CN111232948A - Cotton-derived porous carbon electrode material and synthesis method and application thereof - Google Patents
Cotton-derived porous carbon electrode material and synthesis method and application thereof Download PDFInfo
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Abstract
The invention discloses a cotton-derived porous carbon electrode material and a synthesis method and application thereof, and relates to the field of nano electrode materials. It takes cotton as carbon source; then, taking cobalt nitrate as a cobalt source, carrying out hydrothermal reaction, and attaching cobalt oxide particles on the surfaces of the biomass particles by using an in-situ growth method to obtain a compound; and finally, carrying out one-step carbonization and activation on the obtained composite to obtain the cotton-derived porous carbon electrode material. The synthetic method is simple, the obtained product has uniform appearance and large specific surface area, the advantages of large specific surface area and layered porous structure of the biomass material are combined, and the heteroatom is introduced to form the pseudo-capacitance, so that the pseudo-capacitance has better electrochemical performance and electrochemical stability when being used as an electrode material of a super capacitor, and is suitable for application in the aspects of energy conversion and storage.
Description
Technical Field
The invention belongs to the field of nano electrode materials, and particularly relates to a cotton-derived porous carbon electrode material and a synthesis method and application thereof.
Background
Co3O4The electrode material of the representative super capacitor has attracted great research interest and is considered to be RuO2The best substitute material of (1). However, due to Co3O4The wide bandgap semiconductor has the characteristics of slow reaction kinetics, low conductivity and easy self-polymerization, so that the capacitance performance of the semiconductor is not ideal. Research has shown that the construction of pathways that facilitate electron transport and the tailoring of Transition Metal Oxide (TMO) active materials into different functionalized structures are two major approaches to the promotion of performance in energy storage devices. With Co3O4For example, in one aspect, the introduction of highly conductive carbon material (carbon fiber, carbon nanotube, graphene, etc.) components can produce Co with enhanced conductivity3O4-C composite material, but Co3O4The high specific capacitance performance of the composite material cannot be effectively released due to slow surface chemical reaction caused by agglomeration, and the specific capacitance lifting range is limited. On the other hand, by copying the fine structure of natural species such as cotton, sorghum stalk, banana peel and butterfly wing, Co with special appearance is designed3O4And (3) nano materials. Although the resulting material exhibits specific bulk Co3O4The pseudo capacitance is multiplied by itself, but the charge transmission is blocked due to insufficient conductivity.
Cotton, a common commercial crop, is composed primarily of cellulose and is widely used to produce soft, breathable textiles and garments. The abundance, low cost, and environmental sustainability of natural cotton make it highly practical in a variety of applications. Recent research has led to the successful application of cotton fibers in the fields of energy storage, environmental protection, etc. by forming carbon fibers and doped composites thereof through various synthetic methods. However, studies on its use as a template and a carrier for composite materials are not common.
Disclosure of Invention
The invention aims to provide a cotton-derived porous carbon electrode material and a synthesis method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme.
The invention provides a synthetic method of a cotton-derived porous carbon electrode material, which comprises the following steps: taking cotton as a carbon source, and carrying out pre-carbonization treatment to obtain a porous carbon material; secondly, taking cobalt nitrate as a cobalt source, taking the porous carbon material as a carrier, and carrying out hydrothermal reaction to grow cobalt oxide particles on the surface of the porous carbon material in situ to obtain a compound; and carbonizing the compound to obtain the cotton-derived porous carbon electrode material.
Further, the pre-carbonization treatment step comprises: and (3) ultrasonically cleaning the degreased cotton with an ethanol water solution, drying, cutting into small sections, and pre-carbonizing to obtain the porous carbon material.
Further, the temperature of the pre-carbonization is 250-350 ℃, and the time of the pre-carbonization is 25-35 min.
Further, the hydrothermal reaction step comprises: soaking the porous carbon material subjected to pre-carbonization in a cobalt nitrate solution, placing a solid-liquid mixture in a high-pressure reactor after soaking, and carrying out hydrothermal reaction to obtain a reaction product; and filtering the reaction product, and washing and drying the precipitate obtained by filtering to obtain the compound.
Further, the concentration of cobalt nitrate in the cobalt nitrate solution is 0.5-1.5 mol/L; the mass ratio of the porous carbon material to the cobalt nitrate solution is 1: 30-1: 70.
Furthermore, the temperature of the hydrothermal reaction is 150-210 ℃, and the time of the hydrothermal reaction is 8-16 h.
Further, the step of cleaning the precipitate comprises the step of repeatedly cleaning the precipitate for 3-4 times by using ultrapure water; and grinding the carbonized product after carbonization treatment to obtain the cotton-derived porous carbon electrode material.
Further, the carbonization treatment step includes: and calcining the compound in an air atmosphere at the temperature of 350-450 ℃ for 1.5-2.5 h.
The invention also provides a cotton-derived porous carbon electrode material which is synthesized according to the synthesis method of the cotton-derived porous carbon electrode material.
Further, the cotton-derived porous carbon electrode material is applied to manufacturing of electrodes of supercapacitors.
The invention has the beneficial effects that:
the synthesis method is simple, and the product has uniform appearance by utilizing an in-situ growth mode. The invention combines the advantages of large specific surface area and layered porous structure of the biomass material, introduces heteroatoms to form pseudo capacitance, and has good electrochemical performance and electrochemical stability when being applied to the electrode of the super capacitor. The biologically derived carbon as the matrix material improves the electron conductivity of the electrode material, increases the migration speed of electrons, has larger specific surface area, improves the dispersibility of active substances, and provides more active surface interfaces for Faraday reaction.
Drawings
FIG. 1(a) is an SEM image of cotton provided in example 1;
FIG. 1(b) is an SEM image of the OCM-2 sample provided in example 1.
FIG. 2(a) shows OCM-2 provided in example 1 and pure phase Co provided in comparative example 13O4XRD spectrum of (1);
FIG. 2(b) shows OCM-2 provided in example 1 and pure phase Co provided in comparative example 13O4Raman spectrum of (a).
FIG. 3 is an XPS spectrum of OCM-2 provided in example 1.
FIG. 4(a) shows OCM-2 provided in example 1 and pure phase Co provided in comparative example 1 in 6mol/L KOH solution at a scan rate of 10mV/s3O4A CV curve of (a);
FIG. 4(b) is a CV curve of OCM-2 provided in example 1 at various scan rates;
FIG. 4(c) shows OCM-2 provided in example 1 and pure phase Co provided in comparative example 13O4Performing constant current charge and discharge test at a current density of 1A/g;
FIG. 4(d) is a CP curve of the OCM-2 sample provided in example 1 at different current densities.
FIG. 5(a) shows the OCM-2 material provided in example 1 and the pure phase Co provided in comparative example 13O4A Nyquist diagram with the amplitude of 5mV in the frequency range of 100 KHz-10 mHz;
FIG. 5(b) is a graph of the cycle life of the OCM-2 material provided in example 1 at a current density of 1A/g.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The cotton-derived porous carbon electrode material of the present invention, and the synthesis method and application thereof will be explained in the following in a whole.
The invention provides a synthetic method of a cotton-derived porous carbon electrode material, which comprises the following steps: taking cotton as a carbon source, and carrying out pre-carbonization treatment to obtain a porous carbon material; secondly, taking cobalt nitrate as a cobalt source, taking the porous carbon material as a carrier, and carrying out hydrothermal reaction to grow cobalt oxide particles on the surface of the porous carbon material in situ to obtain a compound; and carbonizing the compound to obtain the cotton-derived porous carbon electrode material. By using the in-situ growth method, the porous carbon composite material with uniformly adhered surface can be obtained, so that the porous carbon composite material has better electrical conductivity.
Further, the pre-carbonization treatment step comprises: and (3) ultrasonically cleaning the degreased cotton with an ethanol aqueous solution, drying, cutting into small sections, and then pre-carbonizing to obtain the porous carbon material, so that the cobalt material can be conveniently doped and attached.
Wherein the pre-carbonization temperature is 250-350 ℃, and the pre-carbonization time is 25-35 min.
Further, the hydrothermal reaction step comprises: soaking the porous carbon material subjected to pre-carbonization in a cobalt nitrate solution, placing a solid-liquid mixture in a high-pressure reactor after soaking, and carrying out hydrothermal reaction to obtain a reaction product; and filtering the reaction product, and washing and drying the precipitate obtained by filtering to obtain the compound. After the hydrothermal reaction, the cobalt nitrate is decomposed into cobalt oxide which is attached to the surface and the interior of the porous carbon material.
Wherein the concentration of cobalt nitrate in the cobalt nitrate solution is 0.5-1.5 mol/L; the mass ratio of the porous carbon material to the cobalt nitrate solution is 1: 30-1: 70.
Wherein the temperature of the hydrothermal reaction is 150-210 ℃, and the time of the hydrothermal reaction is 8-16 h.
Further, the step of cleaning the precipitate comprises the step of repeatedly cleaning the precipitate for 3-4 times by using ultrapure water; and grinding the carbonized product after carbonization treatment to obtain the cotton-derived porous carbon electrode material.
Further, the carbonization treatment step includes: and calcining the compound in an air atmosphere at the temperature of 350-450 ℃ for 1.5-2.5 h. The carbonized carbon substrate further forms a rich porous structure, and ensures that the cobalt nitrate is completely decomposed to form cobalt oxide crystal grains attached to the carbon substrate.
The synthesis method is simple, and the product has uniform appearance by utilizing an in-situ growth mode. The carbonized product forms rich pore channels, provides rich storage and transmission channels for ions, reduces resistance and enhances capacitance.
The invention also provides a cotton-derived porous carbon electrode material which is synthesized according to the synthesis method of the cotton-derived porous carbon electrode material, and the cotton-derived porous carbon electrode material comprises a porous carbon material and cobalt oxide particles growing on the surface of the porous carbon material and is applied to manufacturing electrodes of supercapacitors.
The invention combines the advantages of large specific surface area and layered porous structure of the biomass material, introduces heteroatoms to form pseudo capacitance, and has good electrochemical performance and electrochemical stability when being applied to the electrode of the super capacitor. The biologically derived carbon as the matrix material improves the electron conductivity of the electrode material, increases the migration speed of electrons, has larger specific surface area, improves the dispersibility of active substances, and provides more active surface interfaces for Faraday reaction.
The embodiment of the present invention will be specifically described below by way of examples and comparative examples.
Example 1
In this example, a cotton-derived porous carbon electrode material was synthesized as follows:
(1) ultrasonically cleaning 5g of absorbent cotton with mixed solution of alcohol and ultrapure water for 10min, drying the absorbent cotton at 100 ℃, and cutting the absorbent cotton into small sections smaller than 1mm by using scissors;
(2) the small piece of absorbent cotton is pre-carbonized for 30 minutes in a tube furnace at 300 ℃. After cooling to room temperature, the sample was taken out for further use. Taking a plurality of carbonized samples, respectively soaking in 1mol per liter-1In cobalt nitrate solution;
(3) after complete infiltration, the mixed solution is put into a 100ml high-pressure reaction kettle, reacted at 180 ℃ and kept warm for 12 hours, and the temperature rise speed is 2 ℃ min-1Carrying out hydrothermal reaction;
(4) and filtering the mixed solution, washing the obtained solid product with ultrapure water for 3 times, drying, calcining in a 400 ℃ tubular furnace in air atmosphere for 2 hours respectively, and grinding the calcined sample to obtain the cotton-derived porous carbon electrode material which is marked as OCM-2.
Comparative example 1
The comparative example provides a pure phase cobalt oxide sample obtained by the following steps:
1 mol. L-1The cobalt nitrate solution is put into a 100ml high-pressure reaction kettle, reacts at 180 ℃ and is kept warm for 12 hours, and the temperature rise speed is 2 ℃ min-1Separating out solid;
filtering to obtain solid, cleaning with ultrapure water for 3 times, drying, calcining in a 400 ℃ tube furnace in air atmosphere for 2h, grinding the calcined sample to obtain a pure-phase cobalt oxide sample, and marking the pure-phase cobalt oxide sample as pure-phase Co3O4。
The above samples obtained in example 1 and comparative example 1 were each subjected to the following tabulation and analysis.
Experimental example 1SEM analysis
FIG. 1(a) is an SEM image of cotton before pre-carbonization, wherein the inset is an SEM image of cotton after pre-carbonization, all with a distinct fiber structure, with a diameter of around a few microns.
FIG. 1(b) is an SEM image of OCM-2 sample, which shows that the OCM-2 product perfectly inherits the morphological characteristics of cotton fiber and forms Co3O4One-dimensional core-shell tubular composite material of active substance modified carbon fiber and tubular shell layer Co3O4Is a typical octahedron and a derivative structure characteristic thereof, and the grain size is 80-450 nm.
The porous structure is one of the key factors influencing the electrochemical performance of the supercapacitor, and the OCM-2 sample activated by carbonization can be seen to have a certain pore-size structure. Different pore diameter structures in the layered porous carbon structure have different influences on the electrochemical performance of the supercapacitor, the micropores can improve the specific surface area of the material and enhance the electric double layer capacitance, the mesoporous channels provide a passage for ion transmission, and the formation of macropores is beneficial to buffering and storing ions and effectively shortening the diffusion distance of the ions.
Experimental example 2XRD and Raman test analysis
FIG. 2(a) shows OCM-2 and pure phase Co3O4XRD pattern of the crystal. Composite material OCM-2 and pure phase Co3O4X-ray diffraction (XRD) of (A) shows that the attached cobalt oxide in OCM-2 is pure spinel Co3O4(JCPDS 43-1003) face-centered cubic (fcc) structure. Each curve is located near 19.0 °, 31.2 °, 36.8 °, 44.8 °, 59.3 ° and 65.2 °The diffraction peaks of the spinel can be respectively assigned to pure spinel Co3O4The (111), (220), (311), (400), (511), and (440) diffraction planes of (1).
FIG. 2(b) shows OCM-2 and pure phase Co3O4Raman spectra of the crystals, all curves in the figure being present at 471, 512, 607 and 675cm–1Peak of (1), corresponding to pure phase Co3O4E of (A)g、F1 2g、F2 2gAnd A1 gAnd (4) acoustic mode. OCM-2 material at 1368 and 1563cm–1Raman peaks near the wavenumber can be respectively assigned as the D peak and the G peak of graphitic carbon, and the Raman peaks are respectively assigned to pure-phase Co3O4No presence in the curve indicates the presence of carbon in OCM-2 of the composite. The intensity of the D and G peaks can also be further corroborated to the carbon content of the material.
Test example 3XPS analysis
In FIG. 3, (a) is a full spectrum of X-ray photoelectron spectroscopy (XPS) of OCM-2, showing that the OCM-2 composite contains three elements of Co, C and O.
In fig. 3, (b) is XPS local spectrum of OCM-2, and it can be seen that C1 s is fitted to four peaks at 282.8, 284.6, 286.5 and 288.3eV, which are assigned to C-C, C-C, C-O and C-O covalent bond, respectively.
In FIG. 3, (c) is the XPS local spectrum of OCM-2, it can be seen that the O1 s XPS signal is fitted to two peaks at 530.3 and 532.5eV, which is attributed to cubic spinel Co3O4The lattice oxygen in (a) and the hydroxyl group at the interface of the composite material.
In FIG. 3, (d) is the XPS local spectrum of OCM-2, which is the nano-structured Co in the prepared OCM-23O4Co 2p spectrum of (a). Co3O4Middle Co3+Has binding energy peaks of 780.2 and 795.4eV, respectively, corresponding to 2p3/2And 2p1/2. The partial peaks at the binding energies of 781.3eV and 796.7eV are assigned to Co3O4Of (5) Co 2+2p of3/2And 2p1/2A signal.
The surface elemental composition and the corresponding chemical state of the resulting OCM-2 material can be explained by the above.
Test example 4 electrochemical Performance test
Under the test item, the electrochemical performance test of the material is carried out in 6mol/L KOH electrolyte, and the related electrochemical test characterization methods are as follows: cyclic voltammetry, constant current charge and discharge, and electrochemical impedance spectroscopy.
FIG. 4(a) is OCM-2 and pure phase Co in 6mol/L KOH solution at a scan rate of 10mV/s3O4A CV curve of (a); FIG. 4(b) is a CV curve of OCM-2 at different scan rates; FIG. 4(c) is OCM-2 and pure phase Co3O4Performing constant current charge and discharge test at a current density of 1A/g; FIG. 4(d) is a CP curve of OCM-2 samples at different current densities.
FIG. 5(a) shows the OCM-2 material and pure phase Co3O4A Nyquist diagram with the amplitude of 5mV in the frequency range of 100 KHz-10 mHz; FIG. 5(b) is a graph of the cycle life of the OCM-2 material at a current density of 1A/g.
The system for the test adopts a three-electrode test system, the electrolyte is 6mol/L KOH, and the working voltage window is 0-0.6V (reference Hg/HgO).
As can be seen in FIG. 4(a), significant redox peaks appeared in OCM-2 at 0.3 and 0.42V, pure phase Co3O4The redox peaks of (a) are then at 0.4 and 0.45V. At the same time, the paired appearance of the redox peaks indicates the presence of Co in the prepared material2+And Co3+Can be reversibly switched between. Composite OCM-2 and pure phase Co3O4There are a pair of redox peaks, indicating that the measured capacitance is mainly due to surface reversible faradaic reactions.
Composite OCM-2 and pure phase Co3O4Can be attributed to the presence of carbon in OCM-2. Meanwhile, the introduction of the high-conductivity carbon fiber enables the OCM-2 to have relatively pure phase Co3O4Larger peak current. Wherein the closed area of the CV curve of OCM-2 with biologically derived carbon fiber component is greater than pure phase Co3O4The results show that the pseudocapacitance characteristic prepared by the composite material OCM-2 is superior to that of pure phase Co3O4The results thereof were in accordance with the results of the constant current discharge test shown in FIG. 4 (c).
FIG. 4(b) is a CV test curve of OCM-2 at different voltage scan rates. The current density of the material is increased along with the increase of the scanning speed, and the OCM-2 electrode material has good rate performance. In 6mol/L KOH dielectrics, even if the scanning rate reaches 100mV · s-1The CV profile of the composite electrode OCM-2 remained good, further confirming that the composite material OCM-2 has good reversibility.
FIG. 4(c) shows that composite OCM-2 and pure phase Co can be obtained3O4The relationship between the corresponding specific capacitance and the discharge time can be calculated by the following equation:
Cs＝d(Δq)/d(ΔV) (3)
wherein C iss(F·g-1) Is the capacitance of the pseudocapacitor, q is the charge transfer amount, and V is the potential window. OCM-2 and pure phase Co3O4The specific capacitances at a current density of 1A/g were 284.2 and 58.1 Fg-1OCM-2 greater than pure phase Co3O4More than 4 times of the total weight of the composition.
As shown in FIG. 4(d), the current densities were 1, 2, 3, 4 and 5 A.g-1The specific capacitances of OCM-2 were 284.2, 256.9, 239.4, 233.1 and 220.7 Fg, respectively-1. Possible reasons can be explained as follows: high current density corresponds to a high rate of charge and discharge processes that prevent ions from migrating rapidly and entering the deep interior of the electrode through the surface interface, resulting in less utilization of electroactive species in the electrode.
FIG. 5(a) shows the OCM-2 material and pure phase Co3O4In the frequency range of 100 KHz-10 mHz, the amplitude is 5mV Nyquist map, and the inset is the corresponding high frequency region enlarged view. Charge transfer resistance (R) of composite electrode OCM-2(0.45 omega)ct) Significantly less than pure phase Co3O4(0.55. omega.), TABLEThe bright biologically-derived carbon fibers are beneficial to reducing the contact resistance between the cobalt oxide and the current collector. The OCM-2 has larger specific surface area and pore channels, improves the dispersibility of active substances, reduces agglomeration, is favorable for shortening the diffusion distance of internal active substance ions to a solution, and can further improve the electron conduction and ion diffusion processes of the reaction.
FIG. 5(b) shows that the OCM-2 material is at 1A g-1Cycle life plot at current density. As shown, the capacitance of sample OCM-2 decayed to 94.73% of the initial value over 1000 constant current charge-discharge cycles. Indicating that the materials all have excellent cycling stability.
In conclusion, the prepared cotton-derived porous carbon electrode material has good electrochemical performance and electrochemical stability, and has a wide prospect in the practical application of the super capacitor.
The above-described embodiments are merely some embodiments of the present invention and are not intended to be exhaustive or to limit the scope of the invention to the precise embodiments disclosed, and merely representative of selected embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. A synthetic method of a cotton-derived porous carbon electrode material is characterized by comprising the following steps:
taking cotton as a carbon source, and carrying out pre-carbonization treatment to obtain a porous carbon material;
secondly, taking cobalt nitrate as a cobalt source, taking the porous carbon material as a carrier, and carrying out hydrothermal reaction to grow cobalt oxide particles on the surface of the porous carbon material in situ to obtain a compound;
and carbonizing the compound to obtain the cotton-derived porous carbon electrode material.
2. The method for synthesizing a porous carbon electrode material derived from cotton as claimed in claim 1 wherein the pre-carbonization treatment step comprises:
and (3) ultrasonically cleaning the degreased cotton with an ethanol water solution, drying, cutting into small sections, and pre-carbonizing to obtain the porous carbon material.
3. The method for synthesizing the porous carbon electrode material derived from cotton according to claim 2, wherein the temperature of the pre-carbonization is 250 to 350 ℃, and the time of the pre-carbonization is 25 to 35 min.
4. The method for synthesizing the cotton-derived porous carbon electrode material according to claim 1, wherein the hydrothermal reaction step comprises:
soaking the porous carbon material subjected to pre-carbonization in a cobalt nitrate solution, placing a solid-liquid mixture in a high-pressure reactor after soaking, and carrying out hydrothermal reaction to obtain a reaction product;
and filtering the reaction product, and washing and drying the precipitate obtained by filtering to obtain the compound.
5. The method of synthesizing a cotton-derived porous carbon electrode material of claim 4, wherein: in the cobalt nitrate solution, the concentration of cobalt nitrate is 0.5-1.5 mol/L; the mass ratio of the porous carbon material to the cobalt nitrate solution is 1: 30-1: 70.
6. The method of synthesizing a cotton-derived porous carbon electrode material of claim 4, wherein: the temperature of the hydrothermal reaction is 150-210 ℃, and the time of the hydrothermal reaction is 8-16 h.
7. The method of synthesizing a cotton-derived porous carbon electrode material of claim 4, wherein: the cleaning step of the precipitate comprises the steps of repeatedly cleaning the precipitate for 3-4 times by using ultrapure water; and grinding the carbonized product after carbonization treatment to obtain the cotton-derived porous carbon electrode material.
8. The method for synthesizing a porous carbon electrode material derived from cotton as claimed in claim 1 wherein the carbonization treatment step comprises: and calcining the compound in an air atmosphere at the temperature of 350-450 ℃ for 1.5-2.5 h.
9. The cotton-derived porous carbon electrode material is synthesized according to the synthesis method of any one of claims 1 to 8, and comprises a porous carbon material and cobalt oxide particles growing on the surface of the porous carbon material.
10. Use of the cotton-derived porous carbon electrode material of claim 9 in the manufacture of an electrode for a supercapacitor.
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