CN110853939A - Based on biological charcoal cladding [ Zn ]4O(BDBC)3]8Super capacitor material and its making method - Google Patents

Based on biological charcoal cladding [ Zn ]4O(BDBC)3]8Super capacitor material and its making method Download PDF

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CN110853939A
CN110853939A CN201911017868.1A CN201911017868A CN110853939A CN 110853939 A CN110853939 A CN 110853939A CN 201911017868 A CN201911017868 A CN 201911017868A CN 110853939 A CN110853939 A CN 110853939A
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biochar
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李建龙
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13—Energy storage using capacitors

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  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention relates to the technical field of super capacitor materials and discloses a coating [ Zn ] based on biochar4O(BDBC)3]8The super capacitor material and the preparation method thereof comprise the following formula raw materials: biological straw, biphenyl-4, 4' -dicarboxylic acid and zinc iodide. The coating is based on biochar [ Zn ]4O(BDBC)3]8The super capacitor material and the preparation method thereof, the metal organic framework [ Zn ]4O(BDBC)3]8The internal resistance of the capacitor is small, the capacitor has good conductivity, the resistance of metal ions and charges migrating through electrode materials is reduced, and the specific capacitance and energy of the capacitor are improvedDensity, biochar has huge specific surface area and porosity, surface possesses a large number of highly aromatized oxygen-containing groups, and [ Zn4O(BDBC)3]8The active hydroxyl groups on the surface form hydrogen bonds to enable [ Zn4O(BDBC)3]8Uniformly dispersed and tightly adhered in the pores of the biochar, and increased [ Zn ]4O(BDBC)3]8The contact area with the electrolyte enables a large amount of metal ions and charges to be diffused and transferred between the electrode material and the electrolyte, and the power density and the energy density of the super capacitor are enhanced.

Description

Based on biological charcoal cladding [ Zn ]4O(BDBC)3]8Super capacitor material and its making method
Technical Field
The invention relates to the technical field of sodium ion anode materials, in particular to a coating [ Zn ] based on biochar4O(BDBC)3]8The super capacitor material and the preparation method thereof.
Background
With the increasing exhaustion of fossil fuels and the increasing environmental problems caused by combustion, people are researching and developing new energy devices for replacing internal combustion engines, such as hybrid power, chemical batteries, fuel cells and other products, but these new battery materials have the obvious disadvantages of short service life, poor temperature-sensitive characteristics, high manufacturing cost, environmental pollution of chemical batteries and the like, and the practical application of the new battery materials is hindered.
The super capacitor is a novel energy storage device between a traditional capacitor and a rechargeable battery, has the characteristics of rapid charge and discharge of the capacitor and the energy storage characteristic of the battery, has the characteristics of short charge and discharge time, high energy density, long service life, good temperature-sensitive characteristic, energy conservation, environmental protection and the like, can partially or completely replace the traditional chemical battery to be used as a traction power supply and a starting energy source of a vehicle, and has wider application compared with the traditional chemical battery.
However, the currently developed super capacitor, such as the transition metal oxide and the high molecular polymer faradaic capacitance active electrode material, has a high redox potential and a poor rate capability, and reduces the storage and conversion efficiency of the capacitor to energy.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the [ Zn ] based biochar coating with lower oxidation-reduction potential, higher power density and excellent rate capability4O(BDBC)3]8The super capacitor material and the preparation method thereof solve the problems of poor cycle stability of the super capacitor material caused by low energy density and unstable chemical performance of the metal organic framework material.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: based on biological charcoal cladding [ Zn ]4O(BDBC)3]8Super power ofThe container material and the preparation method thereof comprise the following formula raw materials in parts by weight: 30-35 parts of biological straw, 5-8 parts of biphenyl-4, 4' -dicarboxylic acid and 57-65 parts of zinc iodide, and the preparation method comprises the following experimental medicines: ultra pure waterN-methylpyrrolidone, N2Distilled water, dilute sulfuric acid, absolute ethyl alcohol, dilute hydrochloric acid and sodium hydroxide.
Preferably, the biological straw is any one of recycled rice straw, wheat straw or sugarcane straw.
Preferably, the chemical analysis pure mass fraction of the biphenyl-4, 4' -dicarboxylic acid is more than or equal to 98%.
Preferably, the zinc iodide is chemically pure, wherein the mass fraction of ZnI is more than or equal to 98.5%.
Preferably, the ultrapure waterN-methylpyrrolidone, N2Distilled water, absolute ethyl alcohol and sodium hydroxide are all chemically pure and ultrapureNThe mass fraction of the-methyl pyrrolidone is more than or equal to 99.5 percent, and the water content is less than or equal to 0.010 percent.
Preferably, the dilute sulfuric acid H2SO4The mass fraction is 50-65%, and the mass concentration of the substance is 7.1-10.3 mol/L.
Preferably, the mass fraction of the dilute hydrochloric acid is 10-15%, and the mass concentration of the dilute hydrochloric acid is 2.8-4.4 mol/L.
Preferably, the coating is based on biochar [ Zn ]4O(BDBC)3]8The preparation method of the super capacitor material comprises the following steps: (1) hydrothermal method for preparing metal organic framework [ Zn ]4O(BDBC)3]8: adding 600-800 mL into 2000 mL three-neck bottleN-methylpyrrolidone, N being fed in2The air in the three-neck bottle is dischargedNAdding 5-8 parts of biphenyl-4, 4' -dicarboxylic acid and 57-65 parts of zinc iodide into the methyl pyrrolidone in sequence, placing the three-necked flask into a constant temperature water bath kettle, heating to 85-90 ℃, carrying out uniform stirring reaction for 6-8 h, transferring the materials in the three-necked flask into a hydrothermal synthesis automatic reaction kettle, setting the temperature to be 140-150 ℃, carrying out magnetic stirring reaction for 12-15 h, cooling the reaction kettle to room temperature after the reaction is finished, carrying out suction filtration on the reaction materials through a non-funnel to remove the solvent to obtain a solid mixture, and sequentially using 5000-8000 mL of distilled water and 500-700-plus-oneWashing the solid mixture with mL of absolute ethanol to remove residuesN-methyl pyrrolidone and reaction by-products, putting the washed solid product into an oven, heating to 90-95 ℃, and drying for 5-6 h to obtain light yellow crystal metal organic framework [ Zn ]4O(BDBC)3]8。
(2) In-situ method for preparing biochar coated [ Zn ]4O(BDBC)3]8The supercapacitor material of (a): weighing 30-35 parts of biological straws, adding the biological straws into a ball mill, carrying out ball milling for 10-15H, adding 500-800 mL of dilute sulfuric acid H with the mass fraction of 50-65% into a 2000 mL reaction bottle2SO4Slowly adding ball-milled biological straws and 20-30 g of phosphoric acid, placing a reaction bottle in a constant-temperature water bath kettle, heating to 55-60 ℃, uniformly stirring for 5-8 h to perform a biological straw dehydration carbonization process, filtering the materials in the reaction bottle to remove a solid mixture, obtaining a filtrate containing glucose molecules and other organic small molecules formed by hydrolysis of straw cellulose, slowly adding sodium hydroxide into the filtrate until the filtrate is neutral and has a pH value of 7, adding the filtrate into a hydrothermal synthesis automatic reaction kettle, and adding the metal organic framework [ Zn ] prepared in the step (1)4O(BDBC)3]8Setting the temperature of a hydrothermal synthesis automatic reaction kettle to 70-75 ℃, carrying out small molecule prepolymerization reaction by magnetic stirring, increasing the temperature of the reaction kettle to 120-4O(BDBC)3]8The supercapacitor material of (1).
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
1. the coating is based on biochar [ Zn ]4O(BDBC)3]8By using a metal organic framework [ Zn ] and a method for manufacturing the same4O(BDBC)3]8As a substrate of a supercapacitor, [ Zn ]4O(BDBC)3]8Has a cubic octahedral structure, and [ Zn ]4O(BDBC)3]8The internal resistance of the capacitor is low, the capacitor has good conductivity and conductivity, the resistance of metal ions and charges in the electrolyte to migrate through the electrode material is reduced, the diffusion and migration of the metal ions and the charges between the electrode material and the electrolyte are promoted, and the specific capacitance and the energy density of the capacitor are improved.
2. The coating is based on biochar [ Zn ]4O(BDBC)3]8The super capacitor material and the preparation method thereof use the biochar prepared by recycling straws through a hydrothermal carbonization method, cater to the concept of green chemistry and sustainable development, the biochar has huge specific surface area and porosity, the surface has a large amount of highly aromatized oxygen-containing groups and has excellent conductivity, and the metal organic framework [ Zn ] synthesized by the high-temperature hydrothermal method4O(BDBC)3]8The surface of the biological carbon is provided with a large number of active hydroxyl groups which form hydrogen bonds with oxygen-containing groups aromatized on the surface of the biological carbon, and the biological carbon is coated with [ Zn ]4O(BDBC)3]8To cause [ Zn ] to4O(BDBC)3]8Uniformly dispersed and tightly adhered in the pores of the biochar through hydrogen bonds, increasing [ Zn ]4O(BDBC)3]8The contact area with the electrolyte enables a large amount of metal ions and charges to be diffused and transferred between the electrode material and the electrolyte, the power density and the energy density of the super capacitor are enhanced, and the biochar is coated [ Zn ]4O(BDBC)3]8The structure stability is better, the multiplying power performance of the super capacitor and the electrochemical stability of the matrix are improved, and the practicability and the service life of the super capacitor are effectively improved.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: based on biological charcoal cladding [ Zn ]4O(BDBC)3]8The super capacitor material comprises the following raw materials in parts by weight: 30-35 parts of biological straw,5-8 parts of biphenyl-4, 4' -dicarboxylic acid and 57-65 parts of zinc iodide, and the preparation method comprises the following experimental medicines: ultra pure waterN-methylpyrrolidone, N2Distilled water, dilute sulfuric acid, absolute ethyl alcohol, dilute hydrochloric acid and sodium hydroxide, wherein the biological straw is any one of recycled rice straw, wheat straw or sugarcane straw, the biphenyl-4, 4' -dicarboxylic acid is chemical analysis purity with the mass fraction of more than or equal to 98%, the zinc iodide is chemical analysis purity, the ZnI mass fraction is more than or equal to 98.5%, and the ultrapure water isN-methylpyrrolidone, N2Distilled water, absolute ethyl alcohol and sodium hydroxide are all chemically pure and ultrapureNThe mass fraction of the-methyl pyrrolidone is more than or equal to 99.5 percent, the water content is less than or equal to 0.010 percent, and the dilute sulphuric acid H2SO4The mass fraction is 50-65%, the mass concentration of the substance is 7.1-10.3 mol/L, the mass fraction of the dilute hydrochloric acid is 10-15%, and the mass concentration of the substance is 2.8-4.4 mol/L.
Based on biological charcoal cladding [ Zn ]4O(BDBC)3]8The preparation method of the super capacitor material comprises the following steps: (1) hydrothermal method for preparing metal organic framework [ Zn ]4O(BDBC)3]8: adding 600-800 mL into 2000 mL three-neck bottleN-methylpyrrolidone, N being fed in2The air in the three-neck bottle is dischargedNAdding 5-8 parts of biphenyl-4, 4' -dicarboxylic acid and 57-65 parts of zinc iodide into the methyl pyrrolidone in sequence, placing the three-neck flask into a constant-temperature water bath kettle, heating to 85-90 ℃, uniformly stirring for reaction for 6-8 h, transferring the materials in the three-neck flask into a hydrothermal synthesis automatic reaction kettle, setting the temperature to be 140-150 ℃, magnetically stirring for reaction for 12-15 h, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent from the reaction materials through a non-funnel suction filtration to obtain a solid mixture, washing the solid mixture by using 8000 mL of distilled water and 700mL of anhydrous ethanol in sequence to remove the residualN-methyl pyrrolidone and reaction by-products, putting the washed solid product into an oven, heating to 90-95 ℃, and drying for 5-6 h to obtain light yellow crystal metal organic framework [ Zn ]4O(BDBC)3]8。
(2) In-situ method for preparing biochar coated [ Zn ]4O(BDBC)3]8The supercapacitor material of (a): weighing 30-35 parts of organismsAdding the straws into a ball mill, ball-milling for 10-15H, adding 500 plus 800mL of dilute sulfuric acid H with the mass fraction of 50-65% into a 2000 mL reaction bottle2SO4Slowly adding ball-milled biological straws and 20-30 g of phosphoric acid, placing a reaction bottle in a constant-temperature water bath kettle, heating to 55-60 ℃, uniformly stirring for 5-8 h to perform a biological straw dehydration carbonization process, filtering the materials in the reaction bottle to remove a solid mixture, obtaining a filtrate containing glucose molecules and other organic small molecules formed by hydrolysis of straw cellulose, slowly adding sodium hydroxide into the filtrate until the filtrate is neutral and has a pH value of 7, adding the filtrate into a hydrothermal synthesis automatic reaction kettle, and adding the metal organic framework [ Zn ] prepared in the step (1)4O(BDBC)3]8Setting the temperature of a hydrothermal synthesis automatic reaction kettle to 70-75 ℃, carrying out small molecule prepolymerization reaction by magnetic stirring, increasing the temperature of the reaction kettle to 120-4O(BDBC)3]8The supercapacitor material of (1).
Example 1:
(1) hydrothermal method for preparing metal organic framework [ Zn ]4O(BDBC)3]8: 600mL of the solution was added to a 2000 mL three-necked flaskN-methylpyrrolidone, N being fed in2The air in the three-neck bottle is dischargedN-dissolved oxygen in methyl pyrrolidone, then adding 5 parts of biphenyl-4, 4' -dicarboxylic acid and 65 parts of zinc iodide in sequence, placing a three-necked bottle in a constant-temperature water bath kettle to be heated to 85 ℃, stirring at a constant speed for reaction for 6 hours, then transferring the materials in the three-necked bottle into a hydrothermal synthesis automatic reaction kettle, setting the temperature to be 140 ℃, stirring magnetically for reaction for 12 hours, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent from the reaction materials through suction filtration without a funnel to obtain a solid mixture, washing the solid mixture by using 5000 mL of distilled water and 500 mL of anhydrous ethanol in sequence to remove residualN-methyl pyrrolidone and reactionA byproduct, namely putting the washed solid product into an oven to be heated to 95 ℃ and dried for 5 h to obtain a light yellow crystal metal organic framework [ Zn ]4O(BDBC)3]8And (3) component 1.
(2) In-situ method for preparing biochar coated [ Zn ]4O(BDBC)3]8The supercapacitor material of (a): weighing 30 parts of biological straws, adding the biological straws into a ball mill, carrying out ball milling for 10 hours, and adding 500 mL of dilute sulfuric acid H with the mass fraction of 50% into a 2000 mL reaction bottle2SO4Slowly adding ball-milled biological straws and 20 g of phosphoric acid, placing a reaction bottle in a constant-temperature water bath kettle, heating to 55 ℃, uniformly stirring for 5 hours to perform a biological straw dehydration carbonization process, filtering the materials in the reaction bottle to remove a solid mixture, obtaining a filtrate containing glucose molecules and other organic micromolecules formed by hydrolysis of straw cellulose, slowly adding sodium hydroxide into the filtrate until the filtrate is neutral and has a pH value of 7, adding the filtrate into a hydrothermal synthesis automatic reaction kettle, and adding the metal organic framework [ Zn ] prepared in the step (1)4O(BDBC)3]8Setting the temperature of a hydrothermal synthesis automatic reaction kettle to be 75 ℃, carrying out small molecule prepolymerization reaction by magnetic stirring, heating the reaction kettle to 130 ℃ after 8 hours of reaction, carrying out carbonization reaction for 12 hours, cooling the reaction kettle to room temperature after the reaction is finished, removing liquid from the materials by a Buchner funnel to obtain a solid mixture, washing the solid mixture by sequentially using 800mL of absolute ethyl alcohol and 4000 mL of distilled water, placing the solid mixture in an oven, heating the solid mixture to 95 ℃, and drying the solid mixture for 6 hours to obtain the [ Zn ] based on biochar coating4O(BDBC)3]8The supercapacitor material 1 of (1).
Example 2:
(1) hydrothermal method for preparing metal organic framework [ Zn ]4O(BDBC)3]8: 600mL of the solution was added to a 2000 mL three-necked flaskN-methylpyrrolidone, N being fed in2The air in the three-neck bottle is dischargedNAdding 6 parts of biphenyl-4, 4' -dicarboxylic acid and 63 parts of zinc iodide into the methyl pyrrolidone in sequence, placing the three-necked flask into a constant-temperature water bath kettle, heating to 85 ℃, stirring at a constant speed for reaction for 6 hours, and transferring the materials in the three-necked flask into a hydrothermal synthesis reactorSetting the temperature in a dynamic reaction kettle at 140 ℃, magnetically stirring for reaction for 12 hours, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent from the reaction materials through suction filtration without a funnel to obtain a solid mixture, and washing the solid mixture by using 5000 mL of distilled water and 500 mL of absolute ethyl alcohol in sequence to remove residualN-methyl pyrrolidone and reaction by-products, putting the washed solid product into an oven, heating to 90 ℃ and drying for 5 h to obtain a light yellow crystal metal organic framework [ Zn ]4O(BDBC)3]8And (3) component 2.
(2) In-situ method for preparing biochar coated [ Zn ]4O(BDBC)3]8The supercapacitor material of (a): weighing 31 parts of biological straw, adding the biological straw into a ball mill, carrying out ball milling for 10 hours, adding 500 mL of dilute sulfuric acid H with the mass fraction of 50% into a 2000 mL reaction bottle2SO4Slowly adding ball-milled biological straws and 25 g of phosphoric acid, placing a reaction bottle in a constant-temperature water bath kettle, heating to 55 ℃, uniformly stirring for 5 hours to perform a biological straw dehydration carbonization process, filtering the materials in the reaction bottle to remove a solid mixture, obtaining a filtrate containing glucose molecules and other organic micromolecules formed by hydrolysis of straw cellulose, slowly adding sodium hydroxide into the filtrate until the filtrate is neutral and has a pH value of 7, adding the filtrate into a hydrothermal synthesis automatic reaction kettle, and adding the metal organic framework [ Zn ] prepared in the step (1)4O(BDBC)3]8And (2) setting the temperature of a hydrothermal synthesis automatic reaction kettle to 70 ℃, carrying out small molecule prepolymerization reaction by magnetic stirring, heating the reaction kettle to 120 ℃ after 6 hours of reaction, carrying out carbonization reaction for 10 hours, cooling the reaction kettle to room temperature after the reaction is finished, removing liquid from the materials by a Buchner funnel to obtain a solid mixture, sequentially washing the solid mixture by 600mL of absolute ethyl alcohol and 5000 mL of distilled water, placing the solid mixture in an oven, heating the solid mixture to 90 ℃, and drying the water for 8 hours to obtain the [ Zn ] based on the biochar coating4O(BDBC)3]8The supercapacitor material 2.
Example 3:
(1) hydrothermal method for preparing metal organic framework [ Zn ]4O(BDBC)3]8: to a 2000 mL three-necked flask was added 70 mLN-methylpyrrolidone, N being fed in2The air in the three-neck bottle is dischargedNAdding 7 parts of biphenyl-4, 4' -dicarboxylic acid and 61 parts of zinc iodide into methyl pyrrolidone in sequence, placing a three-necked bottle into a constant-temperature water bath kettle, heating to 85 ℃, stirring at a constant speed for reaction for 7 hours, transferring the materials in the three-necked bottle into a hydrothermal synthesis automatic reaction kettle, setting the temperature to 145 ℃, stirring magnetically for reaction for 14 hours, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent from the reaction materials through suction filtration without a funnel to obtain a solid mixture, washing the solid mixture by using 6000 mL of distilled water and 600mL of absolute ethyl alcohol in sequence to remove residualN-methyl pyrrolidone and reaction by-products, putting the washed solid product into an oven, heating to 90 ℃ and drying for 6h to obtain a light yellow crystal metal organic framework [ Zn ]4O(BDBC)3]8And (3) component.
(2) In-situ method for preparing biochar coated [ Zn ]4O(BDBC)3]8The supercapacitor material of (a): weighing 32 parts of biological straws, adding the biological straws into a ball mill, carrying out ball milling for 12 hours, adding 600mL of dilute sulfuric acid H with the mass fraction of 65% into a 2000 mL reaction bottle2SO4Slowly adding ball-milled biological straws and 25 g of phosphoric acid, placing a reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for 7 hours to perform a biological straw dehydration carbonization process, filtering the materials in the reaction bottle to remove a solid mixture, obtaining a filtrate containing glucose molecules and other organic micromolecules formed by hydrolysis of straw cellulose, slowly adding sodium hydroxide into the filtrate until the filtrate is neutral and has a pH value of 7, adding the filtrate into a hydrothermal synthesis automatic reaction kettle, and adding the metal organic framework [ Zn ] prepared in the step (1)4O(BDBC)3]8And (3) setting the temperature of a hydrothermal synthesis automatic reaction kettle to be 75 ℃, carrying out small molecule prepolymerization reaction by magnetic stirring, heating the temperature of the reaction kettle to 120 ℃ after 6 hours of reaction, carrying out carbonization reaction for 10 hours, cooling the reaction kettle to room temperature after the reaction is finished, removing liquid from the materials by a Buchner funnel to obtain a solid mixture, sequentially washing the solid mixture by using 700mL of absolute ethyl alcohol and 4000 mL of distilled water, placing the solid mixture in an oven, heating the solid mixture to 90 ℃, and drying the water for 8 hours to obtain the compoundTo based on biocarbon coating [ Zn ]4O(BDBC)3]8The supercapacitor material 3.
Example 4:
(1) hydrothermal method for preparing metal organic framework [ Zn ]4O(BDBC)3]8: 700mL was added to a 2000 mL three-necked flaskN-methylpyrrolidone, N being fed in2The air in the three-neck bottle is dischargedNAdding 7 parts of biphenyl-4, 4' -dicarboxylic acid and 59 parts of zinc iodide into methyl pyrrolidone in sequence, placing a three-necked bottle into a constant-temperature water bath kettle, heating to 90 ℃, stirring at a constant speed for reaction for 7 hours, transferring the materials in the three-necked bottle into a hydrothermal synthesis automatic reaction kettle, setting the temperature to 145 ℃, stirring magnetically for reaction for 14 hours, cooling the reaction kettle to room temperature after the reaction is finished, removing the solvent from the reaction materials through suction filtration without a funnel to obtain a solid mixture, washing the solid mixture by using 7000 mL of distilled water and 600mL of absolute ethyl alcohol in sequence to remove residualN-methyl pyrrolidone and reaction byproducts, and placing the washed solid product in an oven to be heated to 95 ℃ and dried for 6 hours to obtain a light yellow crystal metal organic framework [ Zn ]4O(BDBC)3]8And (4) component.
(2) In-situ method for preparing biochar coated [ Zn ]4O(BDBC)3]8The supercapacitor material of (a): weighing 34 parts of biological straw, adding the biological straw into a ball mill, carrying out ball milling for 15H, adding 600mL of dilute sulfuric acid H with the mass fraction of 65% into a 2000 mL reaction bottle2SO4Slowly adding ball-milled biological straws and 30 g of phosphoric acid, placing a reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for 8 hours to perform a biological straw dehydration carbonization process, filtering the materials in the reaction bottle to remove a solid mixture, obtaining a filtrate containing glucose molecules and other organic micromolecules formed by hydrolysis of straw cellulose, slowly adding sodium hydroxide into the filtrate until the filtrate is neutral and has a pH value of 7, adding the filtrate into a hydrothermal synthesis automatic reaction kettle, and adding the metal organic framework [ Zn ] prepared in the step (1)4O(BDBC)3]8Component 4, setting the temperature of the hydrothermal synthesis automatic reaction kettle to be 75 ℃, and carrying out micromolecule prepolymerization by magnetic stirringReacting for 7 hours, raising the temperature of the reaction kettle to 125 ℃, carrying out carbonization reaction for 12 hours, cooling the reaction kettle to room temperature after the reaction is finished, removing liquid from the materials through a Buchner funnel to obtain a solid mixture, washing the solid mixture with 700mL of absolute ethyl alcohol and 5000 mL of distilled water in sequence, placing the solid mixture in an oven, heating the solid mixture to 95 ℃, and drying the solid mixture for 9 hours to obtain the product based on biochar coating [ Zn ] coating4O(BDBC)3]8The supercapacitor material 4.
Example 5:
(1) hydrothermal method for preparing metal organic framework [ Zn ]4O(BDBC)3]8: to a 2000 mL three-necked flask, 800mL was addedN-methylpyrrolidone, N being fed in2The air in the three-neck bottle is dischargedNAdding 8 parts of biphenyl-4, 4' -dicarboxylic acid and 57 parts of zinc iodide into methylpyrrolidone in sequence, placing a three-necked bottle into a constant-temperature water bath kettle, heating to 90 ℃, stirring at a constant speed for 8 hours of reaction, transferring the materials in the three-necked bottle into a hydrothermal synthesis automatic reaction kettle, setting the temperature to 150 ℃, magnetically stirring for 15 hours of reaction, cooling the reaction kettle to room temperature after the reaction is finished, filtering the reaction materials through a funnel to remove the solvent to obtain a solid mixture, washing the solid mixture by using 8000 mL of distilled water and 700mL of absolute ethyl alcohol in sequence to remove residualN-methyl pyrrolidone and reaction byproducts, and placing the washed solid product in an oven to be heated to 95 ℃ and dried for 6 hours to obtain a light yellow crystal metal organic framework [ Zn ]4O(BDBC)3]8And (5) component.
(2) In-situ method for preparing biochar coated [ Zn ]4O(BDBC)3]8The supercapacitor material of (a): weighing 35 parts of biological straws, adding the biological straws into a ball mill, carrying out ball milling for 15H, adding 800mL of 65 mass percent dilute sulfuric acid H into a 2000 mL reaction bottle2SO4Slowly adding ball-milled biological straws and 30 g of phosphoric acid, placing the reaction bottle in a constant-temperature water bath kettle, heating to 60 ℃, uniformly stirring for 8 hours to perform a biological straw dehydration carbonization process, filtering the materials in the reaction bottle to remove a solid mixture, obtaining a filtrate containing glucose molecules and other organic micromolecules formed by hydrolysis of straw cellulose, and adding the filtrate into the filtrateSlowly adding sodium hydroxide until the pH value of the filtrate is 7, adding the filtrate into a hydrothermal synthesis automatic reaction kettle, and adding the metal organic framework [ Zn ] prepared in the step (1)4O(BDBC)3]8And (5) setting the temperature of a hydrothermal synthesis automatic reaction kettle to be 75 ℃, carrying out small molecule prepolymerization reaction by magnetic stirring, raising the temperature of the reaction kettle to 130 ℃ after 8 hours of reaction, carrying out carbonization reaction for 12 hours, cooling the reaction kettle to room temperature after the reaction is finished, removing liquid from the materials by a Buchner funnel to obtain a solid mixture, sequentially washing the solid mixture by using 800mL of absolute ethyl alcohol and 6000 mL of distilled water, placing the solid mixture in an oven, heating the solid mixture to 95 ℃, and drying the solid mixture for 9 hours to obtain the product based on the biochar coating [ Zn ] coating4O(BDBC)3]8The supercapacitor material 5.
The samples of examples 1-5 were tested for power density, rate capability and electrochemical cycling stability, one based on biochar coating [ Zn ]4O(BDBC)3]8By using a metal organic framework [ Zn ] and a method for manufacturing the same4O(BDBC)3]8As a substrate of a supercapacitor, [ Zn ]4O(BDBC)3]8Has a cubic octahedral structure, and [ Zn ]4O(BDBC)3]8The internal resistance of the capacitor is low, the capacitor has good conductivity and conductivity, the resistance of metal ions and charges in the electrolyte to migrate through the electrode material is reduced, the diffusion and migration of the metal ions and the charges between the electrode material and the electrolyte are promoted, and the specific capacitance and the energy density of the capacitor are improved.
The coating is based on biochar [ Zn ]4O(BDBC)3]8The super capacitor material and the preparation method thereof use the biochar prepared by recycling straws through a hydrothermal carbonization method, cater to the concept of green chemistry and sustainable development, the biochar has huge specific surface area and porosity, the surface has a large amount of highly aromatized oxygen-containing groups and has excellent conductivity, and the metal organic framework [ Zn ] synthesized by the high-temperature hydrothermal method4O(BDBC)3]8The surface has a large amount of active hydroxyl groups and is aromatized with the surface of the biocharThe oxidized oxygen-containing groups form hydrogen bonds and are coated by biochar [ Zn ]4O(BDBC)3]8To cause [ Zn ] to4O(BDBC)3]8Uniformly dispersed and tightly adhered in the pores of the biochar through hydrogen bonds, increasing [ Zn ]4O(BDBC)3]8The contact area with the electrolyte enables a large amount of metal ions and charges to be diffused and transferred between the electrode material and the electrolyte, the power density and the energy density of the super capacitor are enhanced, and the biochar is coated [ Zn ]4O(BDBC)3]8The structure stability is better, the multiplying power performance of the super capacitor and the electrochemical stability of the matrix are improved, and the practicability and the service life of the super capacitor are effectively improved.

Claims (8)

1. Based on biological charcoal cladding [ Zn ]4O(BDBC)3]8The super capacitor material and the preparation method thereof comprise the following formula raw materials in parts by weight, and are characterized in that: 30-35 parts of biological straw, 5-8 parts of biphenyl-4, 4' -dicarboxylic acid and 57-65 parts of zinc iodide, and the preparation method comprises the following experimental medicines: ultra pure waterN-methylpyrrolidone, N2Distilled water, dilute sulfuric acid, absolute ethyl alcohol, dilute hydrochloric acid and sodium hydroxide.
2. Biochar based coating [ Zn ] according to claim 14O(BDBC)3]8The super capacitor material and the preparation method thereof are characterized in that: the biological straw is any one of recycled rice straw, wheat straw or sugarcane straw.
3. Biochar based coating [ Zn ] according to claim 14O(BDBC)3]8The super capacitor material and the preparation method thereof are characterized in that: the chemical analysis purity of the biphenyl-4, 4' -dicarboxylic acid is more than or equal to 98 percent.
4. Biochar based coating [ Zn ] according to claim 14O(BDBC)3]8The super capacitor material and the preparation method thereof are characterized in that: the zinc iodide is chemically pure, wherein the mass fraction of ZnI is more than or equal to 98.5%.
5. Biochar based coating [ Zn ] according to claim 14O(BDBC)3]8The super capacitor material and the preparation method thereof are characterized in that: the ultra pureN-methylpyrrolidone, N2Distilled water, absolute ethyl alcohol and sodium hydroxide are all chemically pure and ultrapureNThe mass fraction of the-methyl pyrrolidone is more than or equal to 99.5 percent, and the water content is less than or equal to 0.010 percent.
6. Biochar based coating [ Zn ] according to claim 14O(BDBC)3]8The super capacitor material and the preparation method thereof are characterized in that: dilute sulfuric acid H2SO4The mass fraction is 50-65%, and the mass concentration of the substance is 7.1-10.3 mol/L.
7. Biochar based coating [ Zn ] according to claim 14O(BDBC)3]8The super capacitor material and the preparation method thereof are characterized in that: the mass fraction of the dilute hydrochloric acid is 10-15%, and the mass concentration of the substance is 2.8-4.4 mol/L.
8. Biochar based coating [ Zn ] according to claim 14O(BDBC)3]8The super capacitor material and the preparation method thereof are characterized in that: the coating is based on biochar [ Zn ]4O(BDBC)3]8The preparation method of the super capacitor material comprises the following steps:
(1) hydrothermal method for preparing metal organic framework [ Zn ]4O(BDBC)3]8: adding 600-800 mL into 2000 mL three-neck bottleN-methylpyrrolidone, N being fed in2The air in the three-neck bottle is dischargedNAdding 5-8 parts of biphenyl-4, 4' -dicarboxylic acid and 57-65 parts of zinc iodide into the methyl pyrrolidone, heating the three-necked flask in a constant temperature water bath kettle to 85-90 ℃, stirring at a constant speed for reaction for 6-8 h, and adding the three-necked flask into the constant temperature water bath kettleTransferring the materials in the neck bottle into an automatic hydrothermal synthesis reaction kettle, setting the temperature at 140-N-methyl pyrrolidone and reaction by-products, putting the washed solid product into an oven, heating to 90-95 ℃, and drying for 5-6 h to obtain light yellow crystal metal organic framework [ Zn ]4O(BDBC)3]8；
(2) In-situ method for preparing biochar coated [ Zn ]4O(BDBC)3]8The supercapacitor material of (a): weighing 30-35 parts of biological straws, adding the biological straws into a ball mill, carrying out ball milling for 10-15H, adding 500-800 mL of dilute sulfuric acid H with the mass fraction of 50-65% into a 2000 mL reaction bottle2SO4Slowly adding ball-milled biological straws and 20-30 g of phosphoric acid, placing a reaction bottle in a constant-temperature water bath kettle, heating to 55-60 ℃, uniformly stirring for 5-8 h to perform a biological straw dehydration carbonization process, filtering the materials in the reaction bottle to remove a solid mixture, obtaining a filtrate containing glucose molecules and other organic small molecules formed by hydrolysis of straw cellulose, slowly adding sodium hydroxide into the filtrate until the filtrate is neutral and has a pH value of 7, adding the filtrate into a hydrothermal synthesis automatic reaction kettle, and adding the metal organic framework [ Zn ] prepared in the step (1)4O(BDBC)3]8Setting the temperature of a hydrothermal synthesis automatic reaction kettle to 70-75 ℃, carrying out small molecule prepolymerization reaction by magnetic stirring, increasing the temperature of the reaction kettle to 120-4O(BDBC)3]8The supercapacitor material of (1).
CN201911017868.1A 2019-10-24 2019-10-24 Based on biological charcoal cladding [ Zn ]4O(BDBC)3]8Super capacitor material and its making method Withdrawn CN110853939A (en)

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