CN112174136A - High-nitrogen biochar composite material and preparation method and application thereof - Google Patents
High-nitrogen biochar composite material and preparation method and application thereof Download PDFInfo
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention provides a high-nitrogen biochar composite material and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing, washing and modulating high-nitrogen biomass serving as a carbon source and a nitrogen source with acid; placing the obtained solid product in pyrolysis equipment, introducing carbon-containing gas into the pyrolysis equipment to pyrolyze the solid product in a carbon-rich atmosphere, heating the equipment to a preset temperature from room temperature, treating for a period of time, and cooling to room temperature to realize one-step carbonization and activation of the high-nitrogen biomass and prepare the nitrogen self-doped active biochar; and coating metal oxide on the nitrogen self-doped active biochar to obtain the high-nitrogen biochar composite material. The high-nitrogen biomass one-step carbonization and activation are realized by using non-inert atmosphere carbon-containing gas, the energy density of a carbon electrode is improved by coating transition metal oxide, in-situ nitrogen self-doping and functionalization of a biochar structure are realized, and the high-nitrogen biochar composite material can be used for preparing an electrode of a super capacitor or an ion battery.
Description
Technical Field
The invention relates to the technical field of high-value utilization of organic solid wastes, in particular to a method for preparing a transition metal oxide-coated functional biochar composite material with hierarchical pore canals by utilizing high-nitrogen-content biomass in a carbon-rich atmosphere and a liquid phase system, and then applying the composite material in the energy storage field of a super capacitor and the like.
Background
Biomass is the only CO2A net zero-emission renewable resource. The biomass can be converted into gas, liquid and solid three-state products through pyrolysis, and the method is a simple biomass high-value utilization technology. The biomass is in various types, and one type of biomass has high nitrogen content, such as soybean cake dregs, bean curd dregs, shrimp shells, crab shells, algae and the like. Taking bean cake dregs as an example, the bean cake dregs are byproducts obtained after soybean oil is extracted from soybeans by squeezing, are raw materials with high crude protein content, can reach more than 46 percent, and are often used as livestock and poultry protein feeds. However, the bean cake dregs contain more nutrientsThe nutrient factors and the antigen substances bring certain harm to the growth of livestock and poultry, and are confirmed to be one of the key factors for inducing the incidence of digestive tract diseases of the livestock and poultry, so that the application of the bean cake dregs in the field of feed is limited, and more of the bean cake dregs become organic solid wastes. Bean cake dregs serving as one kind of biomass can be simply and conveniently converted into porous biochar with a higher specific surface area and a more developed pore structure through the pyrolysis technology; and because the bean cake dregs are a natural high-nitrogen-content raw material with high crude protein content, the nitrogen content can reach more than 8 wt%, and nitrogen can be partially retained in a biochar structure in a new form after pyrolysis to form nitrogen self-doped biochar, thereby laying a foundation for subsequent high-value utilization. However, in the traditional pyrolysis process, inert gases such as nitrogen and argon are mostly used as carrier gases, so that the loss of nitrogen is high in the process of generating carbon, and meanwhile, the carbon has poor physical and chemical properties and is difficult to use at a high value, and further activation is needed to prepare the active biochar. Meanwhile, due to the influence of the special components of the soybeans, the bean cake dregs are easy to agglomerate and crosslink in the pyrolysis process, the hardness is greatly increased, and the subsequent utilization of the charcoal is difficult; and for high-nitrogen biomasses such as shrimp shells and crab shells, the high-nitrogen biomasses also contain more inorganic mineral substances such as calcium carbonate and the like, and the subsequent preparation of high-quality carbon materials is also influenced.
The conventional preparation method of the active biochar usually adopts a physical activation method or a chemical activation method, for example, the physical activation method comprises the steps of carrying out further high-temperature (usually more than or equal to 800 ℃) steam or carbon dioxide activation on the biochar obtained after pyrolysis and carbonization of raw materials to expand pores; the chemical activation mostly adopts high proportion (such as the mass ratio of the activating agent to the biochar is more than or equal to 1) and high corrosivity (such as KOH and ZnCl)2) The chemical agent activates the biochar. That is, currently, the activated charcoal is mostly produced and manufactured by a two-step method (firstly, the charcoal is prepared by pyrolysis and carbonization and then the next activation process is carried out), the process is various, and the operation temperature is high and the pores of the charcoal are underdeveloped under the condition of physical activation; under the chemical activation, the chemical agent is consumed excessively, and serious corrosion is caused to equipment.
The super capacitor is a substitute energy storage device with great development prospect, and has the advantages of high power density, safe operation, super long period stability and reversibilityAnd the like, and the method is concerned by people. Carbon materials are considered to be excellent materials for the preparation of supercapacitors due to their low cost, high electrical conductivity and good chemical stability. However, the pure carbon material has the defect of lower theoretical specific capacitance, and the maximum specific capacitance of the pure carbon material does not exceed 250F/g. Research shows that heteroatom doping in a carbon structure such as nitrogen atom can improve the pseudocapacitance characteristic of a capacitor, so that the electrochemical characteristic of an electrode material is greatly improved. The in-situ nitrogen-doped biochar prepared by utilizing the raw material with high nitrogen content in the body can effectively avoid the problems of high cost, complex process, uneven doping and the like caused by the introduction of an exogenous nitrogen dopant. The patent CN105314629A discloses a method for directly preparing a co-doped three-dimensional graphene electrode material by using a biomass carbon source, wherein biomass such as artemia cysts and bean pulp is used as the carbon source, red phosphorus or boric acid is added as a stripping agent, metal nickel salt is used as a catalyst, and the oxygen-nitrogen-phosphorus polyatomic co-doped three-dimensional porous graphene is synthesized by calcining at 700-900 ℃ under an argon atmosphere. Patent CN102874807A discloses an activated carbon material and application thereof as an electrode material of a double electric layer capacitor, wherein the activated carbon material is prepared by taking moso bamboo as a carbon source and adopting a phosphoric acid-carbon dioxide physical and chemical activation method, namely, the raw material is fully soaked in a phosphoric acid solution and then is subjected to N2Heating to 400-800 deg.C under protection of atmosphere, and adding CO2Activating at constant temperature to obtain the activated carbon material. The patent CN105921106A discloses a surface nitrogen-rich activated carbon, a preparation method and an application thereof, which comprises the steps of carbonizing a soybean meal raw material rich in nitrogen elements under the protection of inert gas, fixing nitrogen, and preparing the nitrogen-rich activated carbon with developed micropores by using KOH activation, wherein the nitrogen content is 1.0-2.8%. That is, in the prior art, the raw materials are mostly pyrolyzed in an inert atmosphere, the prepared biochar has high nitrogen loss and poor physical and chemical properties, secondary activation is needed, high-dosage and strong-corrosivity activating agents are mostly used in the secondary activation, and the obtained biochar is mainly microporous (more than or equal to 90%). Research shows that for an ideal carbonaceous electrode material, on one hand, micropores which provide a large number of adsorption sites for ions in an electrolyte are needed, and in addition, mesopores which are necessary for rapid ion transfer are needed. Therefore, a hierarchical pore structure is more suitable for energy storage applications. On the other hand, even if the use of a compound containing heteroThe problem of low energy density of the atom-doped carbon electrode in the application of the super capacitor still exists. Carbon electrodes for ion battery cathodes also face similar problems. How to further improve the electrochemical characteristics of the high-nitrogen activated biochar is a difficulty.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide a high-value utilization method of high-nitrogen biomass wastes.
In order to realize the aim, the invention provides a preparation method of a high-nitrogen biochar composite material, which comprises the following steps:
s1, mixing, washing and modulating high-nitrogen biomass serving as a carbon source and a nitrogen source with acid to obtain a solid product;
s2, placing the solid product obtained in the step S1 in pyrolysis equipment, introducing carbon-containing gas into the pyrolysis equipment to pyrolyze the solid product in a carbon-rich atmosphere, heating the equipment to a preset temperature from room temperature, treating for a period of time, and cooling to room temperature to realize one-step carbonization and activation of the high-nitrogen biomass and prepare the nitrogen self-doped active charcoal;
s3, coating metal oxide on the nitrogen self-doped active biochar to obtain the high-nitrogen biochar composite material.
Preferably, the bulk nitrogen content of the high-nitrogen biomass in step S1 is not less than 4 wt.%, and the high-nitrogen biomass comprises one or more of bean cake dregs, bean curd dregs, shrimp shells, crab shells, algae and the like.
Preferably, the mixed washing preparation in step S1 specifically includes the steps of: mixing the high-nitrogen biomass with acid with a certain concentration, heating to a certain temperature, carrying out magnetic stirring and repeated acid washing, then washing with distilled water until filtrate is neutral to obtain solid-phase washed biomass, wherein the concentration of the acid is 0.5-2M, and the temperature is highThe acid is HCl or HNO at 60-80 deg.C3、H2SO4、H3PO4、CH3One or more combinations of COOH, preferably HCl and HNO3The high-nitrogen biomass is pretreated by mixing, washing and modulating hydrochloric acid or nitric acid, so that the polymerization crosslinking of components and the removal of inorganic mineral substances such as calcium carbonate in the subsequent pyrolysis process can be effectively relieved, and a foundation is laid for the subsequent preparation of high-quality carbon.
Preferably, the mixed washing preparation in step S1 further includes the steps of: and uniformly mixing the solid-phase washing biomass with a trace amount of activator to prepare a trace amount of activator biomass blend, wherein the trace amount of activator is low-corrosivity alkali metal salt. The trace activator can be, but is not limited to, a low corrosivity alkali metal salt, and the trace activator/solid phase washing biomass mass ratio is 0-10%. The subsequent chain activation reaction can be triggered by adding a trace of activating agent.
Preferably, the solid product placed into the pyrolysis apparatus in step S2 is a solid phase washed biomass or a micro-activator biomass blend.
Preferably, the low corrosive alkali metal salt may be, but is not limited to, Li2CO3、Na2CO3、NaHCO3、K2CO3、KHCO3、Rb2CO3、Cs2CO3Etc., preferably K2CO3、KHCO3、Na2CO3、NaHCO3And the selected low corrosive alkali metal salt is not KOH or NaOH. KOH or NaOH are not within the preferred range of the present invention due to their higher corrosiveness.
Preferably, the carbon-containing gas in step S2 is CO2、CH3One or more combinations of COOH, and the carbon-containing gas is preferably CO2The volume concentration of the carbon-containing gas is 20-100%.
Preferably, in the step S2, the solid product is pyrolyzed in a carbon-rich atmosphere, the treatment temperature is 450-900 ℃, and the treatment time is 0.1-4 h; the treatment temperature is preferably 600-800 ℃, and the treatment time is 0.5-2 h.
The solid product is pyrolyzed in a high-temperature carbon-containing atmosphere, volatile components are released, residual solids are continuously aromatized, and meanwhile, carbon-containing gas, the volatile components and coke are subjected to complex interaction to erode a carbon matrix structure, so that pores are formed on the surface and in the bulk of the biochar, and a three-dimensional nanometer multistage pore channel structure with a larger specific surface area and a more regular structure is formed; meanwhile, after the nitrogen-containing and oxygen-containing functional groups on the carbon surface interact with the carbon-containing gas, the nitrogen-containing and oxygen-containing functional groups finally exist in the forms of pyridine nitrogen, pyrrole nitrogen and the like, and through the step, the one-step carbonization and activation of the high-nitrogen biomass are realized. Experiments show that the quantity of nitrogen-containing functional groups on the carbon surface is obviously increased compared with that of inert atmosphere, the nitrogen-containing functional groups are promoted to be fixed by carbon-rich atmosphere, and the nitrogen-containing compounds can obviously influence the surface polarity and the electronic state of a biological carbon structure, so that the band gap between a conduction band and a valence band is changed, the Faraday reaction between electrolyte ions and impurity-containing defects is guided, and the electrochemical performance of the biological carbon is obviously improved. In the case of the micro-activator biomass blend, the intermediate composite structure containing C-O-K is formed in the pyrolysis process in the carbon-rich atmosphere, and then is converted into a K-C complex, and is further oxidized into a new C-O-K intermediate in the carbon-rich atmosphere to form a chain reaction, so that the continuous formation and development of a pore structure are caused (as shown in FIG. 8). Namely, the chain type activation production and the high-efficiency preparation of the active biochar can be realized only by using a trace amount of green low-corrosion activating agent under the carbon-rich atmosphere.
Preferably, the metal oxide in step S3 is a transition metal salt, and the transition metal salt is deposited and coated on the surface of the nitrogen self-doped activated charcoal in the form of metal oxide through a liquid-phase system redox reaction, and this step is achieved through a hydrothermal reaction, so that the energy density of the electrode is further improved. The transition metal salt is TiCl4、KMnO4、Mn(NO3)2、FeCl3、Fe2(SO4)3、CoCl3、CuSO4One of (1); preferably FeCl3Or KMnO4One kind of (1); the concentration of the transition metal salt is 1-50 mmol/L, and the mass ratio of the nitrogen self-doped active biochar to the transition metal salt is 1: (0.5-2). Further, the above-mentionedThe concentration of the transition metal salt is 2-10 mmol/L, and the mass ratio of the nitrogen self-doped active biochar to the transition metal salt is 1: (0.8-1.2).
The invention also provides a high-nitrogen biochar composite material prepared by the preparation method, the high-nitrogen biochar composite material has a three-dimensional nano multistage pore channel structure, the microporosity is not less than 70%, the mesoporosity is not less than 10%, and the macroporosity is not less than 5%. The thickness of the metal oxide is 10-50 nm, and the structure is in a half-microsphere convex shape.
The invention also provides application of the high-nitrogen biochar composite material, and the high-nitrogen biochar composite material is used for preparing an electrode of a super capacitor or an ion battery. The nitrogen self-doping biochar with the hierarchical multi-level pore structure has high conductivity and wettability on one hand, is beneficial to full contact of an electrode material and electrolyte, and has high Faraday pseudo-capacitance characteristic on the other hand, and further, the specific capacitance and energy density of the composite electrode are enhanced by coating of metal oxide. Taking the application in a capacitor as an example, the specific capacitance of the electrode material of the supercapacitor prepared by using the high-nitrogen biochar composite material is more than 150F/g under a three-electrode system, the energy density of the assembled button-type symmetrical supercapacitor is more than 4.5 Wh/kg, and the capacitance retention rate is more than 90% after 10000 charge-discharge cycles.
Compared with the prior art, the invention has the following advantages and effects:
1. the method utilizes the carbon-containing gas to realize the one-step preparation from the high-nitrogen raw material to the high-nitrogen biomass activated carbon, and overcomes the two process steps of carbonization and activation in the traditional biomass activated carbon production.
2. Adding trace low-corrosivity alkali metal salt in a carbon-rich atmosphere to trigger a biochar chain type activation reaction to realize continuous generation of biochar pores, wherein the physical activation in the traditional process needs higher temperature (usually more than or equal to 800 ℃), and the reaming reaction can be triggered at lower temperature (not higher than 700 ℃); the traditional process adopts chemical activation, uses more high-dose activating agent (usually 1 time or more of the biological carbon), only needs not more than 0.1 time of the biological carbon, greatly reduces the reaction temperature of the system and the required amount of the activating agent, and uses the activating agent which is green and environment-friendly.
3. The electrode prepared from the high-nitrogen biochar prepared by the invention has a three-dimensional nano multi-stage pore channel structure, the carbon surface contains more nitrogen functional groups, and experimental tests show that the nitrogen content is improved by more than 10% compared with the carbon material produced in the traditional inert atmosphere.
4. The high-nitrogen biomass is pretreated by acid washing and modulation, so that nitrogen compounds are kept as far as possible, and the problems that the hardness of a carbon solid product is too high due to polymerization crosslinking possibly occurring in subsequent heat treatment of raw materials, the carbon quality is poor due to the influence of minerals such as calcium carbonate and the like are solved.
5. Furthermore, experimental tests prove that the specific capacitance of the supercapacitor electrode prepared from the high-nitrogen biochar prepared by the method is improved by more than 4 times compared with that of biochar prepared by conventional inert atmosphere pyrolysis in a three-electrode system and 6M potassium hydroxide solution at the current density of 1A/g, the specific capacitance reaches more than 150F/g, the 10000-cycle capacitance retention rate of the symmetrical supercapacitor prepared by assembly is more than 90%, and the circulation capacitance retention rate is still more than 84% even if 30000-cycle capacitance retention rates are obtained. The method adopts the carbon-rich atmosphere pyrolysis without special equipment, has low cost and is easy to popularize and use.
The features and advantages of the present invention will be described in detail by embodiments in conjunction with the accompanying drawings.
Drawings
FIG. 1 is a process flow diagram of a preparation method of a high-nitrogen biochar composite material.
FIG. 2 is a Scanning Electron Microscope (SEM) image of a high nitrogen biochar composite and nitrogen autodoped activated biochar in accordance with an embodiment of the invention;
wherein, FIGS (a) - (c) represent the high nitrogen biomass bean cake dregs in CO2Scanning electron micrographs of the activated biochar (designated as BPC) obtained after different treatment temperatures in the atmosphere, the treatment temperatures in each plot: (a) 700 deg.C, (b) 800 deg.C, (c) 900 deg.C; (d) the graph shows the treatment temperature of 800 ℃ plus the metal oxygenThe compound is loaded on the high-nitrogen biochar composite material.
FIG. 3 is an X-ray photoelectron spectroscopy (XPS) spectrum of a high nitrogen biochar composite and nitrogen autodoped activated biochar in accordance with an embodiment of the present invention;
wherein, the graph (a) is an XPS full spectrum of a high-nitrogen biochar composite material and a nitrogen self-doping active biochar sample; (b) the high-nitrogen biochar composite material contains a carbon functional group photoelectron spectrum; (c) the high-nitrogen biochar composite material contains a nitrogen functional group photoelectron spectrum; (d) the high-nitrogen biochar composite material contains a manganese functional group photoelectron spectrum.
FIG. 4 is a graph of cyclic voltammetry characteristics of an electrode prepared from a high nitrogen biochar composite according to an embodiment of the invention;
wherein, (a) the cyclic voltammetry characteristic curve of the high-nitrogen biochar composite material under different scanning rates (20-200 mV/s); (b) the cyclic voltammetry characteristic curve of the high-nitrogen biochar composite material under 10 mV/s; (c) the cyclic voltammetry characteristic curve of the high-nitrogen biochar composite material under 50 mV/s; (d) fitting a voltage logarithm and a current logarithm function of the high-nitrogen biochar composite material; (e) pseudo-capacitance contribution of the high-nitrogen biochar composite material; note: in the figure, the abscissa Potential is the voltage (V) and the ordinate Current is the Current (a).
FIG. 5 is a graph of cyclic voltammetry and galvanostatic charge-discharge characteristics for comparative electrodes of examples of the present invention;
wherein, (a) nitrogen self-doping active biochar cyclic voltammetry characteristic curve; (b) a constant current charge-discharge curve of the nitrogen self-doped active biochar; (c) specific area capacitance of nitrogen self-doped active biochar at different scanning rates; (d) and the specific mass capacitance of the nitrogen self-doped activated charcoal at different scanning rates.
FIG. 6 is a graph of constant current charging and discharging and impedance performance testing of electrodes prepared from the high-nitrogen biochar composite of the embodiment of the invention;
wherein, (a) the high-nitrogen biochar composite material has a constant current charge-discharge curve; (b) impedance characteristic curve of the high-nitrogen biochar composite. Note: (a) in the figure, the abscissa Time is Time(s) and the ordinate Potential is voltage (V); (b) in the figure, the abscissa Z ' and the ordinate-Z ' ' are impedance transformation expressions.
FIG. 7 is a graph of the energy density, power density and high rate cycle characteristics of a symmetrical supercapacitor of an electrode assembly made from a high nitrogen biochar composite in accordance with an embodiment of the present invention;
wherein, (a) an energy comparison graph of nitrogen self-doped activated biochar and high-nitrogen biochar composite materials; (b) testing the cycling stability of the nitrogen self-doped active biochar and high-nitrogen biochar composite material; note: (a) in the figure, the Power Density on the abscissa is the Power Density (W/kg), and the Energy Density on the ordinate is the Energy Density (Wh/kg); (b) in the figure, the abscissa Cycle Number is the Number of cycles, and the ordinate Capacitance Retention (%) is the Capacitance Retention.
FIG. 8 is a schematic diagram of chain reaction formation under a carbon-rich atmosphere.
Detailed Description
The invention is further described in detail below by way of examples with reference to the drawings, which are merely illustrative of the application of the composite material in supercapacitor applications, and the following examples are illustrative of the invention and the invention is not limited to the following examples.
Example 1
The method for preparing the supercapacitor electrode by using the high-nitrogen biochar composite material comprises the following steps:
step 1: weighing bean cake raw materials with certain mass, mixing with 2M hydrochloric acid, heating to 60 ℃, carrying out magnetic stirring and repeated acid washing for 8 hours, filtering, and then washing with distilled water until the filtrate is neutral to obtain solid-phase washed bean cake. After drying, 5g of the solid phase washed okara sample was placed in a tube furnace with 20% volume fraction CO2Premixing the gas and Ar gas, introducing the gas serving as a carrier gas into the tube furnace, heating the tube furnace to 800 ℃ from room temperature after stabilization, and keeping the temperature for 2 hours; taking out the sample after the sample is naturally cooled to prepare nitrogen self-doped active bean cake residue carbon which is marked as BPC-800-20%;
step 2: mixing nitrogen self-doped active bean cake residue carbon BPC-800-20%, acetylene black and polytetrafluoroethylene according to the mass ratio of 8:1:1, adding a proper amount of isopropanol, grinding to prepare an electrode film, placing the electrode film in a vacuum drying oven at 80 ℃ for drying for 8 h, then cutting into a certain 1 cm multiplied by 1 cm film, pressing the film on a 1 cm multiplied by 2 cm foam nickel sheet, keeping the pressure at 10 MPa for 60 s, and preparing an active bean cake residue carbon BPC-800-20% electrode;
and step 3: weighing 56.9mg KMnO4Dissolving in 60mL deionized water, magnetically stirring for 30min to obtain 6mM KMnO solution4A solution; transferring the solution into a high-pressure kettle liner tube with the capacity of 80 mL, soaking the active bean cake residue carbon square electrode in the high-pressure kettle liner tube, and sealing the high-pressure kettle liner tube in a hydrothermal reaction kettle; heating the reaction kettle in an oven at 170 deg.C for 2 h, cooling to room temperature, taking out the sample, washing with ethanol and distilled water for several times, and drying in a vacuum drying oven at 60 deg.C for 8 h to obtain composite bean cake residue carbon electrode BPC-800-20% @ MnO2；
And 4, step 4: the square electrode prepared in the step 3), a platinum electrode and a saturated calomel electrode respectively form a working electrode, a counter electrode and a reference electrode, 6M KOH solution is taken as electrolyte, and the composite bean cake residue carbon BPC-800-20% @ MnO is measured in an electrochemical workstation2The specific capacitance was 50.4F/g (current density = 1A/g). The specific surface area was measured to be 64.2 m2Nitrogen content 4.6 wt.%.
Example 2
Weighing bean cake raw materials with certain mass, mixing the bean cake raw materials with 2M hydrochloric acid, heating to 60 ℃, carrying out magnetic stirring and repeated acid washing, filtering, and then washing with distilled water until the filtrate is neutral to obtain solid-phase washed bean cake. Taking 5g of solid-phase washed bean cake residue sample, placing the sample in a tubular furnace, and adding 100% volume fraction CO2Taking gas as carrier gas, introducing into the tube furnace, heating the tube furnace to 800 ℃ from room temperature after stabilization, and keeping the temperature for 2 h; taking out the sample after natural cooling to obtain active bean cake carbon, and marking as BPC-800;
mixing active bean cake residue carbon BPC-800, acetylene black and polytetrafluoroethylene according to the mass ratio of 8:1:1, adding a proper amount of isopropanol, grinding to prepare an electrode film, drying the electrode film in a vacuum drying oven at 80 ℃ for 8 hours, then cutting the electrode film into a certain 1 cm multiplied by 1 cm film, pressing the film on a 1 cm multiplied by 2 cm foam nickel sheet, or cutting the electrode film into a film with the diameter of 1.5 cm, pressing the film on a 1.5 cm foam nickel sheet, keeping the pressure at 10 MPa for 60 s, and preparing the active bean cake residue carbon BPC-800 electrode;
weighing 56.9mg KMnO4Dissolving in 60mL deionized water, magnetically stirring for 30min to obtain 6mM KMnO solution4A solution; transferring the solution into an autoclave liner tube with the capacity of 80 mL, soaking the square or round electrode into the autoclave liner tube, and sealing the autoclave; heating the reaction kettle in an oven at 170 ℃ for 2 h, cooling to room temperature, taking out the sample, washing with ethanol and distilled water for several times, and drying in a vacuum drying oven at 60 ℃ for 8 h to obtain the composite bean cake residue carbon electrode BPC-800@ MnO2；
The square composite bean cake residue carbon electrode prepared by the method, a platinum electrode and a saturated calomel electrode respectively form a working electrode, a counter electrode and a reference electrode, 6M KOH solution is used as electrolyte, and the composite bean cake residue carbon electrode BPC-800@ MnO is measured at an electrochemical workstation2The specific capacitance was 179F/g (current density = 1A/g).
Assembling the round composite bean cake dreg carbon electrode prepared by the method with a positive and negative electrode shell, diaphragm paper, a gasket and the like to prepare a button type symmetrical supercapacitor, and measuring the composite bean cake dreg carbon electrode BPC-800@ MnO in an electrochemical workstation by taking 6M KOH solution as electrolyte2The energy density is as high as 4.5 Wh/kg when the power density is 62.5W/kg, and the capacity retention rate is 84.3 percent after 30000 charge-discharge cycles.
The specific surface area of the composite was found to be 175.4 m2/g, and the nitrogen content was found to be 5.8 wt.%.
Example 2 differs from example 1 to the greatest extent that example 2 uses a carbon-containing gas CO2The proportion is improved from 20 percent to 100 percent, the specific surface area of the high-nitrogen biochar composite material is improved by about 200 percent, the nitrogen content is improved by more than 25 percent, and the specific capacitance is improved by about 250 percent. The obtained material has excellent comprehensive performance.
Example 3
Weighing bean cake raw materials with certain mass, mixing the bean cake raw materials with 2M hydrochloric acid, heating to 60 ℃, carrying out magnetic stirring and repeated acid washing, filtering, and then washing with distilled water until the filtrate is neutral to obtain solid-phase washed bean cake. 0.025g of potassium carbonate was weighed and dissolved in deionized water, 5g of dried solid phase washed soybean cake residue was added and stirred under constant magnetic force at 70 ℃ until the two were thoroughly mixed. Placing the mixture in a tube furnace, and heating100% volume fraction CO2Gas is used as carrier gas and is introduced into the tube furnace, the tube furnace is heated to 700 ℃ from room temperature after stabilization, and the heat preservation time is 0.5 h; taking out the sample after natural cooling to obtain chain activated bean cake residue carbon, and measuring the specific surface area of the chain activated bean cake residue carbon to be 678 m2Nitrogen content 5.2 wt.%.
From the above results, it is found that in CO2Trace potassium carbonate is added in the pyrolysis atmosphere, the high-nitrogen biomass is effectively activated to prepare charcoal, and the specific surface area of the obtained activated charcoal is greatly improved.
Example 4
Weighing a certain mass of shrimp shell raw materials, mixing the shrimp shell raw materials with 0.5M hydrochloric acid, heating to 80 ℃, carrying out magnetic stirring and repeated acid washing, filtering, and then washing with distilled water until the filtrate is neutral to obtain solid-phase washed shrimp shell. 5g of dried solid-phase washed shrimp shell are placed in a tube furnace, and the volume fraction N of the dried shrimp shell is 100 percent2Gas is used as carrier gas and is introduced into the tube furnace, the tube furnace is heated to 750 ℃ from room temperature after stabilization, and the heat preservation time is 2 hours; and naturally cooling the sample, taking out to obtain the shell carbon of the shrimp ball, and measuring the specific capacitance of the shell carbon electrode of the shrimp ball to be 201.3F/g (current density = 1A/g) under the inert atmosphere by an electrochemical workstation. The specific surface area was found to be 401 m2Nitrogen content 8.2 wt.%.
From the above results, it was found that a carbon electrode material having excellent performance can be obtained by pyrolyzing a crustacean high-nitrogen biomass as a raw material in an inert atmosphere.
Example 5
Weighing a certain mass of shrimp shell raw materials, mixing the shrimp shell raw materials with 0.5M hydrochloric acid, heating to 80 ℃, carrying out magnetic stirring and repeated acid washing, filtering, and then washing with distilled water until the filtrate is neutral to obtain solid-phase washed shrimp shell. 5g of dried solid-phase washed shrimp shell are placed in a tube furnace, and 100 percent of CO by volume fraction is added2Gas is used as carrier gas and is introduced into the tube furnace, the tube furnace is heated to 750 ℃ from room temperature after stabilization, and the heat preservation time is 2 hours; and naturally cooling the sample, taking out to obtain the shell carbon of the shrimp ball, and measuring the specific capacitance of the shell carbon electrode of the shrimp ball to be 262.6F/g (current density = 1A/g) in an inert atmosphere by an electrochemical workstation. The specific surface area was measured to be 608 m2Nitrogen content 9.16 wt.%.
From the above-mentioned results, it was found that the crustacean high-nitrogen biomass was used as a raw material in the presence of CO2And (3) pyrolyzing the carbon material in the atmosphere, so that the electrochemical performance of the obtained carbon material is obviously improved compared with that of the carbon material prepared in the embodiment 4 in an inert atmosphere.
Example 6
Weighing a certain mass of shrimp shell raw materials, mixing the shrimp shell raw materials with 0.5M hydrochloric acid, heating to 80 ℃, carrying out magnetic stirring and repeated acid washing, filtering, and then washing with distilled water until the filtrate is neutral to obtain solid-phase washed shrimp shell. 0.0125g of sodium bicarbonate is weighed and dissolved in deionized water, 5g of dried solid-phase washed shrimp shell is added, and magnetic stirring is continuously carried out at 80 ℃ until the two are fully mixed. The mixture was placed in a tube furnace and 100% volume fraction CO was added2Gas is used as carrier gas and is introduced into the tube furnace, the tube furnace is heated to 750 ℃ from room temperature after stabilization, and the heat preservation time is 0.5 h; taking out the sample after natural cooling to obtain chain type activated shrimp shell carbon with specific surface area of 886 m2Nitrogen content 8.98 wt.%.
From the above-mentioned results, it was found that the crustacean high-nitrogen biomass was used as a raw material in the presence of CO2Trace sodium carbonate is added in the pyrolysis atmosphere, high-nitrogen biomass can be effectively activated to prepare charcoal effectively, and the physical and chemical properties of the obtained activated charcoal are greatly improved.
Example 7
Weighing a certain mass of bean curd residue raw material, mixing the bean curd residue raw material with 1M nitric acid, heating to 70 ℃, carrying out magnetic stirring and repeated acid washing, filtering, and then washing with distilled water until the filtrate is neutral to obtain solid-phase washed bean curd residue. Placing 5g of dried solid-phase washed bean curd residue sample in a tube furnace, and adding 100% volume fraction CO2Taking gas as carrier gas, introducing into the tube furnace, heating the tube furnace to 800 ℃ from room temperature after stabilization, and keeping the temperature for 2 h; taking out the sample after the sample is naturally cooled to prepare active bean curd residue carbon; the specific capacitance of the activated bean curd residue carbon measured at an electrochemical workstation was 118.3F/g (current density = 1A/g), the energy density was 3.5 Wh/kg at a power density of 62.5W/kg, and the capacitance retention rate was 96.7% after 30000 charge-discharge cycles. Measuring the specific surface areaIs 330 m2/g。
From the above-mentioned results, it was found that the carbon electrode obtained by using a high-nitrogen biomass such as soybean curd refuse as a raw material without loading it with a metal oxide had a low energy density although it was excellent in cycle characteristics.
Example 8
Weighing bean cake raw materials with certain mass, crushing, sieving and drying, taking 5g of sample, placing the sample in a tube furnace, and adding 100% volume fraction CO2Taking gas as carrier gas, introducing the gas into the tube furnace, heating the tube furnace to 700 ℃ from room temperature after stabilization, and keeping the temperature for 2 h; and taking out the sample after the sample is naturally cooled to prepare the active bean cake carbon, and marking as BPC-700. The specific capacitance of the active bean cake carbon electrode BPC-700 measured at an electrochemical workstation is 98.4F/g.
According to the detection results, the soybean cake residues are used as raw materials, do not undergo acid pickling pretreatment, and are subjected to low CO treatment2The electrochemical performance of the obtained carbon is poor at the atmosphere pyrolysis temperature without adding trace amount of activating agent.
Example 9
Weighing bean cake raw materials with certain mass, mixing the bean cake raw materials with 1M hydrochloric acid, heating to 80 ℃, carrying out magnetic stirring and repeated acid washing, filtering, and then washing with distilled water until the filtrate is neutral to obtain the washed bean cake. 5g of the washed bean cake residue was dried and the sample was placed in a tube furnace with 100% volume fraction CO2Taking gas as carrier gas, introducing into the tube furnace, heating the tube furnace to 900 ℃ from room temperature after stabilization, and keeping the temperature for 2 h; taking out the sample after natural cooling to obtain active bean cake carbon, and marking as BPC-900; the specific capacitance of the active bean cake carbon BPC-900 measured at the electrochemical workstation is 70.4F/g.
From the above-mentioned test results, it can be seen that the soybean cake dregs are used as the raw material, and the CO content is high2The atmosphere pyrolysis temperature, without the addition of trace amount of activating agent, the electrochemical performance of the obtained carbon is also poor.
Comparative example 1
Weighing bean cake residue raw materials with certain mass, mixing the bean cake residue raw materials with 2M hydrochloric acid, heating to 60 ℃, carrying out magnetic stirring and repeated acid washing, filtering, and then washing with distilled water until filtrate is neutral to obtain washed bean cake residue. 0.1g of carbon was weighedPotassium was dissolved in deionized water and 5g of dried washed soybean cake sample was added and stirred under constant magnetic force at 60 ℃ until the two were thoroughly mixed. Placing the mixture in a tube furnace, introducing 100% volume fraction Ar gas into the tube furnace as a carrier gas, heating the tube furnace to 700 ℃ from room temperature after stabilization, and keeping the temperature for 0.5 h; taking out the sample after natural cooling to obtain bean cake carbon with specific surface area of 73 m2Nitrogen content 3.6 wt.%.
From the above results, it can be seen that comparative example 1 is free of CO2Pyrolysis is carried out under the atmosphere, and only a trace of activating agent is added, so that the effect of implementation is limited.
Comparative example 2
Weighing a certain mass of bean curd residue raw material, crushing, sieving and drying, taking 5g of sample, placing the sample in a tube furnace, and adding 100% volume fraction CO2Taking gas as carrier gas, introducing into the tube furnace, heating the tube furnace to 800 ℃ from room temperature after stabilization, and keeping the temperature for 2 h; taking out the sample after the sample is naturally cooled, and measuring the specific surface area of the sample to be 242 m2/g。
From the above results, it can be seen that comparative example 2 uses only CO without trace amount of activator2Atmospheric pyrolysis has limited effectiveness.
Comparative example 3
Weighing 5g of spirulina raw material by mass, and uniformly mixing with 15g of sodium bicarbonate. The mixture was placed in a tube furnace and 100% volume fraction N was added2Taking gas as carrier gas, introducing into the tube furnace, heating the tube furnace to 800 ℃ from room temperature after stabilization, and keeping the temperature for 1 h; taking out the sample after natural cooling to obtain inert atmosphere spirulina carbon, and measuring the specific capacitance of the spirulina carbon at an electrochemical workstation to be 142.7F/g (current density = 1A/g) and the specific surface area to be 1511 m2Nitrogen content 1.9 wt.%.
From the above results, it can be seen that comparative example 3 is free of CO2Pyrolysis is carried out under atmosphere, and an activating agent with high proportion is used, so that although the activated charcoal with higher specific surface area can be obtained, the loss of nitrogen-containing functional groups on the surface is serious, and the electrochemical performance of the activated charcoal also needs to be improved.
The high-nitrogen biochar composite material is used as a supercapacitor electrode material and is used for preparing a supercapacitor electrode. The specific capacitance of the prepared electrode material of the supercapacitor is more than 150F/g, the energy density of the assembled button-type symmetrical supercapacitor is more than 4.5 Wh/kg, the capacitance retention rate is more than 90% after 10000 times of charge-discharge cycles, and the capacitance retention rate is still more than 84% after 30000 times of cycles. The high-nitrogen biomass carbon electrode prepared by the invention has the advantages that carbonization and activation are completed in one step, trace low-corrosivity alkali metal salt is added in a carbon-rich atmosphere to trigger a biochar chain type activation reaction, so that the continuous generation of biochar pores is realized, the reaction temperature of a system and the demand of an activating agent are greatly reduced, and compared with activated carbon prepared by physical activation and chemical activation in the prior art, the activated carbon prepared by physical activation and chemical activation has a three-dimensional nano multistage pore structure, the carbon surface contains more nitrogen functional groups, the activated carbon is more suitable for energy storage of a super capacitor, and the system process is simple, green and environment-friendly and is suitable for large-scale industrial.
Although the present invention has been described with reference to the above embodiments, it should be understood that the scope of the present invention is not limited thereto, and that various changes and modifications can be made by those skilled in the art without departing from the spirit and scope of the present invention.
Claims (10)
1. A preparation method of a high-nitrogen biochar composite material is characterized by comprising the following steps: the method comprises the following steps:
s1, mixing, washing and modulating high-nitrogen biomass serving as a carbon source and a nitrogen source with acid to obtain a solid product;
s2, placing the solid product obtained in the step S1 in pyrolysis equipment, introducing carbon-containing gas into the pyrolysis equipment to pyrolyze the solid product in a carbon-rich atmosphere, heating the equipment to a preset temperature from room temperature, treating for a period of time, and cooling to room temperature to realize one-step carbonization and activation of the high-nitrogen biomass and prepare the nitrogen self-doped active charcoal;
s3, coating metal oxide on the nitrogen self-doped active biochar to obtain the high-nitrogen biochar composite material.
2. The method for preparing the high-nitrogen biochar composite material as claimed in claim 1, wherein the method comprises the following steps: in the step S1, the nitrogen content of the high-nitrogen biomass is not less than 4 wt.%, and the high-nitrogen biomass comprises one or more of bean cake dregs, bean curd dregs, shrimp shells, crab shells and algae.
3. The method for preparing the high-nitrogen biochar composite material as claimed in claim 2, wherein the method comprises the following steps: the mixing, washing and preparing in step S1 specifically includes the following steps: mixing the high-nitrogen biomass with acid with a certain concentration, heating to a certain temperature, carrying out magnetic stirring and repeated acid washing, then washing with distilled water until filtrate is neutral to obtain solid-phase washed biomass, wherein the concentration of the acid is 0.5-2M, the temperature is 60-80 ℃, and the acid is HCl or HNO3、H2SO4、H3PO4、CH3One or more combinations of COOH.
4. The method for preparing the high-nitrogen biochar composite material as claimed in claim 3, wherein the method comprises the following steps: the mixed washing preparation in step S1 further includes the steps of: and uniformly mixing the solid-phase washing biomass with a trace amount of activator to prepare a trace amount of activator biomass blend, wherein the trace amount of activator is low-corrosivity alkali metal salt.
5. The method for preparing the high-nitrogen biochar composite material as claimed in claim 4, wherein the method comprises the following steps: the solid product placed into the pyrolysis device in step S2 is either solid phase washed biomass or a trace activator biomass blend.
6. The method for preparing the high-nitrogen biochar composite material as claimed in claim 4, wherein the method comprises the following steps: the low-corrosiveness alkali metal salt is Li2CO3、Na2CO3、NaHCO3、K2CO3、KHCO3、Rb2CO3、Cs2CO3One or more combinations thereof.
7. As claimed inThe preparation method of the high-nitrogen biochar composite material is characterized by comprising the following steps of: the carbon-containing gas is CO in step S22、CH3One or more combinations in COOH, and the volume concentration of the carbon-containing gas is 20-100%.
8. The method for preparing the high-nitrogen biochar composite material as claimed in claim 7, wherein the method comprises the following steps: in the step S3, the metal oxide is transition metal salt, the transition metal salt is deposited and coated on the surface of the nitrogen self-doping activated charcoal in the form of metal oxide through redox reaction of a liquid phase system, and the transition metal salt is TiCl4、KMnO4、Mn(NO3)2、FeCl3、Fe2(SO4)3、CoCl3、CuSO4One of (1); the concentration of the transition metal salt is 1-50 mmol/L, and the mass ratio of the nitrogen self-doped active biochar to the transition metal salt is 1: (0.5-2).
9. A high nitrogen biochar composite prepared by the preparation method according to any one of claims 1 to 8, characterized in that: the high-nitrogen biochar composite material has a three-dimensional nano multi-level pore channel structure, the microporosity is not less than 70%, the mesoporosity is not less than 10%, the macroporosity is not less than 5%, the thickness of a metal oxide is 10-50 nm, and the structure is in a half-microsphere convex shape.
10. Use of a high nitrogen biochar composite prepared by the preparation method according to any one of claims 1 to 8, characterized in that: the high-nitrogen biochar composite material is used for preparing electrodes of super capacitors or ion batteries.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040218A (en) * | 2011-01-19 | 2011-05-04 | 成都信息工程学院 | New method for producing active carbon by using biomass wastes |
| CN104386685A (en) * | 2014-10-22 | 2015-03-04 | 北京化工大学 | Method for preparing nitrogen-doped active carbon from nitrogen-enriched biomass raw material |
| CN105236407A (en) * | 2015-09-14 | 2016-01-13 | 中国东方电气集团有限公司 | Double-layer capacitor electrode spherical active carbon material preparation method |
| CN106698425A (en) * | 2017-02-06 | 2017-05-24 | 武汉理工大学 | Preparation method of CO2-adsorbing shrimp-shell-base nitrogenous activated carbon |
| CN110723735A (en) * | 2018-07-16 | 2020-01-24 | 深圳市环球绿地新材料有限公司 | Spherical super-capacity carbon, preparation method and application thereof |
| CN111137889A (en) * | 2020-01-09 | 2020-05-12 | 中国烟草总公司四川省公司 | Tobacco matrix activated carbon and preparation method thereof |
| CN111180214A (en) * | 2018-11-13 | 2020-05-19 | 北京化工大学 | Bamboo-based porous carbon/manganese dioxide nano composite electrode material for supercapacitor and preparation method thereof |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106978206A (en) * | 2017-03-29 | 2017-07-25 | 昆明理工大学 | A kind of microwave catalysis is pyrolyzed Eupatorium adenophorum production method |
| CN107151016A (en) * | 2017-06-28 | 2017-09-12 | 宿州市逢源生物科技有限公司 | A kind of preparation method that straw biomass charcoal is prepared under carbon dioxide atmosphere |
| CN109589979A (en) * | 2017-09-30 | 2019-04-09 | 黑龙江大学 | A kind of metal oxide/carbon material compound and its preparation method and application |
| KR102142684B1 (en) * | 2018-10-31 | 2020-08-10 | 한국철도기술연구원 | Directly heated microwave thermal desorption and disassembly facility, and method for manufacturing low carbon and eco-friendly material from waste wood using directly heated microwave thermal desorption and disassembly facility |
| CN109609151B (en) * | 2018-11-28 | 2021-01-05 | 大连理工大学 | Device and method for preparing ordered mesoporous carbon-metal composite material from solid waste biomass |
-
2020
- 2020-08-20 CN CN202010840785.9A patent/CN112174136B/en active Active
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Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102040218A (en) * | 2011-01-19 | 2011-05-04 | 成都信息工程学院 | New method for producing active carbon by using biomass wastes |
| CN104386685A (en) * | 2014-10-22 | 2015-03-04 | 北京化工大学 | Method for preparing nitrogen-doped active carbon from nitrogen-enriched biomass raw material |
| CN105236407A (en) * | 2015-09-14 | 2016-01-13 | 中国东方电气集团有限公司 | Double-layer capacitor electrode spherical active carbon material preparation method |
| CN106698425A (en) * | 2017-02-06 | 2017-05-24 | 武汉理工大学 | Preparation method of CO2-adsorbing shrimp-shell-base nitrogenous activated carbon |
| CN110723735A (en) * | 2018-07-16 | 2020-01-24 | 深圳市环球绿地新材料有限公司 | Spherical super-capacity carbon, preparation method and application thereof |
| CN111180214A (en) * | 2018-11-13 | 2020-05-19 | 北京化工大学 | Bamboo-based porous carbon/manganese dioxide nano composite electrode material for supercapacitor and preparation method thereof |
| CN111137889A (en) * | 2020-01-09 | 2020-05-12 | 中国烟草总公司四川省公司 | Tobacco matrix activated carbon and preparation method thereof |
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| CN113200545A (en) * | 2021-04-30 | 2021-08-03 | 中国科学院山西煤炭化学研究所 | Capacitance carbon and preparation method thereof |
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| CN115285991B (en) * | 2022-07-06 | 2023-11-28 | 浙江大学 | Method for generating hierarchical porous carbon based on biomass derivative self-assembly and application thereof |
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| CN112174136B (en) | 2022-12-02 |
| WO2022036878A1 (en) | 2022-02-24 |
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