CN113247893A - Woody biomass-based porous carbon material prepared by high-temperature hydrothermal assisted hydrolysis of cellulase, and application and method thereof - Google Patents
Woody biomass-based porous carbon material prepared by high-temperature hydrothermal assisted hydrolysis of cellulase, and application and method thereof Download PDFInfo
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- 239000003990 capacitor Substances 0.000 claims description 14
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- 229910052757 nitrogen Inorganic materials 0.000 claims description 9
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- ALSPKRWQCLSJLV-UHFFFAOYSA-N azanium;acetic acid;acetate Chemical compound [NH4+].CC(O)=O.CC([O-])=O ALSPKRWQCLSJLV-UHFFFAOYSA-N 0.000 claims description 3
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- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
- C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
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- 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
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
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Abstract
The invention discloses a woody biomass-based porous carbon material prepared by a high-temperature hydrothermal assisted cellulase hydrolysis method, which comprises the following preparation steps: mixing the air-dried woody biomass raw material with deionized water to perform high-temperature hydrothermal pretreatment; filtering and washing; naturally drying after soaking, repeatedly operating for many times, and refrigerating for later use; mixing the woody biomass subjected to high-temperature hydrothermal pretreatment with cellulase powder in an acetic acid-sodium acetate buffer solution, taking out, freezing and freeze-drying; carbonizing, washing to neutrality, and drying to obtain the wood biomass-based porous carbon material. The preparation process is simple, the activating agent is green and environment-friendly, strong acid, strong alkali and harsh conditions are not needed, and the wood biomass-based porous carbon material has a large specific surface area and a high specific capacitance when being used as a working electrode material of a supercapacitor.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a woody biomass-based porous carbon material prepared by using high-temperature hydrothermal assisted cellulase hydrolysis, and application and a method thereof.
Background
As a novel energy storage device, the super capacitor has attracted much attention because of its advantages of high power density, fast charge and discharge, and ultra-long cycle life. However, the energy density of the super capacitor is not high, which limits the large-scale commercial application of the super capacitor. The electrochemical performance of the electrode material is determined by taking the electrode material as a core device in the super capacitor. Currently, biomass-derived porous carbon has been widely used as an electrode material due to its high specific surface area and high porosity. Many researchers have used KOH, NaOH, H3PO4Activating the precursor by using an activating agent to prepare the biomass-based porous carbon with rich pore diameter. The activator has strong corrosivity and is easy to pollute the environment, so that the long-term development of the activator is restricted. Therefore, the biomass-based porous carbon material prepared by using cheap biomass as a substrate and a better activation mode as an electrode material of a supercapacitor has important significance.
Compared with other wood biomass, the carbonized wood can be used as a self-supporting electrode material without adding any binder or conductive agent. This advantage is derived from the good multi-stage, porous structure of the wood itself, as well as the good mechanical strength and natural pore structure that can be maintained after carbonization. The carbonized wood also has the advantages of light weight and fast ion/electron conduction, so that the biomass carbon material prepared by taking the wood as the raw material becomes an ideal material for constructing a high-performance super capacitor.
However, the composition of wood is complex, lignin, hemicellulose and cellulose are intertwined, and if only single carbonized wood is used, the obtained wood-based porous carbon has small specific surface area and single pore structure, and cannot fully exert the energy storage performance when applied to a supercapacitor electrode. Different from the activation commonly used at presentAgents KOH, H3PO4The method has strong corrosivity, and the biological enzyme is used as a novel pore-forming agent to activate the wood biomass to prepare the porous carbon, so that the method has the advantages of greenness and no toxicity. The cellulase can effectively hydrolyze part of cellulose in the wood to form a large number of nano-pores, which is beneficial to improving the specific surface area and further improving the electrochemical performance. However, from the viewpoint of the composition and chemical structure of wood, the high crystallinity of cellulose itself and the physical barrier formed by the wrapping of lignin make the effect of wood treated by hydrolysis with cellulase poor. The literature reports that a large amount of hemicellulose in wood can be dissolved out through high-temperature hydrothermal pretreatment, the lignin is partially removed from the wood, and the tight combination of the three components can be reduced to a certain extent.
Therefore, in order to reasonably utilize the natural excellent pore channel structure of the woody biomass matrix and improve the defects of the traditional chemical activating agent, the woody biomass based porous carbon material for the electrode material is prepared by adopting a high-temperature hydrothermal assisted cellulase hydrolysis dual mild activation method, and the regulation and control of the morphology and the pore size structure are very necessary.
Through searching, the following two patent publications related to the patent application of the invention are found:
1. a woody biomass-based porous carbon material prepared by using inorganic molten salt hydrate and a preparation method and application thereof (CN111960414A) comprise the following preparation steps: air-dried wood biomass raw materials and preheated deionized water are filled into a closed pressure container to be fully mixed, and self-hydrolysis pretreatment is carried out; filtering and washing; naturally drying after soaking, repeatedly operating for many times, and refrigerating for later use; preparing 0.1-6M of inorganic strong acid solution; preparing an inorganic molten salt hydrate solution, adding the standby raw materials into the inorganic molten salt hydrate solution, carrying out ultrasonic treatment, freezing and freeze-drying treatment; carbonizing, washing to neutrality, and drying to obtain the wood biomass-based porous carbon material. The preparation process is simple, harsh conditions such as high temperature and high pressure are not needed, and the wood biomass-based porous carbon material has larger specific surface area, better mesopore occupation ratio and higher specific capacity when being used as a working electrode material of a super capacitor.
2. Preparation and application of biomass-based porous carbon material based on sycamore seed (CN109626370A), specifically comprising the following steps: crushing and sieving the sycamore seeds to obtain sycamore seed powder; putting 5-10 parts by weight of the powder of the seed of the trident sycamore, 5-10 parts by weight of solid alkali and 80-90 parts by weight of water into a hydrothermal reaction kettle for pretreatment, taking out the mixture and then drying to obtain pretreated powder; carbonizing the pretreated powder under the protection of inert gas to obtain a carbonized product; and sequentially carrying out acid washing, water washing and drying to constant weight to obtain the biomass-based porous carbon material. The preparation method adopts the alkali water heat treatment-high temperature carbonization process, thereby not only simplifying the preparation process of the biomass carbon material, but also reducing the use amount of the strong base of the activating agent and the pollution to the environment. And the obtained porous carbon material has excellent performance when being used as an electrode material of a super capacitor, and has wide market application prospect.
By contrast, the present patent application is substantially different from the above patent publications.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a woody biomass-based porous carbon material prepared by using high-temperature hydrothermal assisted cellulase hydrolysis, and application and a method thereof.
The technical scheme adopted by the invention for solving the technical problem is as follows:
a woody biomass-based porous carbon material prepared by using high-temperature hydrothermal assisted cellulase hydrolysis comprises the following preparation steps:
mixing a wood biomass raw material which is air-dried to contain 1% -50% of moisture with deionized water according to a solid-liquid ratio of 1: 3-20 kg/L, heating to 100-200 ℃ from room temperature under a sealed condition, and keeping the temperature for 30-120 min to perform high-temperature hydrothermal pretreatment;
cooling the wooden biomass raw material obtained in the step to 30-60 ℃, then filtering the wooden biomass raw material by using a 80-200 mesh nylon sieve, and then fully washing the wooden biomass raw material subjected to high-temperature hydrothermal by using deionized water until filtrate is colorless and the pH value of the filtrate is neutral; then naturally drying the mixture and storing the mixture in a refrigerating chamber at 4 ℃ for later use;
thirdly, adding the woody biomass and the cellulase powder obtained in the second step into a buffer solution with the pH value of 3.0-6.0, and uniformly mixing; then putting the whole system into a constant-temperature culture oscillator with the temperature of 30-80 ℃ for reaction, rotating at 90-180 rpm, and after the reaction, putting the whole reaction system into a constant-temperature water bath with the temperature of 40-100 ℃ to denature and inactivate the cellulase; then, the woody biomass is washed until the woody biomass is neutral, then is frozen at minus 80 ℃ for 4-36 hours, and is quickly taken out for freeze-drying treatment, and finally, the dried woody biomass material after the high-temperature hydrothermal assisted cellulase hydrolysis treatment is obtained;
fourthly, the wooden biomass material obtained in the step three is placed in inert gas for carbonization, then washed to be neutral, and then dried at 70-100 ℃ for 12-48 hours to obtain the self-supporting structure-maintained wooden biomass-based porous carbon material.
Furthermore, the wooden biomass in the step is one of poplar, eucalyptus, basswood and birch, and the axial direction multiplied by the tangential direction multiplied by the radial dimension is 1-4 mm multiplied by 30 mm.
Further, adding deionized water into the double-cylinder rotary cooking pot according to the solid-liquid ratio of 1: 3-20 kg/L; and then heating the sealed double-cylinder rotary cooking pot to 100-200 ℃ from room temperature.
Further, the enzyme activity of the cellulase powder in the step three is 10000U/g, and the ligneous biomass and the cellulase powder are mixed according to the mass ratio of 5: 1-20: 1.
Further, the buffer solution in the step three is one of acetic acid-sodium acetate and acetic acid-ammonium acetate.
Further, in the step three, 20-100 mL of buffer solution is added in per gram of total mass of the woody biomass and the cellulase powder.
Further, the reaction time of the hydrolysis of the cellulase in the step three is 12-72 hours.
Further, the carbonization treatment in the fourth step is carried out at 600-1000 ℃ for 1-8 hours, and the inert gas is one of nitrogen, argon and helium.
The application of the wood biomass-based porous carbon material in the preparation of a supercapacitor three-electrode system is disclosed.
The method for preparing the supercapacitor three-electrode system by using the wood biomass-based porous carbon material comprises the following assembly steps:
the method comprises the steps of washing a wooden biomass-based porous carbon material with deionized water for multiple times to remove impurities, washing until the pH value is neutral, and drying;
preparing 2-6M KOH solution, and placing the KOH solution in an electrolytic cell; weighing a wood biomass-based porous carbon material after drying treatment, and directly installing the wood biomass-based porous carbon material on a working electrode in a three-electrode system of a super capacitor;
and after the assembly and connection of the instrument are completed, standing for 0.5-1 h to obtain the stable three-electrode system of the supercapacitor.
The invention has the advantages and positive effects that:
1. the preparation process is simple, the activating agent is green and environment-friendly, strong acid, strong alkali and harsh conditions are not needed, and the wood biomass-based porous carbon material has a large specific surface area and a high specific capacitance when being used as a working electrode material of a supercapacitor.
2. The preparation process of the porous carbon material is simple, harsh conditions such as high temperature and high pressure are not needed, and the wood biomass-based porous carbon material has a large specific surface area and a high specific capacitance when being used as a supercapacitor electrode material.
3. The method prepares the wood-based biomass porous carbon by a high-temperature hydrothermal assisted cellulose hydrolysis method, and meets the preparation requirements of environmental protection and low cost.
4. The invention utilizes natural carbon skeleton and multi-pore channel structure in the wood biomass to prepare the all-carbon material with micro-mesopores and a completely self-supporting structure. The process steps for preparing the electrode plate are simplified, and the cost can be effectively saved. In the process of preparing the wood-based porous carbon material, the wood biomass structure is regulated and controlled by a simple, convenient and low-loss high-temperature hydrothermal auxiliary enzymolysis treatment means, so that the electrochemical performance of the wood-based porous carbon material is improved. Meanwhile, the invention fully and effectively utilizes the wood biomass widely existing in nature, and expands the application range and field thereof.
5. According to the invention, the woody biomass-based porous carbon material is finally obtained by treating the woody biomass with high-temperature hydrothermal auxiliary cellulase, freeze-drying the woody biomass, and then carrying out a series of treatments such as high-temperature carbonization and the like. The wood biomass subjected to high-temperature hydrothermal pretreatment can effectively destroy the anti-degradation barrier of cellulose in the wood chips, so that the accessible surface area of cellulase hydrolysis is increased, the porosity of the matrix is improved, and the energy storage performance of the wood biomass when the wood biomass is used as a supercapacitor electrode material is improved. By controlling the reaction of different dosages of cellulase and the woody biomass and subsequent carbonization treatment, the morphology design and the pore structure of the woody biomass-based carbon material can be optimized, and the material can be used as an electrode material of a super capacitor.
Drawings
FIG. 1 is a graph of the chronopotentiometric (GCD) graph of the woody biomass-based porous carbon material prepared in example 1 of the present invention;
fig. 2 is a Cyclic Voltammogram (CV) of the woody biomass-based porous carbon material prepared in example 1 of the present invention;
FIG. 3 is an Electrochemical Impedance Spectroscopy (EIS) plot of a woody biomass-based porous carbon material prepared in example 1 of the present invention;
fig. 4 is a nitrogen adsorption-desorption curve and a pore size distribution diagram of the woody biomass-based porous carbon material prepared in example 1 of the present invention;
FIG. 5 is a graph of the chronopotentiometric (GCD) graph of the woody biomass-based porous carbon material prepared in example 2 of the present invention;
fig. 6 is a Cyclic Voltammogram (CV) of the woody biomass-based porous carbon material prepared in example 2 of the present invention;
FIG. 7 is an Electrochemical Impedance Spectroscopy (EIS) plot of a woody biomass-based porous carbon material prepared in example 2 of the present invention;
fig. 8 is a nitrogen adsorption-desorption curve and a pore size distribution diagram of the woody biomass-based porous carbon material prepared in example 2 of the present invention;
FIG. 9 is a graph of the chronopotentiometric (GCD) graph of the woody biomass-based porous carbon material prepared in example 3 of the present invention;
fig. 10 is a Cyclic Voltammogram (CV) of the woody biomass-based porous carbon material prepared in example 3 of the present invention;
fig. 11 is an electrochemical impedance spectroscopy plot (EIS) of the woody biomass-based porous carbon material prepared in example 3 of the present invention;
fig. 12 is a nitrogen adsorption-desorption curve and a pore size distribution diagram of the woody biomass-based porous carbon material prepared in example 3 of the present invention;
wherein the legends in figures 1 to 12 are all named for different mass ratios of ligneous biomass to cellulase in each example.
Detailed Description
The present invention is further illustrated by the following examples, which are intended to be illustrative, not limiting and are not intended to limit the scope of the invention.
The raw materials used in the invention are all conventional commercial products if no special description is provided, the method used in the invention is all conventional methods in the field if no special description is provided, and the mass of all the materials used in the invention is the conventional use mass.
A woody biomass-based porous carbon material prepared by using high-temperature hydrothermal assisted cellulase hydrolysis comprises the following preparation steps:
mixing a wood biomass raw material which is air-dried to contain 1% -50% of moisture with deionized water according to a solid-liquid ratio of 1: 3-20 kg/L, heating to 100-200 ℃ from room temperature under a sealed condition, and keeping the temperature for 30-120 min to perform high-temperature hydrothermal pretreatment;
cooling the wooden biomass raw material obtained in the step to 30-60 ℃, then filtering the wooden biomass raw material by using a 80-200 mesh nylon sieve, and then fully washing the wooden biomass raw material subjected to high-temperature hydrothermal by using deionized water until filtrate is colorless and the pH value of the filtrate is neutral; then naturally drying the mixture and storing the mixture in a refrigerating chamber at 4 ℃ for later use;
thirdly, adding the woody biomass and the cellulase powder obtained in the second step into a buffer solution with the pH value of 3.0-6.0, and uniformly mixing; then putting the whole system into a constant-temperature culture oscillator with the temperature of 30-80 ℃ for reaction, rotating at 90-180 rpm, and after the reaction, putting the whole reaction system into a constant-temperature water bath with the temperature of 40-100 ℃ to denature and inactivate the cellulase; then, the woody biomass is washed until the woody biomass is neutral, then is frozen at minus 80 ℃ for 4-36 hours, and is quickly taken out for freeze-drying treatment, and finally, the dried woody biomass material after the high-temperature hydrothermal assisted cellulase hydrolysis treatment is obtained;
fourthly, the wooden biomass material obtained in the step three is placed in inert gas for carbonization, then washed to be neutral, and then dried at 70-100 ℃ for 12-48 hours to obtain the self-supporting structure-maintained wooden biomass-based porous carbon material.
Preferably, the wooden biomass in the step is one of poplar, eucalyptus, basswood and birch, and the axial direction × the tangential direction × the radial direction is 1-4 mm × 30mm × 30 mm.
Preferably, the method comprises the steps of adding deionized water into a double-cylinder rotary cooking pan according to a solid-to-liquid ratio of 1: 3-20 kg/L; and then heating the sealed double-cylinder rotary cooking pot to 100-200 ℃ from room temperature.
Preferably, the enzyme activity of the cellulase powder in the step three is 10000U/g, and the ligneous biomass and the cellulase powder are mixed according to the mass ratio of 5: 1-20: 1.
Preferably, the buffer solution in the step three is one of acetic acid-sodium acetate and acetic acid-ammonium acetate.
Preferably, in the step three, 20-100 mL of buffer solution is added in per gram of total mass of the woody biomass and the cellulase powder.
Preferably, the reaction time of the hydrolysis of the cellulase in the step three is 12-72 hours.
Preferably, the carbonization treatment in the fourth step is performed at 600-1000 ℃ for 1-8 hours, and the inert gas is one of nitrogen, argon and helium.
The application of the wood biomass-based porous carbon material in the preparation of a supercapacitor three-electrode system is disclosed.
The method for preparing the supercapacitor three-electrode system by using the wood biomass-based porous carbon material comprises the following assembly steps:
the method comprises the steps of washing a wooden biomass-based porous carbon material with deionized water for multiple times to remove impurities, washing until the pH value is neutral, and drying;
preparing 2-6M KOH solution, and placing the KOH solution in an electrolytic cell; weighing a wood biomass-based porous carbon material after drying treatment, and directly installing the wood biomass-based porous carbon material on a working electrode in a three-electrode system of a super capacitor;
and after the assembly and connection of the instrument are completed, standing for 0.5-1 h to obtain the stable three-electrode system of the supercapacitor.
Specifically, the preparation and detection are as follows:
example 1
A woody biomass-based porous carbon material prepared by using high-temperature hydrothermal assisted cellulase hydrolysis comprises the following preparation steps:
firstly, drying 100g of poplar wood chips (3mm multiplied by 30mm, axial multiplied by tangential multiplied by radial) which are air-dried to contain 10% of moisture, and adding the poplar wood chips and deionized water into a double-cylinder rotary cooking pot according to the solid-liquid ratio of 1:10 kg/L; heating the closed double-cylinder rotary digester from room temperature to 160 ℃, and keeping the temperature for 120min for high-temperature hydrothermal pretreatment;
cooling the wooden biomass raw material obtained in the step to 30 ℃, then filtering the wooden biomass raw material by using a 80-mesh nylon sieve, and then fully washing the wooden biomass raw material subjected to high-temperature hydrothermal treatment by using deionized water until filtrate is colorless and the pH value of the filtrate is neutral; naturally drying, and storing in a refrigerating chamber at about 4 deg.C;
thirdly, adding the woody biomass and cellulase powder (enzyme activity, 10000U/g) obtained in the step II into 50ml of acetic acid-sodium acetate buffer solution with the pH value of 5.0 according to the mass ratio of 10: 1, and uniformly mixing; then putting the whole system into a constant-temperature culture oscillator (with the rotating speed of 150rpm) at the temperature of 60 ℃ for reaction, putting the whole reaction system into a constant-temperature water bath at the temperature of 80 ℃ after the reaction reaches 48 hours to denature and inactivate the cellulase, then washing the woody biomass until the woody biomass is neutral, freezing the woody biomass at the temperature of-80 ℃ for 24 hours, quickly taking out the woody biomass for freeze-drying treatment, and finally obtaining the dried woody biomass material after the high-temperature hydrothermal assisted cellulase hydrolysis treatment;
and fourthly, placing the wooden biomass material obtained in the step three in inert gas for carbonization treatment for 4h, wherein the carbonization temperature is 800 ℃, and then washing until the pH value is neutral and drying to obtain the wooden biomass-based porous carbon material with the self-supporting structure. The correlation graphs of the electrochemical performance test and the nitrogen adsorption-desorption curve test of the wood biomass-based material are shown in figures 1 to 4.
The material obtained in example 1 was assembled into a supercapacitor as follows:
[1] washing the wood biomass-based porous carbon material with deionized water until the pH value is neutral, and drying;
[2] 6M KOH solution is prepared, and a certain volume of the solution is placed in an electrolytic cell. And weighing the dried woody biomass-based porous carbon material, and directly installing the weighed material on a working electrode in a three-electrode system of the supercapacitor.
[3]After the electrolyte fully soaks the material, various electrochemical performance tests can be carried out. The test is carried out by adopting a constant current charging and discharging method, the test instrument is a Shanghai Chenghua 660E test system, the test current density is 0.1A/g, and the voltage range is-1-0V. Different electrochemical performance tests and N are carried out on the manufactured supercapacitor three-electrode system2Adsorption-desorption test. The electrochemical performance and structural characteristics data for the woody biomass-based porous carbon material of this example are shown in table 1.
Table 1 electrochemical performance and structural characteristics of the woody biomass-based porous carbon material of example 1
The results show that:
the prepared wood biomass-based porous carbon material is black, rectangular and flatShape; specific surface area of 384.62m2Per g, total pore volume of 0.16cm3(ii)/g; under the condition of a small current density of 0.1A/g, the specific capacitance of the capacitor can reach 133.75F/g, and a good approximately rectangular shape is kept; at 104Hz～10-3Under Hz, the electrochemical alternating current impedance reaches 0.88ohm in a high-frequency semicircular arc area.
Example 2
A woody biomass-based porous carbon material prepared by using high-temperature hydrothermal assisted cellulase hydrolysis comprises the following preparation steps:
firstly, drying 100g of poplar wood chips (3mm multiplied by 30mm, axial multiplied by tangential multiplied by radial) which are air-dried to contain 10% of moisture, and adding the poplar wood chips and deionized water into a double-cylinder rotary cooking pot according to the solid-liquid ratio of 1:10 kg/L; heating the closed double-cylinder rotary digester from room temperature to 160 ℃, and keeping the temperature for 120min for high-temperature hydrothermal pretreatment;
cooling the wooden biomass raw material obtained in the step to 30 ℃, then filtering the wooden biomass raw material by using a 80-mesh nylon sieve, and then fully washing the wooden biomass raw material subjected to high-temperature hydrothermal treatment by using deionized water until filtrate is colorless and the pH value of the filtrate is neutral; naturally drying, and storing in a refrigerating chamber at about 4 deg.C;
thirdly, adding the woody biomass and cellulase powder (enzyme activity, 10000U/g) obtained in the step II into 50mL of acetic acid-sodium acetate buffer solution with the pH value of 5.0 according to the mass ratio of 15: 1, and uniformly mixing; then putting the whole system into a constant-temperature culture oscillator (with the rotating speed of 150rpm) at the temperature of 60 ℃ for reaction, putting the whole reaction system into a constant-temperature water bath at the temperature of 80 ℃ after the reaction reaches 48 hours to denature and inactivate the cellulase, then washing the woody biomass until the woody biomass is neutral, freezing the woody biomass at the temperature of-80 ℃ for 24 hours, quickly taking out the woody biomass for freeze-drying treatment, and finally obtaining the dried woody biomass material after the high-temperature hydrothermal assisted cellulase hydrolysis treatment;
and fourthly, placing the wooden biomass material obtained in the step three in inert gas for carbonization treatment for 4h, wherein the carbonization temperature is 800 ℃, and then washing until the pH value is neutral and drying to obtain the wooden biomass-based porous carbon material with the self-supporting structure. The correlation graphs of the electrochemical performance test and the nitrogen adsorption-desorption curve test of the wood biomass-based material are shown in figures 5 to 8.
The material obtained in example 2 was assembled into a supercapacitor as follows:
[1] washing the wood biomass-based porous carbon material with deionized water until the pH value is neutral, and drying;
[2] 6M KOH solution is prepared, and a certain volume of the solution is placed in an electrolytic cell. And weighing the dried woody biomass-based porous carbon material, and directly installing the weighed material on a working electrode in a three-electrode system of the supercapacitor.
[3]After the electrolyte fully soaks the material, various electrochemical performance tests can be carried out. The test is carried out by adopting a constant current charging and discharging method, the test instrument is a Shanghai Chenghua 660E test system, the test current density is 0.1A/g, and the voltage range is-1-0V. Different electrochemical performance tests and N are carried out on the manufactured supercapacitor three-electrode system2Adsorption-desorption test. The electrochemical performance and structural characteristics data for the woody biomass-based porous carbon material of this example are shown in table 2.
Table 2 electrochemical performance and structural characteristics of the woody biomass-based porous carbon material of example 2
The results show that:
the prepared wood biomass-based porous carbon material is in a black rectangular flat shape; specific surface area of 671.51m2Per g, total pore volume of 0.26cm3(ii)/g; under the condition of a small current density of 0.1A/g, the specific capacitance of the capacitor can reach 149.70F/g, and a good approximately rectangular shape is kept; at 104Hz～10-3Under Hz, the electrochemical alternating current impedance reaches 0.43ohm in a high-frequency semicircular arc area.
Example 3
A woody biomass-based porous carbon material prepared by using high-temperature hydrothermal assisted cellulase hydrolysis comprises the following preparation steps:
firstly, drying 100g of poplar wood chips (3mm multiplied by 30mm, axial multiplied by tangential multiplied by radial) which are air-dried to contain 10% of moisture, and adding the poplar wood chips and deionized water into a double-cylinder rotary cooking pot according to the solid-liquid ratio of 1:10 kg/L; heating the closed double-cylinder rotary digester from room temperature to 160 ℃, and keeping the temperature for 120min for high-temperature hydrothermal pretreatment;
cooling the wooden biomass raw material obtained in the step to 30 ℃, then filtering the wooden biomass raw material by using a 80-mesh nylon sieve, and then fully washing the wooden biomass raw material subjected to high-temperature hydrothermal treatment by using deionized water until filtrate is colorless and the pH value of the filtrate is neutral; naturally drying, and storing in a refrigerating chamber at about 4 deg.C;
thirdly, adding the woody biomass and cellulase powder (enzyme activity, 10000U/g) obtained in the step II into 50mL of acetic acid-sodium acetate buffer solution with the pH value of 5.0 according to the mass ratio of 20: 1, and uniformly mixing; then putting the whole system into a constant-temperature culture oscillator (with the rotating speed of 150rpm) at the temperature of 60 ℃ for reaction, putting the whole reaction system into a constant-temperature water bath at the temperature of 80 ℃ after the reaction reaches 48 hours to denature and inactivate the cellulase, then washing the woody biomass until the woody biomass is neutral, freezing the woody biomass at the temperature of-80 ℃ for 24 hours, quickly taking out the woody biomass for freeze-drying treatment, and finally obtaining the dried woody biomass material after the high-temperature hydrothermal assisted cellulase hydrolysis treatment;
and fourthly, placing the wooden biomass material obtained in the step three in inert gas for carbonization treatment for 4h, wherein the carbonization temperature is 800 ℃, and then washing until the pH value is neutral and drying to obtain the wooden biomass-based porous carbon material with the self-supporting structure. The correlation graphs of the electrochemical performance test and the nitrogen adsorption-desorption curve test of the wood biomass-based material are shown in figures 10 to 12.
The material obtained in example 3 was assembled into a supercapacitor as follows:
[1] washing the wood biomass-based porous carbon material with deionized water until the pH value is neutral, and drying;
[2] 6M KOH solution is prepared, and a certain volume of the solution is placed in an electrolytic cell. And weighing the dried woody biomass-based porous carbon material, and directly installing the weighed material on a working electrode in a three-electrode system of the supercapacitor.
[3]After the electrolyte fully soaks the material, various electrochemical performance tests can be carried out. The test is carried out by adopting a constant current charging and discharging method, the test instrument is a Shanghai Chenghua 660E test system, the test current density is 0.1A/g, and the voltage range is-1-0V. Different electrochemical performance tests and N are carried out on the manufactured supercapacitor three-electrode system2Adsorption-desorption test. The electrochemical performance and structural characteristics data for the woody biomass-based porous carbon material of this example are shown in table 3.
Table 3 electrochemical performance and structural characteristics of the woody biomass-based porous carbon material of example 3
The results show that:
the prepared wood biomass-based porous carbon material is in a black rectangular flat shape; specific surface area of 516.41m2Per g, total pore volume of 0.28cm3(ii)/g; under the condition of a small current density of 0.1A/g, the specific capacitance of the capacitor can reach 124.40F/g, and a good approximately rectangular shape is kept; at 104Hz～10-3In Hz, the electrochemical alternating current impedance reaches 0.46ohm in a high-frequency semicircular arc area.
Although the embodiments of the present invention have been disclosed for illustrative purposes, those skilled in the art will appreciate that: various substitutions, changes and modifications are possible without departing from the spirit and scope of the invention and the appended claims, and therefore the scope of the invention is not limited to the embodiments disclosed.
Claims (10)
1. A woody biomass-based porous carbon material prepared by using high-temperature hydrothermal assisted cellulase hydrolysis is characterized in that: the preparation steps are as follows:
mixing a wood biomass raw material which is air-dried to contain 1% -50% of moisture with deionized water according to a solid-liquid ratio of 1: 3-20 kg/L, heating to 100-200 ℃ from room temperature under a sealed condition, and keeping the temperature for 30-120 min to perform high-temperature hydrothermal pretreatment;
cooling the wooden biomass raw material obtained in the step to 30-60 ℃, then filtering the wooden biomass raw material by using a 80-200 mesh nylon sieve, and then fully washing the wooden biomass raw material subjected to high-temperature hydrothermal by using deionized water until filtrate is colorless and the pH value of the filtrate is neutral; then naturally drying the mixture and storing the mixture in a refrigerating chamber at 4 ℃ for later use;
thirdly, adding the woody biomass and the cellulase powder obtained in the second step into a buffer solution with the pH value of 3.0-6.0, and uniformly mixing; then putting the whole system into a constant-temperature culture oscillator with the temperature of 30-80 ℃ for reaction, rotating at 90-180 rpm, and after the reaction, putting the whole reaction system into a constant-temperature water bath with the temperature of 40-100 ℃ to denature and inactivate the cellulase; then, the woody biomass is washed until the woody biomass is neutral, then is frozen at minus 80 ℃ for 4-36 hours, and is quickly taken out for freeze-drying treatment, and finally, the dried woody biomass material after the high-temperature hydrothermal assisted cellulase hydrolysis treatment is obtained;
fourthly, the wooden biomass material obtained in the step three is placed in inert gas for carbonization, then washed to be neutral, and then dried at 70-100 ℃ for 12-48 hours to obtain the self-supporting structure-maintained wooden biomass-based porous carbon material.
2. The woody biomass-based porous carbon material produced by the hydrolysis of cellulase enzymes assisted by high temperature hydrothermal conditions as claimed in claim 1, wherein: the method comprises the steps that the wooden biomass is one of poplar, eucalyptus, basswood and birch, and the axial multiplied by tangential multiplied by radial dimension is 1-4 mm multiplied by 30 mm.
3. The woody biomass-based porous carbon material produced by the hydrolysis of cellulase enzymes assisted by high temperature hydrothermal conditions as claimed in claim 1, wherein: the method comprises the steps of adding deionized water into a double-cylinder rotary cooking pan according to a solid-liquid ratio of 1: 3-20 kg/L; and then heating the sealed double-cylinder rotary cooking pot to 100-200 ℃ from room temperature.
4. The woody biomass-based porous carbon material produced by the hydrolysis of cellulase enzymes assisted by high temperature hydrothermal conditions as claimed in claim 1, wherein: in the step three, the enzyme activity of the cellulase powder is 10000U/g, and the ligneous biomass and the cellulase powder are mixed according to the mass ratio of 5: 1-20: 1.
5. The woody biomass-based porous carbon material produced by the hydrolysis of cellulase enzymes assisted by high temperature hydrothermal conditions as claimed in claim 1, wherein: and in the step three, the buffer solution is one of acetic acid-sodium acetate and acetic acid-ammonium acetate.
6. The woody biomass-based porous carbon material produced by the hydrolysis of cellulase enzymes assisted by high temperature hydrothermal conditions as claimed in claim 1, wherein: and in the step three, 20-100 mL of buffer solution is added in the total mass of each gram of the woody biomass and the cellulase powder.
7. The woody biomass-based porous carbon material produced by the hydrolysis of cellulase enzymes assisted by high temperature hydrothermal conditions as claimed in claim 1, wherein: and the reaction time of the hydrolysis of the cellulase in the step three is 12-72 hours.
8. The woody biomass-based porous carbon material produced by the hydrolysis of cellulase enzymes with the assistance of high temperature hydrothermal according to any one of claims 1 to 7, wherein: and step four, the carbonization treatment is carried out at the temperature of 600-1000 ℃ for 1-8 hours, and the inert gas is one of nitrogen, argon and helium.
9. Use of the woody biomass-based porous carbon material of any one of claims 1 to 8 in the preparation of a supercapacitor three-electrode system.
10. The method for preparing a supercapacitor three-electrode system by using the woody biomass-based porous carbon material according to any one of claims 1 to 8, wherein: the assembling steps are as follows:
the method comprises the steps of washing a wooden biomass-based porous carbon material with deionized water for multiple times to remove impurities, washing until the pH value is neutral, and drying;
preparing 2-6M KOH solution, and placing the KOH solution in an electrolytic cell; weighing a wood biomass-based porous carbon material after drying treatment, and directly installing the wood biomass-based porous carbon material on a working electrode in a three-electrode system of a super capacitor;
and after the assembly and connection of the instrument are completed, standing for 0.5-1 h to obtain the stable three-electrode system of the supercapacitor.
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