CN112723336A - Cellulose-based SiO2-C composite material and preparation and application thereof - Google Patents

Cellulose-based SiO2-C composite material and preparation and application thereof Download PDF

Info

Publication number
CN112723336A
CN112723336A CN202011604494.6A CN202011604494A CN112723336A CN 112723336 A CN112723336 A CN 112723336A CN 202011604494 A CN202011604494 A CN 202011604494A CN 112723336 A CN112723336 A CN 112723336A
Authority
CN
China
Prior art keywords
composite material
cellulose
sio
drying
temperature
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN202011604494.6A
Other languages
Chinese (zh)
Inventor
蔺华林
李梦琰
王云云
王爱民
李欣
袁铭霞
陈哲
严春阳
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shanghai Institute of Technology
Original Assignee
Shanghai Institute of Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Shanghai Institute of Technology filed Critical Shanghai Institute of Technology
Priority to CN202011604494.6A priority Critical patent/CN112723336A/en
Publication of CN112723336A publication Critical patent/CN112723336A/en
Pending legal-status Critical Current

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • 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, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/34—Carbon-based characterised by carbonisation or activation of carbon
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/32—Carbon-based
    • H01G11/44—Raw materials therefor, e.g. resins or coal
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Power Engineering (AREA)
  • Materials Engineering (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Electric Double-Layer Capacitors Or The Like (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention relates to cellulose-based SiO2-C composite material and preparation and application thereof, wherein the preparation method specifically comprises the following steps: (1) adding cellulose and phenol into acid liquor for liquefaction to obtain liquefied liquid; (2) adjusting ph of the liquefied liquid obtained in the step (1) to be alkaline, and adding SiO2Heating in water bath to react to obtain precursor; (3) filtering and washing the precursor obtained in the step (2), drying, and carrying out pre-carbonization treatment to obtain coarse productA product; (4) uniformly mixing the crude product obtained in the step (3) with alkali liquor, drying, continuously calcining, and performing post-treatment to obtain the target product SiO2-a C composite material. Compared with the prior art, the composite material prepared by the invention has a pore structure and Si active groups with excellent appearance, improves the capacitance, the cycling stability and the conductivity of the composite material, and further improves the SiO content of cellulose base2The capacitance of the-C composite material greatly enhances the electricity storage capacity of the composite material.

Description

Cellulose-based SiO2-C composite material and preparation and application thereof
Technical Field
The invention belongs to the field of preparation of electrode materials of supercapacitors, and particularly relates to cellulose-based SiO2-C composite material and preparation and application thereof.
Background
The increasing growth of energy crisis has prompted the research and application of new energy sources. Super capacitors, as a new type of energy storage device, are widely used in portable devices that address energy and environmental concerns due to their high energy density and high capacitance capabilities. Therefore, the carbon material and the metal nano material which can be used for preparing the electrode material of the super capacitor are widely concerned, and how to efficiently and controllably prepare the carbon material and the metal nano material with regular morphology and pore structure becomes a hotspot of research. The carbon material with controllable morphology and pore structure can be specifically and effectively utilized in the fields of water treatment, gas adsorption and separation, catalyst carriers, energy storage and the like.
Biomass, a low-cost, widely available and renewable resource, is often used as a carbon source for synthesizing porous carbon materials by researchers. However, the complex stacking rule and the non-oriented structure of the anisotropic hexagonal carbon layer in the carbon material often hinder the efficiency of electron transfer, which leads to poor electrical conductivity of the supercapacitor made of the carbon material, and thus the carbon material is required to be usedThe material is improved doped. In consideration of the complexity of biomass, the traditional technology has difficulty in controlling the morphology and structure of biomass-based carbon material, so that if an SiO suitable for a supercapacitor can be explored2The method of the-C composite material has great practical significance.
Disclosure of Invention
The invention aims to provide cellulose-based SiO2the-C composite material and the preparation and the application thereof have the advantages that the excellent-appearance pore structure and the Si active group improve the capacitance, the circulation stability and the conductivity of the composite material, and further improve the SiO of the cellulose base2The capacitance of the-C composite material greatly enhances the electricity storage capacity of the composite material.
The purpose of the invention is realized by the following technical scheme:
cellulose-based SiO2-C composite material preparation method, the preparation method specifically comprising the steps of:
(1) adding cellulose and phenol into acid liquor for liquefaction to obtain liquefied liquid, wherein the liquefaction refers to the fact that the cellulose is converted from a solid state into a liquid state by using the acid liquor, and the phenol has the effect of a polymerization inhibitor in the wood liquefaction reaction;
(2) adjusting ph of the liquefied liquid obtained in the step (1) to be alkaline, and adding SiO2Heating in water bath to react to obtain precursor;
(3) carrying out suction filtration and washing on the precursor obtained in the step (2), drying, and carrying out pre-carbonization treatment to obtain a crude product;
(4) uniformly mixing the crude product obtained in the step (3) with alkali liquor, drying, continuously calcining, and performing post-treatment to obtain the target product SiO2-a C composite material.
In the step (1), the cellulose is in the form of powder.
In the step (1), the acid solution consists of sulfuric acid and phosphoric acid, and the volume ratio of the sulfuric acid to the phosphoric acid is 1: 2.
In the step (1), the mass-to-volume ratio of the cellulose to the phenol is 10g to 30 ml.
In the step (1), an oil bath is used for magnetic stirring and heating in the liquefaction process, the liquefaction temperature is 150-.
In the step (2), the pH is adjusted to 9-14 by adopting a sodium hydroxide solution, the water bath heating temperature is 60-80 ℃, the preferred temperature is 70 ℃, and the reaction time is 2.5-3.5h, the preferred time is 3 h.
In the step (3), acetone and water are alternately washed for multiple times, the drying temperature is 60-80 ℃, and the drying time is 8-12 h. The acetone is adopted to wash redundant oil (biomass, namely, cellulose can generate coke, biological oil and the like in the hydrothermal process) and acid, and the suction filtration is adopted in the washing process.
In the step (3), the pre-carbonization treatment is carried out in a nitrogen atmosphere, the temperature rise rate is 5 ℃/min, the pre-carbonization temperature is 450-.
In the step (4), the alkali liquor comprises KOH and water, and the mass ratio of the crude product to the KOH is 1 (1-4), preferably 1 (1-2).
In the step (4), the temperature for the continuous calcination treatment is 600-900 ℃, the time is 1.5-2.5h, preferably 2h, and the temperature rise rate is 5-10 ℃/min.
In the step (4), the post-treatment process specifically comprises the following steps: washing the obtained calcined sample to be neutral by adopting hydrochloric acid and water alternately for multiple times, and then drying the calcined sample for 8 to 12 hours at the temperature of between 60 and 80 ℃. Hydrochloric acid was used to adjust ph and remove impurities, and deionized water was used to wash to remove impurities.
Cellulose-based SiO prepared by the preparation method2-a C composite material.
A cellulose-based SiO as described above2Application of-C composite material in super capacitor and SiO obtained by using2Grinding the-C composite material, mixing the ground-C composite material with carbon black and PTFE, placing the mixture in an ultrasonic cleaner for ultrasonic mixing, and drying to obtain SiO used for the super capacitor2-C composite electrode material.
The drying temperature is 60 ℃, and the drying time is 12 h.
SiO2The mass ratio of the-C composite material to the carbon black to the PTFE is 8 (0.8-1.2) to (0.8-1.2).
SiO obtained by the invention2the-C composite electrode material takes KOH solution as electricityElectrolyte solution, selecting a three-electrode system to measure the electrochemical performance, wherein the three-electrode system takes an Ag/AgCl electrode as a reference electrode, a platinum wire electrode as a counter electrode and SiO2SiO made of-C composite electrode material2-C electrode as working electrode.
The doping of the non-metal oxide with specific morphology, pore structure and active group is crucial to improving the specific capacitance and rate performance of the carbon electrode in the super capacitor. In the non-metal field, silicon has a special morphology and excellent texture stability, and has been used for preparing electronic anode materials to further improve energy storage performance. The ordered structure of the silicon-carbon composite material can adapt to volume change, effectively avoid mechanical fracture, improve conductivity and prolong the service life of the material.
In the invention, cellulose is used as a carbon precursor, and the solid cellulose is converted into liquid by using acid liquor, so that the effective utilization of biomass waste is realized, and the degradation, the repolymerization, the cyclization and the aromatization of the carbon precursor are realized, namely the liquefaction process in the step one, and the carbonization temperature and the SiO aromatization are carried out at higher temperature2Number of particles (SiO)2+C→Si+CO↑+CO2×) releases secondary gas, the pore structure of the composite material forms a contraction further depending on the skeleton, and finally, silica is covered around the ordered carbon skeleton material to reduce the volume expansion. Furthermore, SiO2the-C composite has a lattice plane (111) of silicon of 0.301 nm, which indicates that the structure of the sample can control the pore size structure through the interaction of silicon dioxide and carbon at high temperature, so that the ion transport can be enhanced, thereby further improving the capacitance, the cycling stability and the conductivity thereof. In addition, the characteristics can provide a large storage space, the electron transport resistance of the electrode material is greatly reduced, and the capacitance of the carbon-based super capacitor is further improved. The Si group on the surface of the material also improves SiO2Structural stability and electrical conductivity of the-C composite.
Compared with the prior art, the invention has the following advantages:
1) the invention dopes SiO on carbon precursor2The material can be controlled by the interaction of silica and carbon at high temperatureAnd (4) material structure.
2) The porous carbon material prepared by the method can provide a large storage space, greatly reduces the electron transport impedance of the electrode material, and further improves the capacitance of the carbon-based supercapacitor.
3) The invention uses the cellulose existing in nature in large quantity as the carbon precursor, thereby saving the cost, being cheap and environment-friendly.
Drawings
FIG. 1 shows SiO obtained in example 12-C composite material at 0.5Ag-1(ii) the lower GCD plot;
FIG. 2 shows SiO obtained in example 12-a TEM image of the C composite;
FIG. 3 shows SiO obtained in example 12-C composite at 10mVs-1CV curve at sweep speed.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments. The present embodiment is implemented on the premise of the technical solution of the present invention, and a detailed implementation manner and a specific operation process are given, but the scope of the present invention is not limited to the following embodiments.
In the following examples, the starting products or processing techniques are not specifically described, but are all conventional commercial products or conventional processing techniques in the art.
Cellulose-based SiO2-C composite material preparation method, the preparation method specifically comprising the steps of:
(1) adding cellulose and phenol into acid liquor for liquefaction to obtain liquefied liquid;
(2) adjusting ph of the liquefied liquid obtained in the step (1) to be alkaline, and adding SiO2Heating in water bath to react to obtain precursor;
(3) carrying out suction filtration and washing on the precursor obtained in the step (2), drying, and carrying out pre-carbonization treatment to obtain a crude product;
(4) uniformly mixing the crude product obtained in the step (3) with alkali liquor, drying, continuously calcining, and performing post-treatment to obtain the target product SiO2-a C composite material.
In the step (1), the acid solution consists of sulfuric acid and phosphoric acid, the volume ratio of the sulfuric acid to the phosphoric acid is 1:2, the mass volume ratio of the cellulose powder to the phenol is 10g:30ml, the liquefaction process is carried out by using an oil bath for magnetic stirring and heating, the liquefaction temperature is 150 ℃ and 180 ℃, and the liquefaction time is 1-3 h.
In the step (2), the pH is adjusted to 9-14 by adopting a sodium hydroxide solution, the water bath heating temperature is 60-80 ℃, and the reaction time is 2.5-3.5 h.
In the step (3), acetone and water are alternately washed for multiple times, the drying temperature is 60-80 ℃, the drying time is 8-12h, the pre-carbonization treatment is carried out in the nitrogen atmosphere, the pre-carbonization temperature is 450-550 ℃, the preferred temperature is 500 ℃, and the pre-carbonization time is 1.5-2.5 h.
In the step (4), the alkali liquor comprises KOH and water, the mass ratio of the crude product to the KOH is 1 (1-2), the temperature for continuous calcination treatment is 600-900 ℃, the time is 1.5-2.5h, the temperature rise rate is 5-10 ℃/min, and the post-treatment process specifically comprises the following steps: washing the obtained calcined sample to be neutral by adopting hydrochloric acid and water alternately for multiple times, and then drying the calcined sample for 8 to 12 hours at the temperature of between 60 and 80 ℃. The invention is used for SiO of a super capacitor2In the preparation process of the-C composite material, each process condition can be adjusted at will within the above process range according to needs (namely, the middle point value or the end value is selected at will).
Cellulose-based SiO prepared by the preparation method2-a C composite material.
A cellulose-based SiO as described above2Application of-C composite material in super capacitor and SiO obtained by using2Grinding the-C composite material, mixing the ground-C composite material with carbon black and PTFE, placing the mixture in an ultrasonic cleaner for ultrasonic mixing, and drying to obtain SiO used for the super capacitor2-C composite electrode material, SiO2The mass ratio of the-C composite material to the carbon black to the PTFE is 8 (0.8-1.2) to (0.8-1.2).
Example 1
Cellulose-based SiO2-C composite material preparation method comprising the steps of:
1) taking 10g of cellulose powder and 30ml of phenol, adding 1ml of sulfuric acid and 2ml of phosphoric acid, and liquefying under an acidic condition, wherein an oil bath is used for magnetic stirring and heating in the liquefying process, the temperature is 150 ℃, and the time is 3 hours;
2) regulating the pH of the liquefied liquid in the step (1) to 9-14 by using a sodium hydroxide solution, and then adding SiO2Carrying out water bath heating reaction to obtain a precursor, wherein the temperature is 70 ℃, and the reaction time is 3 h;
3) washing the precursor obtained in the step (2) with acetone and deionized water, performing suction filtration, then placing in a vacuum drying oven for drying, wherein the temperature in the drying process is 80 ℃ and the time is 10 hours, then performing pre-carbonization treatment to obtain a crude product, and performing the pre-carbonization treatment under the nitrogen atmosphere, wherein the temperature rise rate is 5 ℃/min, the pre-carbonization temperature is 500 ℃ and the time is 2 hours;
4) uniformly mixing the pre-carbonized crude product obtained in the step (3) with KOH and deionized water, drying, continuously calcining, washing and drying to obtain the target product SiO2-C composite carbon material, as shown in FIG. 2, which is a TEM image of the material, it can be seen that the material surface is flat. The mass ratio of the pre-carbonized crude product to KOH is 1:2, hydrochloric acid and deionized water are adopted for washing, the calcining temperature for continuous calcining is 600 ℃, the time is 2 hours, the temperature for drying is 80 ℃, and the time is 10 hours;
5) grinding the carbon material obtained in the step 4), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8:1.2:0.8, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, drying the mixture at the temperature of 60 ℃ for 12 hours to obtain SiO for the supercapacitor2-C composite electrode material.
SiO2-electrochemical performance test of the C composite electrode material:
and (3) performing electrochemical performance test on the prepared nitrogen-phosphorus co-doped carbon electrode in a three-electrode system by adopting an electrochemical workstation. The working electrode is SiO2SiO made of-C composite electrode material2-C electrode, counter electrode platinum wire electrode, reference electrode Ag/AgCl electrode, 6M KOH solution as electrolyte, CV curve and GCD curve were tested, the CV curve is shown in FIG. 3, and it can be seen that at 10mVs-1At the scanning speed, the cyclic voltammogram exhibited a typical parallelogram-like shape, indicating that this is typical double layer capacitor behavior, and the GCD curve is specifically shown in fig. 1It can be seen that the silver content is 0.5Ag-1The potential can reach the maximum value when the discharge time is about 220s, which shows that the composite material has higher specific capacitance.
Example 2
Cellulose-based SiO2-C composite material preparation method comprising the steps of:
1) taking 10g of cellulose powder and 30ml of phenol, adding 1ml of sulfuric acid and 2ml of phosphoric acid, and liquefying under an acidic condition, wherein an oil bath is used for magnetic stirring and heating in the liquefying process, the temperature is 170 ℃, and the time is 2 hours;
2) regulating the pH of the liquefied liquid in the step (1) to 9-14 by using a sodium hydroxide solution, and then adding SiO2Carrying out water bath heating reaction to obtain a precursor, wherein the temperature is 70 ℃, and the reaction time is 3 h;
3) washing the precursor obtained in the step (2) with acetone and deionized water, performing suction filtration, then placing in a vacuum drying oven for drying, wherein the temperature in the drying process is 80 ℃ and the time is 10 hours, then performing pre-carbonization treatment to obtain a crude product, and performing the pre-carbonization treatment under the nitrogen atmosphere, wherein the temperature rise rate is 5 ℃/min, the pre-carbonization temperature is 500 ℃ and the time is 2 hours;
4) uniformly mixing the pre-carbonized crude product obtained in the step (3) with KOH and deionized water, drying, continuously calcining at high temperature, washing and drying to obtain the target product SiO2The mass ratio of a pre-carbonized sample to KOH is 1:1, the pre-carbonized sample is washed by hydrochloric acid and deionized water, the calcining temperature for continuous calcining is 700 ℃, the time is 2 hours, and the temperature for the drying process is 80 ℃, and the time is 10 hours;
5) grinding the carbon material obtained in the step 4), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8:1:1, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, drying the mixture at the temperature of 60 ℃ for 12 hours to obtain SiO for the supercapacitor2-C composite electrode material.
Example 3
Cellulose-based SiO2-C composite material preparation method comprising the steps of:
1) taking 10g of cellulose powder and 30ml of phenol, adding 1ml of sulfuric acid and 2ml of phosphoric acid, and liquefying under an acidic condition, wherein an oil bath is used for magnetic stirring and heating in the liquefying process, the temperature is 180 ℃, and the time is 2 hours;
2) regulating the pH of the liquefied liquid in the step (1) to 9-14 by using a sodium hydroxide solution, and then adding SiO2Carrying out water bath heating reaction to obtain a precursor, wherein the temperature is 70 ℃, and the reaction time is 3 h;
3) washing the precursor obtained in the step (2) with acetone and deionized water, performing suction filtration, then placing in a vacuum drying oven for drying, wherein the temperature in the drying process is 60 ℃, the time is 12 hours, then performing pre-carbonization treatment to obtain a crude product, and performing the pre-carbonization treatment under the nitrogen atmosphere, wherein the temperature rise rate is 5 ℃/min, the pre-carbonization temperature is 500 ℃, and the time is 2 hours;
4) uniformly mixing the pre-carbonized crude product obtained in the step (3) with KOH and deionized water, drying, continuously calcining at high temperature, washing and drying to obtain the target product SiO2The mass ratio of a pre-carbonized sample to KOH is 1:2, the pre-carbonized sample is washed by hydrochloric acid and deionized water, the calcining temperature is 800 ℃, the time is 2 hours, and the drying temperature is 60 ℃, the time is 12 hours;
5) grinding the carbon material obtained in the step 4), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8:1:1, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, drying the mixture at the temperature of 60 ℃ for 12 hours to obtain SiO for the supercapacitor2-C composite electrode material.
Example 4
Cellulose-based SiO2-C composite material preparation method comprising the steps of:
1) taking 10g of cellulose powder and 30ml of phenol, adding 1ml of sulfuric acid and 2ml of phosphoric acid, and liquefying under an acidic condition, wherein an oil bath is used for magnetic stirring and heating in the liquefying process, the temperature is 180 ℃, and the time is 2 hours;
2) regulating the pH of the liquefied liquid in the step (1) to 9-14 by using a sodium hydroxide solution, and then adding SiO2Carrying out water bath heating reaction to obtain a precursor, wherein the temperature is 70 ℃, and the reaction time is 3 h;
3) washing the precursor obtained in the step (2) with acetone and deionized water, performing suction filtration, then placing in a vacuum drying oven for drying, wherein the temperature in the drying process is 60 ℃, the time is 12 hours, then performing pre-carbonization treatment to obtain a crude product, and performing the pre-carbonization treatment under the nitrogen atmosphere, wherein the temperature rise rate is 5 ℃/min, the pre-carbonization temperature is 500 ℃, and the time is 2 hours;
4) uniformly mixing the pre-carbonized crude product obtained in the step (3) with KOH and deionized water, drying, continuously calcining at high temperature, washing and drying to obtain the target product SiO2The mass ratio of a pre-carbonized sample to KOH is 1:1, the pre-carbonized sample is washed by hydrochloric acid and deionized water, the calcining temperature is 800 ℃, the time is 2 hours, and the drying temperature is 60 ℃, the time is 12 hours;
5) grinding the carbon material obtained in the step 4), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8:1:1, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, drying the mixture at the temperature of 60 ℃ for 12 hours to obtain SiO for the supercapacitor2-C composite electrode material.
Example 5
Cellulose-based SiO2-C composite material preparation method comprising the steps of:
1) taking 10g of cellulose powder and 30ml of phenol, adding 1ml of sulfuric acid and 2ml of phosphoric acid, and liquefying under an acidic condition, wherein an oil bath is used for magnetic stirring and heating in the liquefying process, the temperature is 160 ℃, and the time is 3 hours;
2) regulating the pH of the liquefied liquid in the step (1) to 9-14 by using a sodium hydroxide solution, and then adding SiO2Carrying out water bath heating reaction to obtain a precursor, wherein the temperature is 70 ℃, and the reaction time is 3 h;
3) washing the precursor obtained in the step (2) with acetone and deionized water, performing suction filtration, then placing in a vacuum drying oven for drying, wherein the temperature in the drying process is 80 ℃, the time is 12 hours, then performing pre-carbonization treatment to obtain a crude product, and performing the pre-carbonization treatment under the nitrogen atmosphere, wherein the temperature rise rate is 5 ℃/min, the pre-carbonization temperature is 500 ℃, and the time is 2 hours;
4) uniformly mixing the pre-carbonized crude product obtained in the step (3) with KOH and deionized water, drying, continuously calcining at high temperature, washing and drying to obtain the target product SiO2The mass ratio of a pre-carbonized sample to KOH is 1:1, the pre-carbonized sample is washed by hydrochloric acid and deionized water, the calcining temperature is 900 ℃, the time is 2 hours, and the pre-carbonized sample is driedThe temperature in the drying process is 80 ℃, and the time is 12 hours;
5) grinding the carbon material obtained in the step 4), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8:1:1, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, drying the mixture at the temperature of 60 ℃ for 12 hours to obtain SiO for the supercapacitor2-C composite electrode material.
Example 6
Cellulose-based SiO2-C composite material preparation method comprising the steps of:
1) taking 10g of cellulose powder and 30ml of phenol, adding 1ml of sulfuric acid and 2ml of phosphoric acid, and liquefying under an acidic condition, wherein an oil bath is used for magnetic stirring and heating in the liquefying process, the temperature is 170 ℃, and the time is 3 hours;
2) regulating the pH of the liquefied liquid in the step (1) to 9-14 by using a sodium hydroxide solution, and then adding SiO2Carrying out water bath heating reaction to obtain a precursor, wherein the temperature is 70 ℃, and the reaction time is 3 h;
3) washing the precursor obtained in the step (2) with acetone and deionized water, performing suction filtration, then placing in a vacuum drying oven for drying, wherein the temperature in the drying process is 80 ℃, the time is 11 hours, then performing pre-carbonization treatment to obtain a crude product, and performing the pre-carbonization treatment under the nitrogen atmosphere, wherein the temperature rise rate is 5 ℃/min, the pre-carbonization temperature is 500 ℃, and the time is 2 hours;
4) uniformly mixing the pre-carbonized crude product obtained in the step (3) with KOH and deionized water, drying, continuously calcining at high temperature, washing and drying to obtain the target product SiO2The mass ratio of a pre-carbonized sample to KOH is 1:2, the pre-carbonized sample is washed by hydrochloric acid and deionized water, the calcining temperature is 900 ℃, the time is 2 hours, and the drying temperature is 80 ℃, and the time is 11 hours;
5) grinding the carbon material obtained in the step 4), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8:0.8:1.2, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, drying the mixture at the temperature of 60 ℃ for 12 hours to obtain SiO for the supercapacitor2-C composite electrode material.
Example 7
Cellulose-based SiO2-C composite material preparation method comprising the steps of:
1) taking 10g of cellulose powder and 30ml of phenol, adding 1ml of sulfuric acid and 2ml of phosphoric acid, and liquefying under an acidic condition, wherein an oil bath is used for magnetic stirring and heating in the liquefying process, the temperature is 160 ℃, and the time is 3 hours;
2) regulating the pH of the liquefied liquid in the step (1) to 9-14 by using a sodium hydroxide solution, and then adding SiO2Carrying out water bath heating reaction to obtain a precursor, wherein the temperature is 70 ℃, and the reaction time is 3 h;
3) washing the precursor obtained in the step (2) with acetone and deionized water, performing suction filtration, then placing in a vacuum drying oven for drying, wherein the temperature in the drying process is 80 ℃, the time is 8 hours, then performing pre-carbonization treatment to obtain a crude product, and performing the pre-carbonization treatment under the nitrogen atmosphere, wherein the temperature rise rate is 5 ℃/min, the pre-carbonization temperature is 500 ℃, and the time is 2 hours;
4) uniformly mixing the pre-carbonized crude product obtained in the step (3) with KOH and deionized water, drying, continuously calcining at high temperature, washing and drying to obtain the target product SiO2The mass ratio of a pre-carbonized sample to KOH is 1:1, the pre-carbonized sample is washed by hydrochloric acid and deionized water, the calcining temperature is 900 ℃, the time is 2 hours, and the drying temperature is 80 ℃, and the time is 8 hours;
5) grinding the carbon material obtained in the step 4), mixing the ground carbon material with carbon black and PTFE according to the mass ratio of 8:1:1, then placing the mixture into an ultrasonic cleaner for ultrasonic mixing, drying the mixture at the temperature of 60 ℃ for 12 hours to obtain SiO for the supercapacitor2-C composite electrode material.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. Cellulose-based SiO2-C composite materialThe preparation method is characterized by comprising the following steps:
(1) adding cellulose and phenol into acid liquor for liquefaction to obtain liquefied liquid;
(2) adjusting ph of the liquefied liquid obtained in the step (1) to be alkaline, and adding SiO2Heating in water bath to react to obtain precursor;
(3) carrying out suction filtration and washing on the precursor obtained in the step (2), drying, and carrying out pre-carbonization treatment to obtain a crude product;
(4) uniformly mixing the crude product obtained in the step (3) with alkali liquor, drying, continuing to calcine, adjusting ph to be neutral by hydrochloric acid, washing with deionized water, and drying to obtain the target product SiO2-a C composite material.
2. Cellulose-based SiO according to claim 12The preparation method of the-C composite material is characterized in that in the step (1), the acid solution consists of sulfuric acid and phosphoric acid, and the volume ratio of the sulfuric acid to the phosphoric acid is 1: 2.
3. Cellulose-based SiO according to claim 12The preparation method of the-C composite material is characterized in that in the step (1), an oil bath is used for magnetic stirring and heating in the liquefaction process, the liquefaction temperature is 150 ℃ and 180 ℃, and the liquefaction time is 1-3 h.
4. Cellulose-based SiO according to claim 12The preparation method of the-C composite material is characterized in that in the step (2), the pH is adjusted to 9-14 by adopting a sodium hydroxide solution, the water bath heating temperature is 60-80 ℃, and the reaction time is 2.5-3.5 h.
5. Cellulose-based SiO according to claim 12The preparation method of the-C composite material is characterized in that in the step (3), acetone and water are alternately washed for multiple times, the drying temperature is 60-80 ℃, and the drying time is 8-12 h.
6. Cellulose-based SiO according to claim 12The preparation method of the-C composite material is characterized in that in the step (3), the pre-carbonization treatment is carried out in a nitrogen atmosphere, the pre-carbonization temperature is 450-550 ℃, and the pre-carbonization time is 1.5-2.5 h.
7. Cellulose-based SiO according to claim 12The preparation method of the-C composite material is characterized in that in the step (4), the temperature for continuous calcination treatment is 600-900 ℃, and the time is 1.5-2.5 h.
8. Cellulose-based SiO according to claim 12The preparation method of the-C composite material is characterized in that in the step (4), the alkali liquor comprises KOH and water, and the mass ratio of the crude product to the KOH is 1 (1-4);
in the step (4), the post-treatment process specifically comprises the following steps: washing the obtained calcined sample to be neutral by adopting hydrochloric acid and water alternately for multiple times, and then drying the calcined sample for 8 to 12 hours at the temperature of between 60 and 80 ℃.
9. Cellulose-based SiO obtainable by the preparation process according to any one of claims 1 to 82-a C composite material.
10. Cellulose-based SiO as claimed in claim 92-C composite material for use in supercapacitors, characterized in that the SiO obtained2Grinding the-C composite material, mixing the ground-C composite material with carbon black and PTFE, placing the mixture in an ultrasonic cleaner for ultrasonic mixing, and drying to obtain SiO used for the super capacitor2-C composite electrode material.
CN202011604494.6A 2020-12-29 2020-12-29 Cellulose-based SiO2-C composite material and preparation and application thereof Pending CN112723336A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202011604494.6A CN112723336A (en) 2020-12-29 2020-12-29 Cellulose-based SiO2-C composite material and preparation and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202011604494.6A CN112723336A (en) 2020-12-29 2020-12-29 Cellulose-based SiO2-C composite material and preparation and application thereof

Publications (1)

Publication Number Publication Date
CN112723336A true CN112723336A (en) 2021-04-30

Family

ID=75610786

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202011604494.6A Pending CN112723336A (en) 2020-12-29 2020-12-29 Cellulose-based SiO2-C composite material and preparation and application thereof

Country Status (1)

Country Link
CN (1) CN112723336A (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108878813A (en) * 2018-06-15 2018-11-23 华南理工大学 A kind of silica/lignin porous carbon composite and preparation method thereof and the application in lithium ion battery negative material
CN109516458A (en) * 2018-12-05 2019-03-26 华南师范大学 A kind of biomass-based graded porous carbon and preparation method thereof
CN109659154A (en) * 2018-12-26 2019-04-19 武汉工程大学 A kind of preparation method and applications of Carbon-based supercapacitor electrode material
CN110690439A (en) * 2019-10-25 2020-01-14 河南大森林生物科技有限公司 P, N co-doped C/SiO prepared from silicon-containing biomassxGreen method for composite negative electrode material of lithium ion battery
CN110975833A (en) * 2019-12-18 2020-04-10 昆明理工大学 Preparation method and application of silicon dioxide/cellulose composite porous material

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108878813A (en) * 2018-06-15 2018-11-23 华南理工大学 A kind of silica/lignin porous carbon composite and preparation method thereof and the application in lithium ion battery negative material
CN109516458A (en) * 2018-12-05 2019-03-26 华南师范大学 A kind of biomass-based graded porous carbon and preparation method thereof
CN109659154A (en) * 2018-12-26 2019-04-19 武汉工程大学 A kind of preparation method and applications of Carbon-based supercapacitor electrode material
CN110690439A (en) * 2019-10-25 2020-01-14 河南大森林生物科技有限公司 P, N co-doped C/SiO prepared from silicon-containing biomassxGreen method for composite negative electrode material of lithium ion battery
CN110975833A (en) * 2019-12-18 2020-04-10 昆明理工大学 Preparation method and application of silicon dioxide/cellulose composite porous material

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
《化工百科全书》编辑委员会: "《化工百科全书 第3卷 刀具材料—发电》", 31 March 1993 *

Similar Documents

Publication Publication Date Title
CN105780364B (en) A kind of method for preparing ultramicropore flexibility carbon cloth and products thereof and application
CN109637829B (en) Method for preparing nitrogen-doped porous carbon through crosslinking of sodium alginate and diamine compound
CN111261431B (en) Preparation method of nano cobaltosic oxide/nitrogen-doped three-dimensional porous carbon skeleton composite material for super capacitor
CN110707323B (en) Anion layer-expanding carbon material and preparation method and application thereof
CN112830472A (en) Preparation method of porous carbon, porous carbon obtained by preparation method and application of porous carbon
CN111268675A (en) Method for preparing nitrogen-phosphorus co-doped carbon material by taking durian peel as raw material
CN109319762B (en) Preparation of biomass porous carbon material with ultrahigh specific surface area and application of biomass porous carbon material as electrode material
CN111333129A (en) Preparation method of nano nickel sulfide/nitrogen-doped porous carbon composite material for super capacitor
CN114408919A (en) Coconut shell material-based porous carbon material subjected to high-temperature thermal shock carbonization and KOH activation, and preparation method and application thereof
CN108807000B (en) Preparation method of nano porous carbon for high-performance super capacitor
CN110589823A (en) Shaddock peel porous carbon material and preparation method and application thereof
Xiang et al. Supercapacitor properties of N/S/O co-doped and hydrothermally sculpted porous carbon cloth in pH-universal aqueous electrolytes: Mechanism of performance enhancement
CN107680826B (en) A kind of preparation method of the layering porous active carbon electrode material for supercapacitor
US20230234851A1 (en) Boron-sulfur-codoped porous carbon material and preparation method and use thereof
CN112723336A (en) Cellulose-based SiO2-C composite material and preparation and application thereof
CN113380555B (en) Hexadecylamine intercalated alpha-MoO 3 Material, preparation method thereof and application of material as supercapacitor electrode material
CN112185709B (en) High-rate mesoporous RuO 2 Preparation method of/C composite electrode material
CN113044839B (en) Preparation method and application of hierarchical porous carbon material
CN112837947B (en) Nitrogen and sulfur co-doped layered porous carbon hybrid material prepared from inorganic-cellulose raw material, and preparation and application thereof
CN110817876B (en) Preparation method and application of eggshell membrane derived carbon/MXene/manganese dioxide composite material
CN113838677A (en) N-doped porous carbon composite hollow NiCo2O4Preparation and application of electrode material
CN112897526A (en) Preparation method and application of porous carbon dot material based on industrial glucose
CN112735858A (en) Preparation method of nitrogen and sulfur co-doped layered porous carbon hybrid material for super capacitor
CN113077997B (en) Preparation method of spirulina-based carbon material for super capacitor
CN113371752B (en) Ni (OH) applied to super capacitor 2 /CuO@Cu 7 S 4 Composite electrode material and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication

Application publication date: 20210430

RJ01 Rejection of invention patent application after publication