CN112938930B - Bacterial cellulose composite metal organic framework material derived carbon aerogel and preparation method and application thereof - Google Patents
Bacterial cellulose composite metal organic framework material derived carbon aerogel and preparation method and application thereof Download PDFInfo
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- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 62
- 229920002749 Bacterial cellulose Polymers 0.000 title claims abstract description 49
- 239000005016 bacterial cellulose Substances 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 25
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 25
- 239000002131 composite material Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- 238000003763 carbonization Methods 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 239000000017 hydrogel Substances 0.000 claims description 29
- 238000006243 chemical reaction Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 27
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 claims description 24
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 22
- 239000011148 porous material Substances 0.000 claims description 22
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 20
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000243 solution Substances 0.000 claims description 15
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
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- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 3
- 241000589220 Acetobacter Species 0.000 claims description 2
- 241000894006 Bacteria Species 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 20
- 239000007772 electrode material Substances 0.000 abstract description 8
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- 238000001704 evaporation Methods 0.000 abstract description 3
- 238000007792 addition Methods 0.000 description 21
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 12
- 239000003990 capacitor Substances 0.000 description 10
- 229910052799 carbon Inorganic materials 0.000 description 10
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- 238000007254 oxidation reaction Methods 0.000 description 9
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- 239000002253 acid Substances 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
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- -1 carboxylate anions Chemical class 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 125000002791 glucosyl group Chemical group C1([C@H](O)[C@@H](O)[C@H](O)[C@H](O1)CO)* 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000013110 organic ligand Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
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- RKMGAJGJIURJSJ-UHFFFAOYSA-N 2,2,6,6-tetramethylpiperidine Chemical compound CC1(C)CCCC(C)(C)N1 RKMGAJGJIURJSJ-UHFFFAOYSA-N 0.000 description 1
- AEMOLEFTQBMNLQ-AQKNRBDQSA-N D-glucopyranuronic acid Chemical compound OC1O[C@H](C(O)=O)[C@@H](O)[C@H](O)[C@H]1O AEMOLEFTQBMNLQ-AQKNRBDQSA-N 0.000 description 1
- IAJILQKETJEXLJ-UHFFFAOYSA-N Galacturonsaeure Natural products O=CC(O)C(O)C(O)C(O)C(O)=O IAJILQKETJEXLJ-UHFFFAOYSA-N 0.000 description 1
- 229920001046 Nanocellulose Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910021401 carbide-derived carbon Inorganic materials 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 229940097043 glucuronic acid Drugs 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
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- 230000014759 maintenance of location Effects 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000001404 mediated effect Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000002133 porous carbon nanofiber Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
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- H—ELECTRICITY
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- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
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- H—ELECTRICITY
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Abstract
The invention belongs to the technical field of biological nano materials, and particularly relates to a bacterial cellulose composite metal organic framework material derived carbon aerogel, and a preparation method and application thereof. The invention takes bacterial cellulose as a precursor, selects a clean, efficient and stable soft template method, and utilizes Zn in the pyrolysis process 2+ Gasifying and evaporating and etching to generate a large amount of defects and a large amount of micropores and mesopores in the BC derived nano-fiber, and optimizing through a drying and high-temperature carbonization process to prepare the carbon aerogel with high specific surface area, specific capacity and high cycle stability, thereby providing the electrode active material with excellent electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of biological nano materials, and particularly relates to a bacterial cellulose composite metal organic framework material derived carbon aerogel, and a preparation method and application thereof.
Background
With the rapid development of sustainable and renewable energy sources, due to the high power characteristics, rapid charge and discharge capabilities, extremely long service life of Supercapacitors (SC) ((>10 ten thousand cycles), high safetyAnd reliability, and thus is recognized as an integral part of future power systems. Various carbon nanomaterials such as activated carbon, templated porous carbon, carbide-derived carbon, carbon nanofibers, carbon nanotubes and graphene, which are typical representatives of electrode materials for Electric Double Layer Capacitors (EDLCs), have been extensively studied due to their excellent structural characteristics such as high chemical stability, high porosity, large specific surface area and high electrical conductivity. Among carbon nanomaterials, activated carbon dominates the commercial market. However, the energy density of current commercial SC based on activated carbon electrode materials is not satisfactory
Because of their low specific capacitance (typically less than 200F g in aqueous electrolytes) -1 ). For practical applications, there is a need to produce high performance carbon electrode materials with higher specific capacitance without sacrificing its power performance and cycling stability.
In general, the capacitance enhancement of carbon electrodes can be achieved by chemical modification methods such as adding a pore structure to itself, or synthesizing pseudocapacitive materials. Faradaic reactions generated by pseudocapacitive materials such as metal oxides/hydroxides or conducting polymers can enhance charge storage resulting in higher specific capacitance, but cycling performance is much poorer than EDLC due to the irreversibility of faradaic reactions and the decrease in conductivity. Heteroatom doping can enhance the spin density and charge distribution of the surrounding carbon atoms, thereby promoting wettability and creating pseudocapacitive active sites, resulting in enhanced specific capacity while still having unsatisfactory cycling stability. A suitably distributed macroporous/mesoporous/microporous porous carbon material with a high specific surface area is capable of rapidly promoting mass transport and repeated exposure of active sites, and allows for high charge storage under rapid charge and discharge conditions. However, to achieve the desired porous structure, hard templates (MgO, ZnO, SiO) are used 2 Etc.), physical activation method (CO) 2 Steam, etc.), chemical activation process (H) 3 PO 4 ，H 2 SO 4 ，ZnCl 2 KOH, etc.), these methods can effectively form a large number of pores, but are resource and time consuming, complicated multi-step treatment, low in efficiency, and extremely harmful to the environment. Soft templates provide a simpler, more efficient and less polluting strategy for the synthesis of porous carbon with a well-defined pore structure and a tight pore size distribution. But the use of suitable surfactants is a crucial issue and these surfactants can be converted into amorphous carbon with relatively large diffusion limitations and low conductivity. Despite great efforts to improve the capacitance of carbon electrode materials, it is a challenge to develop porous carbon with high specific capacitance and excellent cycle performance for practical application.
Chinese patent application document (publication No. CN202010858972X) discloses a preparation method of bacterial cellulose-based carbon aerogel, wherein bacterial cellulose is used as a precursor, a proper ionic solution is selected, and the carbon aerogel with a stable structure is prepared by a drying and high-temperature carbonization process, but the carbon aerogel is assembled into a symmetrical super capacitor, so that the specific capacity and the energy density are required to be improved, and further improvement is required.
Recently, Metal Organic Frameworks (MOFs) have been demonstrated as precursors of porous carbon materials, which generally have large surface areas and high specific capacitances, but whose cycling performance is unsatisfactory due to the pseudocapacitive properties of metal-containing or nitrogen-containing chemicals.
Disclosure of Invention
The invention aims to solve the technical problems and provide the bacterial cellulose composite metal organic framework material-derived carbon aerogel with large specific surface area, high specific capacity, high energy density and excellent cycle performance.
The above object of the present invention is achieved by the following technical solutions:
a bacterial cellulose composite metal organic framework material derived carbon aerogel, the specific surface area of the carbon aerogel is 860-930m 2 g -1 Pore volume of 0.2-0.4cm 3 g –1 The pore size is 5-10 nm.
Preferably, the specific surface area of the carbon aerogel is 890-895m 2 g -1 Pore volume of 0.28-0.32cm 3 g –1 And the pore size is 6-7 nm.
The invention also provides a preparation method of the bacterial cellulose composite metal organic framework material derived carbon aerogel, which comprises the following steps:
s1: dissolving TEMPO and sodium bromide in water, and stirring to obtain a mixed solution;
s2: adding the BC dispersion liquid into the mixed solution, adding a sodium hypochlorite solution and hydrochloric acid, then adding a sodium hydroxide solution for reaction, continuously dropwise adding until the reaction is finished, adding zinc nitrate hexahydrate for reaction to obtain a reaction product, and then washing with water;
s3: after cleaning, adding water and a mixed solution of tert-butyl alcohol, uniformly stirring, adding zinc nitrate hexahydrate and trimesic acid, and fully reacting at 80 ℃ to form hydrogel;
s4: and (3) freezing and drying the hydrogel to obtain aerogel, and carbonizing the aerogel to obtain the bacterial cellulose composite metal organic framework material-derived carbon aerogel.
Most metal chemicals are very stable at high temperatures, with only Zn 2+ Can be reduced to metallic Zn and then evaporated and diffused at a temperature higher than 800 ℃. The invention is therefore based on the cation being Zn 2+ And metal organic framework materials containing only ligands of O, C atoms as ideal pore-forming soft templates, improve the specific capacitance and energy density of EDLC carbon materials while maintaining their unique cycling properties.
The carbon aerogel prepared by the soft template method is a layered porous carbon nanofiber block prepared by carbonizing Zn-1,3, 5-benzene tricarboxylic acid (BTC) (Zn-BTC) composite three-dimensional (3D) Bacterial Cellulose (BC). Wherein 2,6, 6-tetramethylpiperidine 1-oxyl (TEMPO) oxidized BC provides a carboxylic acid group (COOH) having a high density distribution - ) The carboxyl group and Zn are mixed with cellulose nano fiber (TOCN) uniformly and highly dispersed 2+ The ions have a strong affinity, i.e. many active sites of contact between BC and Zn-BTC, and then to Zn during pyrolysis 2+ Vaporization and vapor etching are performed to create controlled defects and micropores and mesopores in the BC-derived nanofibers.Compared with pure BC-derived carbon and most reported activated porous carbon, the carbon aerogel has larger specific surface area due to controllable defects, micropores and mesopores, and the 3D carbon network provides higher specific capacitance for the carbon aerogel. The symmetrical super capacitor constructed by the carbon aerogel has higher specific capacity, obvious energy and power density and excellent stability, which shows that the symmetrical super capacitor has excellent integral energy storage performance and can realize practical application with great prospect.
Preferably, the concentration of the BC dispersion in step S1 is 0.55-0.65%. The concentration and uniformity of BC can affect the pore structure and mechanical properties of the carbon aerogel.
Further preferably, the bacterial cellulose is synthesized by a bacterium of the genus acetobacter.
Preferably, the concentration of TEMPO in the mixed solution of the step S1 is 0.02-0.18g/L, and the concentration of NaBr is 0.8-2.5 g/L.
The TEMPO-mediated oxidation reaction has a specific regioselectivity for the surface modification of nanocrystalline cellulose. Under the alkaline condition, when TEMPO coexists with NaBr and NaClO, C6 primary alcohol hydroxyl on the surface of the bacterial cellulose can be selectively converted into carboxyl, and a large number of uniformly distributed carboxyl on the surface are favorable for increasing the solubility of the bacterial cellulose in water. With the continuous reaction, the cellulose molecules can generate peeling reaction to generate glucosyl and cellulose terminal biased sugar acid group, wherein the glucosyl can be oxidized into micromolecular acid such as glucuronic acid, and the dispersibility and stability of the bacterial cellulose are further improved. Although the oxidation reaction changes the surface structure of the cellulose, the original crystal structure of the cellulose molecules is not changed, and the crystallinity and the grain size after oxidation are not obviously changed. The surface of the oxidized bacterial cellulose is provided with a large amount of carboxylate anions, electrostatic repulsion and permeation effects exist among the carboxylate anions, and the bacterial cellulose can be completely and uniformly dispersed in an aqueous solution under slight mechanical stirring treatment, so that the cellulose gel with high transparency, high flexibility and tensile strength is obtained.
Preferably, the concentration of the sodium hypochlorite aqueous solution in step S2 is 7-13%.
The invention adopts TEMPO as an oxidation catalyst to form a TEMPO/NaBr/NaClO oxidation system with sodium bromide and sodium hypochlorite, performs functional group oxidation on bacterial cellulose, and then maintains the stability of the oxidation system under an acidic condition. The unoxidized bacterial cellulose can not be completely dissolved in water, and the oxidation system provided by the invention can effectively solve the problem of dispersion of the bacterial cellulose in water, so that fiber welding is formed among fibers, the stability of a carbon aerogel structure is facilitated, and the mechanical strength of the carbon aerogel structure can be improved.
Preferably, the volume ratio of the sodium hypochlorite solution to the hydrochloric acid in the step S2 is 1: 1.
Preferably, the concentration of the sodium hydroxide solution in the step S2 is 0.4-0.6 mol/L. In the oxidation system of the present invention, the pH value has a great influence on the reaction rate. When the reaction starts, the pH value of the reaction system is increased along with the addition of NaOH, the reaction rate is increased continuously, and the reaction rate reaches the maximum value when the pH value is 9.5-10.5.
Further preferably, the pH of the solution is controlled to 10 during the reaction of step S2.
Preferably, the volume ratio of water to tert-butanol in the mixed solution of step S3 is 4-7: 1.
Preferably, the molar ratio of zinc nitrate hexahydrate to trimesic acid in step S3 is (1-2): 1. in the invention, zinc nitrate hexahydrate in the step S3 is used as a precursor raw material of a metal organic framework material, if the addition amount is too much, a great amount of defects exist in the final carbon aerogel, and the excessive defects cause the reduction of the specific capacitance; zn in the pyrolysis process when the addition amount is too small 2+ The carbon aerogel has the advantages that the carbon aerogel only plays a little role in gasification and evaporation etching, so that the specific surface area is not very large, and the performance of the carbon aerogel cannot be obviously improved.
And dissolving zinc nitrate hexahydrate and organic ligand trimesic acid in water, uniformly mixing in the water, allowing metal ions and the organic ligand to enter a mutual system in a diffusion mode to perform self-assembly reaction, and obtaining the MOF material.
Preferably, the carbonization temperature in step S4 is 800-1000 ℃ and the time is 1-3 h.
More preferably, the temperature for carbonization is 900 ℃.
More preferably, the carbonization is performed in an inert atmosphere such as nitrogen or argon.
The invention also provides application of the bacterial cellulose composite metal organic framework material derived carbon aerogel in a super capacitor, and the carbon aerogel is used in the super capacitor as a binderless electrode.
Compared with the prior art, the invention has the following beneficial effects:
1. the invention takes bacterial cellulose as a precursor, selects a clean, efficient and stable soft template method, and utilizes Zn in the pyrolysis process 2+ Gasifying and evaporating and etching to generate a large amount of defects and a large amount of micropores and mesopores in the BC derived nano-fiber, and optimizing through a drying and high-temperature carbonization process to prepare the carbon aerogel with high specific surface area, specific capacity and high cycle stability, thereby providing the electrode active material with excellent electrochemical performance.
2. The method effectively enhances the structural stability of the carbon aerogel, and enables the carbon aerogel to have good mechanical properties.
3. According to the invention, the bacterial cellulose-based carbon aerogel is used for the super capacitor and can be used as an electrode active material to prepare the super capacitor with high specific capacitance and high stability.
4. The method has the advantages of simple and controllable process, good repeatability and easy realization of industrialization, and can be popularized and applied in the field of green energy.
Drawings
FIG. 1 is an SEM image of the carbon aerogel obtained in example 1.
FIG. 2 is a cyclic voltammogram measured at 100mV/s for two carbon aerogel electrodes of example 1 and comparative example 1.
FIG. 3 is a graph showing the charge and discharge curves of the carbon aerogel electrodes of example 1 and comparative example 1 under the condition of 1A/g.
Fig. 4 is a graph showing the cycle stability of both electrodes of the carbon aerogel electrode obtained in example 1.
Fig. 5 is a graph showing energy density and power density of both electrodes of the carbon aerogel electrode obtained in example 1.
Detailed Description
The technical solution of the present invention is further described and illustrated by the following specific examples. The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified. It should be understood that the specific embodiments described herein are merely to aid in the understanding of the invention and are not intended to limit the invention specifically.
Example 1:
s1: mixing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of deionized water, and stirring for 1 hour to obtain a mixed solution;
s2: 14mg of 0.6% BC dispersion was added to the above mixture, followed by addition of 2mL of 10% NaClO aqueous solution and 2mL of hydrochloric acid at room temperature, followed by addition of 0.5M NaOH aqueous solution for reaction, and the dropwise addition was continued to maintain the pH of the reaction mixture at about 10.0. Adding 89mg (0.3mmol) of zinc nitrate hexahydrate for full reaction, and thoroughly cleaning the obtained reaction product with deionized water;
s3: then, 25mL of a mixed solution of water and t-butanol (5:1, v/v) was added, followed by addition of 238mg (0.8mmol) of zinc nitrate hexahydrate and 75.45. mu.L (0.533mmol) of trimesic acid and stirring at 80 ℃ for 2 hours to form a uniform hydrogel;
s4: pre-freezing the obtained hydrogel in liquid nitrogen for 24 hours, then placing the hydrogel into a vacuum freeze dryer for drying treatment for 48 hours, then placing the dried aerogel into a tubular resistance furnace for high-temperature carbonization, raising the temperature to 900 ℃ at the speed of 2 ℃/min in argon, preserving the temperature for 2 hours, and taking out the hydrogel after the tubular resistance furnace is cooled to obtain the hydrogel with the specific surface area of 893m 2 g -1 Pore volume of 0.3cm 3 g –1 And a carbon aerogel having a pore size of 6.71 nm.
Example 2:
s1: mixing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of deionized water, and stirring for 1 hour to obtain a mixed solution;
s2: 14mg of 0.6% BC dispersion was added to the above mixture, followed by addition of 2mL of 10% NaClO aqueous solution and 2mL of hydrochloric acid at room temperature, followed by addition of 0.5M NaOH aqueous solution for reaction, and the dropwise addition was continued to maintain the pH of the reaction mixture at about 10.0. Adding 89mg (0.3mmol) of zinc nitrate hexahydrate for full reaction, and thoroughly cleaning the obtained reaction product with deionized water;
s3: then, 25mL of a mixed solution of water and t-butanol (5:1, v/v) was added, followed by 238mg (0.8mmol) of zinc nitrate hexahydrate and 75.45. mu.L (0.533mmol) of trimesic acid, and the mixture was stirred at 80 ℃ for 2 hours to form a uniform hydrogel;
s4: pre-freezing the obtained hydrogel in liquid nitrogen for 24 hours, then placing the hydrogel into a vacuum freeze dryer for drying treatment for 48 hours, then placing the dried aerogel into a tubular resistance furnace for high-temperature carbonization, raising the temperature to 800 ℃ at the speed of 2 ℃/min in argon, preserving the temperature for 2 hours, and taking out the hydrogel after the tubular resistance furnace is cooled to obtain the hydrogel with the specific surface area of 572m 2 g -1 Pore volume of 0.15cm 3 g –1 And carbon aerogel with the pore size of 10.4 nm.
Example 3:
s1: mixing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of deionized water, and stirring for 1 hour to obtain a mixed solution;
s2: 14mg of 0.6% BC dispersion was added to the above mixture, followed by addition of 2mL of 10% NaClO aqueous solution and 2mL of hydrochloric acid at room temperature, followed by addition of 0.5M NaOH aqueous solution for reaction, and the dropwise addition was continued to maintain the pH of the reaction mixture at about 10.0. Adding 89mg (0.3mmol) of zinc nitrate hexahydrate for full reaction, and thoroughly cleaning the obtained reaction product with deionized water;
s3: then, 25mL of a mixed solution of water and t-butanol (5:1, v/v) was added, followed by addition of 238mg (0.8mmol) of zinc nitrate hexahydrate and 75.45. mu.L (0.533mmol) of trimesic acid and stirring at 80 ℃ for 2 hours to form a uniform hydrogel;
s4: pre-freezing the obtained hydrogel in liquid nitrogen for 24 hours, then putting the hydrogel into a vacuum freeze dryer for drying treatment for 48 hours, then putting the dried aerogel into a tubular resistance furnace for high-temperature carbonization, raising the temperature to 1000 ℃ at the speed of 2 ℃/min in argon, preserving the temperature for 2 hours, and taking out the hydrogel after the tubular resistance furnace is cooled to obtain the hydrogel with the specific surface area of 676m 2 g -1 Pore volume of 0.14cm 3 g –1 And carbon aerogel with the pore size of 8.88 nm.
Example 4:
s1: mixing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of deionized water, and stirring for 1 hour to obtain a mixed solution;
s2: 14mg of 0.6% BC dispersion was added to the above mixture, followed by addition of 2mL of 10% NaClO aqueous solution and 2mL of hydrochloric acid at room temperature, followed by addition of 0.5M NaOH aqueous solution for reaction, and the dropwise addition was continued to maintain the pH of the reaction mixture at about 10.0. Adding 89mg (0.3mmol) of zinc nitrate hexahydrate for full reaction, and thoroughly cleaning the obtained reaction product with deionized water;
s3: then, 25mL of a mixed solution of water and t-butanol (5:1, v/v) was added, and 59.5mg (0.2mmol) of zinc nitrate hexahydrate and 18.8. mu.L (0.133mmol) of trimesic acid were added and stirred at 80 ℃ for 2 hours to form a uniform hydrogel;
s4: pre-freezing the obtained hydrogel in liquid nitrogen for 24 hours, then placing the hydrogel into a vacuum freeze dryer for drying treatment for 48 hours, then placing the dried aerogel into a tubular resistance furnace for high-temperature carbonization, raising the temperature to 900 ℃ at the speed of 2 ℃/min in argon, preserving the temperature for 2 hours, taking out the hydrogel after the tubular resistance furnace is cooled to obtain the hydrogel with the specific surface area of 606m 2 g -1 Pore volume of 0.28cm 3 g –1 And a carbon aerogel having a pore size of 7.13 nm.
Example 5:
s1: mixing 0.016g of TEMPO and 0.1g of NaBr, dissolving in 100mL of deionized water, and stirring for 1 hour to obtain a mixed solution;
s2: 14mg of 0.6% BC dispersion was added to the above mixture, followed by addition of 2mL of 10% NaClO aqueous solution and 2mL of hydrochloric acid at room temperature, followed by addition of 0.5M NaOH aqueous solution for reaction, and dropwise addition was continued to maintain the pH of the reaction solution at about 10.0. Adding 89mg (0.3mmol) of zinc nitrate hexahydrate for full reaction, and thoroughly cleaning the obtained reaction product with deionized water;
s3: then, 25mL of a mixed solution of water and t-butanol (5:1, v/v) was added, and 297.5mg (1.0mmol) of zinc nitrate hexahydrate and 94.4. mu.L (0.667mmol) of trimesic acid were added and stirred at 80 ℃ for 2 hours to form a uniform hydrogel;
s4: pre-freezing the obtained hydrogel in liquid nitrogen for 24 hours, then placing the hydrogel into a vacuum freeze dryer for drying treatment for 48 hours, then placing the dried aerogel into a tubular resistance furnace for high-temperature carbonization, raising the temperature to 900 ℃ at the speed of 2 ℃/min in argon, preserving the temperature for 2 hours, taking out the hydrogel after the tubular resistance furnace is cooled to obtain the hydrogel with the specific surface area of 605m 2 g -1 Pore volume of 0.27cm 3 g –1 And a carbon aerogel having a pore size of 9.81 nm.
Comparative example 1:
the carbon aerogel was prepared according to the method described in example 1 of chinese patent application (publication No. CN202010858972X), i.e., the difference from example 1 of the present invention is that zinc nitrate hexahydrate and trimesic acid were not added in the whole preparation process.
The carbon aerogel sample of the BC composite metal organic framework material obtained in example 1 was scanned with a field emission scanning electron microscope to characterize its morphology and structure. As can be seen from FIG. 1, the bacterial cellulose-based carbon aerogel prepared in example 1 has a rich chemical structure, the arrangement of the nanopores is dense, the porous network structure of the cellulose gel is well maintained, and the pores are adhered to one another. Therefore, the prepared carbon aerogel has a large three-dimensional network structure.
Two carbon aerogels obtained in example 1 and comparative example 1 are named as supercapacitor electrodes A and B, and are wrapped on foamed nickel and clamped on an electrode clamp respectively. In a three-electrode system, an Ag/AgCl electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, and 6M KOH solution is used as electrolyte, and the electrochemical performance of the three-electrode system is respectively tested at room temperature.
FIG. 2 is a cyclic voltammogram of two carbon aerogels at a sweep rate of 100mV/s, from which it was found that the carbon aerogel obtained in example 1 had a larger, wider rectangular area, indicating a higher energy storage capacity of the electrode.
FIG. 3 is a charge-discharge curve measured under the condition of 1A/g, and the specific capacitances of the electrodes A and B of the super capacitor are calculated to be 352F/g and 178F/g respectively, which are consistent with the result of the cyclic voltammetry curve.
FIG. 4 is a cycle stability curve of the two electrodes of the electrode A measured under the condition of 6A/g, and after 70000 cycles, the cycle retention rate is close to 100%, which shows that the electrode has good cycle stability.
FIG. 5 is a graph of the power density and energy density of the two electrodes of electrode A, with an energy density of 14.83Wh/kg at a power density of 0.60kW/kg and an energy density of 9.065Wh/kg at a power density of 24.35kW/kg, indicating that the electrodes have a very high energy density.
From the above results, it can be seen that the method of the present invention effectively increases the specific capacity of the prepared carbon material and well maintains the cycling stability, compared to the supercapacitor performance of commercial activated carbon in the prior art. The method selects a proper metal organic framework material as a soft template, optimizes and improves the pore structure of the cellulose carbon aerogel through the processes of simple stirring, drying and high-temperature carbonization, not only effectively enhances the specific surface area of the carbon aerogel and introduces adjustable defects, but also provides an electrode material with good performance for the super capacitor, and can be used for preparing green energy storage devices with high specific capacitance, long cycle life and high energy density.
The technical scope of the invention claimed by the embodiments of the present application is not exhaustive, and new technical solutions formed by equivalent replacement of single or multiple technical features in the technical solutions of the embodiments are also within the scope of the invention claimed by the present application; in all the embodiments of the present invention, which are listed or not listed, each parameter in the same embodiment only represents an example (i.e., a feasible embodiment) of the technical solution, and there is no strict matching and limiting relationship between the parameters, wherein the parameters may be replaced with each other without departing from the axiom and the requirements of the present invention, unless otherwise specified.
The technical means disclosed by the scheme of the invention are not limited to the technical means disclosed by the technical means, and the technical scheme also comprises the technical scheme formed by any combination of the technical characteristics. While the foregoing is directed to embodiments of the present invention, it will be appreciated by those skilled in the art that various changes may be made in the embodiments without departing from the principles of the invention, and that such changes and modifications are intended to be included within the scope of the invention.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (8)
1. The bacterial cellulose composite metal organic framework material-derived carbon aerogel is characterized in that the specific surface area of the carbon aerogel is 890-895m 2 g -1 Pore volume of 0.28-0.32cm 3 g –1 The aperture size is 6-7 nm; the preparation method of the carbon aerogel comprises the following steps:
s1: dissolving TEMPO and sodium bromide in water, and stirring to obtain a mixed solution;
s2: adding the BC dispersion liquid into the mixed solution, adding a sodium hypochlorite solution and hydrochloric acid, then adding a sodium hydroxide solution for reaction, continuously dropwise adding until the reaction is finished, adding zinc nitrate hexahydrate for reaction to obtain a reaction product, and then washing with water;
s3: after cleaning, adding water and a mixed solution of tert-butyl alcohol, uniformly stirring, adding zinc nitrate hexahydrate and trimesic acid, and fully reacting at 80 ℃ to form hydrogel;
s4: and (3) freezing and drying the hydrogel to obtain aerogel, and carbonizing the aerogel to obtain the bacterial cellulose composite metal organic framework material-derived carbon aerogel.
2. The bacterial cellulose composite metal organic framework material-derived carbon aerogel according to claim 1, wherein the concentration of the BC dispersion in step S1 is 0.55-0.65%.
3. The bacterial cellulose composite metal organic framework material-derived carbon aerogel according to claim 2, wherein the BC is synthesized by bacteria of the genus Acetobacter.
4. The bacterial cellulose composite metal organic framework material-derived carbon aerogel according to claim 1, wherein the concentration of TEMPO in the mixed solution of step S1 is 0.02-0.18g/L, and the concentration of NaBr is 0.8-2.5 g/L.
5. The bacterial cellulose composite metal organic framework material-derived carbon aerogel according to claim 1, wherein the volume ratio of water to tert-butyl alcohol in the mixed solution of step S3 is (4-7): 1.
6. The bacterial cellulose composite metal organic framework material-derived carbon aerogel according to claim 1, wherein the molar ratio of zinc nitrate hexahydrate to trimesic acid in step S3 is (1-2): 1.
7. the bacterial cellulose composite metal organic framework material-derived carbon aerogel as claimed in claim 1, wherein the carbonization temperature in step S4 is 800-1000 ℃ and the carbonization time is 1-3 h.
8. Use of the bacterial cellulose composite metal organic framework material-derived carbon aerogel according to claim 1 in a supercapacitor, wherein the carbon aerogel according to any one of claims 1-7 is used as a binderless electrode in a supercapacitor.
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