
FIG. 2 (a) N of different temperature activated materials 2 Adsorption-desorption isotherms and (b) pore size distribution.
Fig. 3 characteristics of graphene-based porous carbon material: (a) Raman spectrum of GPC-900, (b) XPS spectrum, (C-d) GPC-900 (C) C1s, (d) O1s, (e) XRD
Raman spectra of gpc-1000 materials.
FIG. 5 shows the electrochemical performance of the graphene-like porous carbon material synthesized according to the present invention in a three-electrode system, (a) CV curve of GPC-900; (b) a GCD curve of GPC-900; (c) CV of different electrodes at 50mV s scan rate -1 ；(d)1A g -1 Constant current charge-discharge curve; (e) specific capacitance at different current densities; (f) nyquist plot.
Fig. 6 is a baud diagram of different electrodes.
FIG. 7. (a) CV curves of GPC-900-SC at different scan rates of 0-1.2V; (b) GCD curves of GPC-900-sC at different current densities. (c) Nyquist plot of GPC-900-SC.
FIG. 8A super capacitor prepared by GPC-900 at 10A g -1 Cycling stability under test conditions.
Fig. 9 is an energy density-power density plot.
FIG. 10 (a) catechol-Zn-KHCO 3 (b) catechol-Zn-KOH, (c) catechol-Ru-KHCO 3 A TEM image of (a).
Detailed Description
Example 1:
the invention provides a method for synthesizing porous graphene-like nanosheets by taking biomass as a raw material, which comprises the steps of 1) dissolving precursor plant polyphenol or lignin biomass in solvents such as absolute ethyl alcohol or acetone, and the like, and precursorsThe precursor with the mass of 0.5 g-1 g, preferably 0.5g, is added with 50mL of absolute ethyl alcohol and mixed to obtain a precursor solution. 2) Nonionic surfactant block copolymer F127 (1 g) was sonicated-assisted dissolved in 30mL of absolute ethanol to prepare F127 solution. And (3) dropwise adding the precursor solution into the F127 solution, and magnetically stirring the whole process. 3) Zinc nitrate hexahydrate (0.5-1.0 g, preferably 0.8 g) was dissolved in absolute ethanol (5-10 mL) and then slowly added to the precursor solution obtained in step 1 (m Precursor body ：m F127 :m Zn(NO3)2·6H2O =1:2:0.8). After stirring for 30 minutes, the resulting solution was poured onto a polytetrafluoroethylene sheet and evaporated in a fume hood at room temperature for 6-12 hours, and then crosslinked by heating at 100-160 ℃ (preferably 100 ℃) for 12-24 hours, and self-assembled to form a composite film. 4) The crosslinked membrane material and an activator KHCO are treated 3 Mixing uniformly to obtain powder, cutting the obtained film into small pieces, using agate mortar to make KHCO 3 Thoroughly grinding and/or mixing into powder by adopting a ball milling way. KHCO (KHCO) 3 The mass ratio of the polymer to the film material obtained after crosslinking is 8:1-1:1, preferably 3:1. 5) The mixture is calcined at 600 c to 1000 c for 2 hours, preferably 900 c, under a nitrogen atmosphere at a heating rate of 1 c/min. The sample was washed several times with 2M HCl and then repeatedly washed with ultrapure water until a neutral pH was obtained, and then dried at 80 ℃ for 12 hours. The resulting sample is expressed as GPC-T, where T is the calcination temperature (t=600, 750, 900, 1000). The physical properties of the materials are shown in Table 1, and SBET is the specific surface area calculated by the Brunauer-Emmett-Teller (BET) method. The microwell surface area was estimated by the t-plot method. The pore volume and pore size distribution (D) were calculated using the mesoporous pore size distribution calculation method (BJH method).
TABLE 1 physical Property parameters of the inventive materials
Term interpretation:
GPC-T: graphene-like hierarchical porous carbon-like Graphene grades a porous carbon, and T refers to a calcination temperature (DEG C). Wherein GPC-900 refers to materials prepared by calcination and carbonization at 900 ℃.
I D /I G : the G band obtained by Raman spectrum test provides evidence for the existence of sp2 hybridized carbon atoms, and the D band shows defects such as disorder, edges and boundaries of graphene. The 2D band provides information about the number of layers of graphene material. G belt (I) G ) D belt (I) D ) And 2D band (I) 2D ) Provides evidence for studying the properties of the graphene material. Due to the defect characteristics of graphene-like materials, the D, G peak is subdivided into an ideal graphite lattice G, a disordered graphite lattice (graphene layer edge) D1, a surface graphene layer D2, amorphous carbon D3 and polyene/ion impurities D4.
FIG. 1a is a scanning electron microscope SEM image of GPC-900 material, showing a thin nanoplatelet layer structure with many folds on the surface, curling with the attachment of the carbon nanoplatelets. Fig. 1b,1c are TEM and HRTEM images, clearly showing the ultra-thin two-dimensional lamellar structure with a large number of lamellar grapheme carbons and nanopores, and the defect abundance. The electron diffraction image (sea) of fig. 1d, presenting typical ring characteristics also demonstrates that the inventive material is curled or folded graphene with rich defects. The pore structure of the material was studied by nitrogen adsorption-desorption isotherm measurements, as shown in fig. 2. The adsorption-desorption isotherms of all samples were in accordance with the type I/IV combined isotherm (fig. 3 a), and a type H4 hysteresis loop was observed in the relative pressure range (P/P0) of 0.45 to 1.0, indicating that the material had a multi-stage pore structure with both micropores and mesopores coexisting. The pore size distribution curve calculated according to Barrett-Joyner-Halenda (BJH) equation (FIG. 3 b) shows that the average pore size of the material is 4-7nm.
Analysis of defect levels of materials using raman spectroscopy (fig. 3 a) was performed by assessing the relative integrated intensity ratio of raman bands D1 and G (denoted as I D1 /I G ) To explore the degree of disorder of the material. As expected, GPC-900 materials showed the highest I among GPC materials D1 /I G Values (Table 1) showing enhanced carbon defect density, particularly disordered graphene edges, and demonstratingIt is true that Zn promotes the generation of defects. X-ray photoelectron spectroscopy (XPS) was performed to analyze the surface elemental composition and chemical state of the material (fig. 3 b). FIGS. 3C-d show high resolution XPS spectra of C1s, O1s of GPC materials. Figure 3e shows the X-ray diffraction pattern of the prepared sample. The material calcined above 750 ℃ showed two main peaks centered at 24 ° and 42.5 °, corresponding to the (002) and (100) crystal planes of graphite-like carbon and ordered hexagonal carbon, respectively.
Notably, XRD showed that the strong peak of GPC-1000 at 26 ° (fig. 3 e) corresponds to graphene, indicating the presence of graphene sheet structures in the material. And from Raman spectrum, GPC-1000 material has lower I D1 /I G Values (Table 1) and higher I 2D /I G The value shows that the graphene with higher graphitization degree and fewer defects is obtained at the temperature of 1000 ℃, and the preparation mode of the high-quality graphene is also provided.
The above examples of the present invention are not the only embodiments, and the raw materials and amounts thereof may be selected as follows: the precursor described in step 1) is preferably 4-nitrocatechol, and lignin or other plant polyphenols may be used instead. The zinc nitrate hexahydrate in the step 3) can also select Fe 3+ 、Mg 2+ 、Ce 2+ 、Ni 2+ 、Ru 3+ The metal salt replaces or incorporates the complex metal salt ion. KHCO in step 4) 3 The activator may also be KOH, K 2 CO 3 、NaOH、NaHCO 3 And the like. In the technical scheme, the absolute ethyl alcohol solvent can be replaced by acetone and tetrahydrofuran. Which has the same technical effects as the above-described embodiments.
Application example 1:
the electrochemical performance of the materials of the present invention was evaluated in a three electrode system. The material according to the present invention was prepared as a working electrode by mixing the prepared sample (80 wt%), polytetrafluoroethylene binder (10 wt%, aldrich,60wt% aqueous suspension) and acetylene black (10 w%) in ethanol and coating the material on a foamed nickel collector (10 mm x 10 mm). Further, a platinum plate (1 cm. Times.1 cm) and Hg/HgO electrode were used as a counter electrode and a reference electrode, respectively. The pre-fabricated electrode was pressed at 10MPa for 3 minutes and dried overnight in a vacuum oven at 80 ℃.
Cyclic Voltammetry (CV) testing as shown in fig. 5a, the CV curve is rectangular, at high scan rates (200 mV s -1 ) No curve deformation was observed at 50mV s -1 Comparing CV curves (5 c) of samples prepared at different temperatures with those of sample obtained at a scanning rate of 1A g -1 The constant current charge-discharge curve (5 d) below, and the GCD curve (b) of GPC-900 showed that the GPC-900 material had the highest current density and the largest integrated area of the sample, had the highest specific capacitance, at 0.2A g -1 The specific capacitance under the condition is 367F g -1 At 40A g -1 At a retention of 62.1% (228F g) -1 ) The material has enough capacitance and retention rate and can be used as a supercapacitor material. Electrochemical Impedance Spectroscopy (EIS) as shown in fig. 5f, the electrode material prepared by the present invention has faster frequency response, higher charge transfer efficiency and excellent ion diffusion capability.
The electrochemical impedance profile of the material prepared in accordance with the present invention was tested in the three electrode system described above. FIG. 6 shows the Bode diagrams of graphene-like nanoplatelet electrode materials prepared according to the present invention at different temperatures. At low frequencies, the phase angle approaches 90 °, indicating good capacitive behavior.
Application example 2:
to evaluate the performance of GPC-900 electrodes in practical applications, the materials prepared according to the invention were used as positive and negative electrodes for a double electrode system in 6.0M KOH aqueous solution, using two identical active substance electrodes (mass 5 mg), and an ion porous separator (NKK TF 4030) was inserted between the two electrodes to assemble a symmetrical supercapacitor, called GPC-900-SC. CV, GCD, EIS was measured and the CV curve was quasi-rectangular at different scan rates as shown in fig. 7 a. Even if the scanning rate is increased to 200mV s -1 A quasi-rectangular shape can still be maintained, reflecting excellent double layer capacitive behavior and rate capability. The GCD curve of GPC-900-SC approximates a symmetric triangle at different current densities, showing good double layer capacitance behavior as shown in FIG. 7 b. In 7c, the EIS test results also reflect the excellent electrochemical performance of GPC-900-SC. Near vertical line of low frequency region, small X-axis projection intercept of intermediate frequency region and high frequency regionThe small semicircle diameter and the small X-axis intercept of the ion-exchange membrane indicate that the ion-exchange membrane has the characteristics of high ion diffusion rate, ideal capacitance behavior, small equivalent series resistance and small charge transfer resistance. GPC-900-SC Equivalent Series Resistance (ESR) is mainly composed of Rs, R ct And R is W Composition is prepared. R calculated from voltage drop and current value ESR The value was 0.35 Ω, indicating that the device had a fast ion diffusion rate and excellent conductivity.
Application example 3:
the stability of supercapacitors prepared from the materials of the present invention was tested. The results showed that at 10A g -1 After 3000 cycles, the specific capacitance retention of GPC-900-SC was 98.04%. Figure 8 shows the GCD curves before and after 3000 cycles. It can be seen that the GCD curve remains symmetrically triangular after 3000 cycles, with little variation, which confirms its cycling stability.
Application example 4:
for the super capacitor (6.0 m KOH aqueous solution system) composed of the two-electrode system, the energy density (E) is calculated based on formulas (1) - (2), and the performance of the energy storage device prepared by the material is compared with other documents, and an energy comparison Lagong chart is shown in fig. 9.
E＝Cs(ΔV) 2 /(8×3.6) (2)
Wherein C (F g) -1 ) The mass ratio capacitance, t(s) the discharge time, I (a) the current, V (V) the voltage window, and m (g) the mass of the active material.
Comparative example 1:
compared with other reported physical structure parameters and electrochemical performances of various grapheme carbon materials in recent years, the material has obvious advantages as shown in Table 2.
TABLE 2 comparison of physical structural parameters and electrochemical Properties of carbon materials reported in recent years
In the present invention, lignin is preferable as the precursor, and other plant polyphenols may be selected as the precursor instead. Besides zinc nitrate, fe can also be selected 3+ 、Mg 2+ 、Ce 2+ 、Ni 2+ 、Ru 3+ The metal salt can be used for replacing or doping composite metal salt ions, and can be applied to different occasions, such as electrochemical desalination, catalytic conversion and the like. KHCO (KHCO) 3 The activator may also be KOH, K 2 CO 3 、NaOH、NaHCO 3 And the like. Fig. 10 is a partial characterization result.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Reference to the literature
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Claims (6)
1. The synthesis method of the porous graphene-like nano sheet with biomass as a raw material is characterized by comprising the following steps of:
1) Dissolving 0.5 g-1 g of precursor in a solvent, and mixing to obtain a precursor solution;
2) 1g of nonionic surfactant block copolymer F127 is dissolved in 30mL of solvent in an ultrasonic-assisted manner to prepare F127 solution, and the precursor solution is dropwise added into the F127 solution and magnetically stirred in the whole process;
3) Dissolving 0.5-1.0g of metal salt in 5-10mL of solvent, and slowly adding into the mixed solution obtained in the step 2; after stirring for 30 minutes, pouring the obtained solution onto a polytetrafluoroethylene plate, evaporating for 6-12 hours at room temperature in a fume hood, crosslinking by heating for 12-24 hours at 100-160 ℃, and self-assembling to form a composite film;
4) Uniformly mixing the crosslinked film material with an activator to form powder: cutting the obtained film into small pieces, adding an activating agent, and thoroughly grinding the small pieces by an agate mortar or mixing the small pieces into powder by adopting a ball milling mode, wherein the mass ratio of the activating agent to the precursor is 8:1-1:1;
5) Calcining the mixture obtained in the step 4) at a heating rate of 1 ℃/min under nitrogen atmosphere at 600-1000 ℃ for 2 hours, washing a sample with 2M HCl, repeatedly washing with ultrapure water until neutral pH is obtained, and drying at 80 ℃ for 12 hours to obtain a final product.
The precursor in the step 1) is plant polyphenol or lignin and derivatives thereof;
the metal salt in the step 3) is Zn 2+ 、Fe 3+ 、Mg 2+ 、Ce 2+ 、Ni 2+ 、Ru 3+ Metal salts, or complexes thereof.
2. The method for synthesizing the porous graphene-like nanosheets by using biomass as a raw material according to claim 1, wherein the method is characterized by comprising the following steps: the precursor in step 1) is lignin.
3. The method for synthesizing the porous graphene-like nanosheets by using biomass as a raw material according to claim 1, wherein the method is characterized by comprising the following steps: the solvent in the steps 1) -3) is one of absolute ethyl alcohol, acetone and tetrahydrofuran.
4. The method for synthesizing the porous graphene-like nanosheets by using biomass as a raw material according to claim 1, wherein the method is characterized by comprising the following steps: the activator in the step 4) is KHCO 3 、KOH、K 2 CO 3 、NaOH、NaHCO 3 One of them.
5. The method for synthesizing the porous graphene-like nanosheets by using biomass as a raw material according to claim 1, wherein the method is characterized by comprising the following steps: the precursor addition in step 1) was 0.5g and the solvent volume was 50mL.
6. The method for synthesizing the porous graphene-like nanosheets by using biomass as a raw material according to claim 1, wherein the method is characterized by comprising the following steps: the mass ratio of activator to precursor in step 4) was 3:1.
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