WO2023056774A1 - Composite material, and preparation method therefor and use thereof - Google Patents

Composite material, and preparation method therefor and use thereof Download PDF

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WO2023056774A1
WO2023056774A1 PCT/CN2022/109233 CN2022109233W WO2023056774A1 WO 2023056774 A1 WO2023056774 A1 WO 2023056774A1 CN 2022109233 W CN2022109233 W CN 2022109233W WO 2023056774 A1 WO2023056774 A1 WO 2023056774A1
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composite material
preparation
heat treatment
cellulose
hours
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PCT/CN2022/109233
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French (fr)
Chinese (zh)
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张振华
李长东
范霞
毛林林
阮丁山
蔡勇
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • 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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • H01M4/606—Polymers containing aromatic main chain polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • 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
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of inorganic non-metallic materials, and in particular relates to a composite material and its preparation method and application.
  • Carbon conductive materials have broad development potential since they were discovered. As a new type of conductive material, it has both good conductivity and high reversible capacity. At the same time, carbon materials are widely used in the preparation of lithium batteries because of their low insertion voltage, high stability, and tunable microstructure. With the increasing demand for the development of high-efficiency and high-storage energy storage battery materials, research on new battery systems to replace lithium-ion batteries has received extensive attention.
  • Carbon-based materials have become a research hotspot for battery anode materials due to their high conductivity, low cost and chemical stability, but some carbon materials also have problems of low capacity and poor rate performance.
  • the theoretical capacity of graphite in batteries is only 279mA h g -1 , while the huge volume expansion and low diffusion kinetics of potassium ion intercalation/extraction limit its application.
  • many efforts have been made to optimize carbon anode materials, such as increasing defects to improve active sites, increasing specific surface area to improve potassium storage capacity, etc.
  • the existing technology has limited effects on increasing the specific surface area, increasing the capacity of the material, and improving the electrochemical performance of the carbon material.
  • the present invention at least solves one of the above-mentioned problems existing in the prior art problems, for this reason the present invention provides a kind of composite material, the composite material provided by the present invention, by introducing hierarchical structure and nitrogen-containing structure (pyridine nitrogen, pyrrole nitrogen, oxidation Nitrogen, etc.), can effectively improve the electrochemical performance of the material; the composite material after nitrogen doping is activated by carbonization, and a porous carbon material with a hierarchical pore structure is synthesized, which is helpful for the migration and storage of lithium ions, and improves the capacity of the material.
  • the core-shell structure alleviates the volume change during the lithium ion deintercalation process.
  • the present invention also provides a preparation method of the composite material.
  • the present invention also provides an energy storage device comprising the above-mentioned composite material.
  • a kind of composite material comprise carbon fiber and the polyaniline particle that is attached on the described carbon fiber;
  • Pores are present in the composite material
  • the diameter of the pores is ⁇ 4nm.
  • the present invention can effectively improve the electrochemical performance of the material by introducing a hierarchical structure and a nitrogen-containing structure (pyridine nitrogen, pyrrole nitrogen, nitrogen oxide, etc.).
  • the present invention activates the nitrogen-doped composite material through carbonization to synthesize a porous carbon material containing a hierarchical pore structure, which is helpful for the migration and storage of lithium ions, and improves the capacity of the material.
  • the composite material has a concentrated distribution of pore sizes between 3-4 nm and below 2 nm, and an average pore volume of about 0.75 cm 3 /g.
  • the carbon fiber has a diameter of 85-105 nm.
  • the raw material for the preparation of the cellulose includes bacterial cellulose.
  • the raw material for the preparation of bacterial cellulose includes Bacillus hansenii.
  • the invention uses bacterial cellulose nanofibers as the core and polyaniline as the shell to form a core-shell structure, thereby alleviating the volume change generated during the deintercalation process of lithium ions.
  • the invention synthesizes polyaniline with bacterial cellulose as the base, reduces the aggregation degree of the polymer, improves the uniformity of dispersion, and strengthens the contact between the polymer and the bacterial cellulose.
  • Another aspect of the present invention proposes the preparation method of described composite material, comprises the following steps:
  • step S2 heat treating the mixture obtained in step S1 under nitrogen atmosphere
  • step S3 Mix the mixture obtained in step S2 with the porogen, heat treat, remove impurities, and dry to obtain the composite material.
  • the preparation method of the cellulose comprises the following steps:
  • A1 Add citric acid to the culture medium, mix, and ferment with the Bacillus hansenii as the strain to form bacterial cellulose;
  • A2 washing the bacterial cellulose with an alkaline solution to remove impurities to obtain the cellulose.
  • the medium is a mixture composed of glucose, yeast extract, peptone, and sodium dihydrogen phosphate.
  • the mass ratio of the glucose, the yeast extract, the peptone, and the sodium dihydrogen phosphate is 1:(0.2 ⁇ 0.3):(0.2 ⁇ 0.3):(0.1 ⁇ 0.2 ).
  • the concentration of the citric acid is 1-5 g/L.
  • step A1 the fermentation time of the Bacillus hansiformis is 15-30 days.
  • step A1 the fermentation temperature of the Bacillus hansiformis is 25-50°C.
  • the alkaline solution includes one of KOH solution or NaOH solution.
  • the concentration of the alkaline solution is 0.1-3 mol/L.
  • the impurity removal process is stirring in an alkaline solution for 10-30 hours.
  • step A2 after stirring in an alkaline solution, wash with deionized water several times until the pH is close to 7.
  • step S1 the mass ratio of the cellulose to the volume ratio of the aniline stock solution (ie solid-to-liquid ratio) is 1g:5-20ml, and the purity AR of the aniline stock solution is ⁇ 99.5%.
  • the initiator in step S1, includes one of persulfate, hydrogen peroxide, dichromate and ferric chloride.
  • the initiator in step S1, includes persulfate.
  • the initiator in step S1, includes ammonium persulfate.
  • step S1 the molar ratio of the aniline to the initiator is 1:(1-2).
  • the dopant in step S1, includes at least one of HCl solution or H 2 SO 4 solution.
  • the concentration of the HCl solution or the H 2 SO 4 solution is 0.1-2 mol/L.
  • step S1 the mixing temperature is 0-30°C.
  • step S1 the mixing time is 24-50 hours.
  • a large number of hydroxyl groups in cellulose form hydrogen bonds with the amine functional groups in aniline, which act as bridging ligands and help the aniline monomer to adsorb on its surface, while ammonium persulfate acts as the initiator of the polymerization reaction, and the acid As a dopant, the entire fiber network undergoes a uniform polymerization reaction, thereby synthesizing a composite material of cellulose and polyaniline.
  • step S1 the impurity removal is washing the mixture obtained in step S1 with deionized water for 3-7 times.
  • step S1 the drying time is 5-24 hours.
  • step S1 the drying temperature is 50-120°C.
  • the heat treatment includes a first heat treatment and a second heat treatment.
  • the temperature of the first heat treatment is 200-400°C.
  • the time for the first heat treatment is 0.5-14 hours.
  • the hydroxyl groups on the cellulose will form ether bonds, and cross-links will occur between the single chains, thereby stabilizing the material.
  • the temperature of the second heat treatment is 900-1200°C.
  • the time of the second heat treatment is 1-5 hours.
  • the second heat treatment can remove impurity molecules while repairing a small number of defects to increase the degree of graphitization.
  • nitrogen exists in the form of dopants, which can improve the wettability of the obtained material and the electrolyte , the formed pyrrole nitrogen, pyridinium nitrogen, and nitrogen oxide cause defects such as sheet edge bending and vacancies that will serve as active sites to store lithium ions.
  • the porogen includes one of KOH and NaOH.
  • step S3 the porogen is KOH.
  • step S3 the mass ratio of the mixture obtained in step S2 to the porogen is 1:(2-10).
  • step S3 the temperature of the heat treatment is 700-900°C.
  • step S3 the time of the heat treatment is 1-4 hours.
  • step S3 the impurity removal includes pickling.
  • step S3 the acid used in the pickling process is one of HCl or H 2 SO 4 .
  • step S3 the temperature of the pickling is 25-50°C.
  • step S3 the acid washing time is 1-6 hours.
  • potassium and its compounds are obtained.
  • Potassium and its compounds include K, K 2 CO 3 and K 2 O, wherein CO 2 and CO produced by the continuous reaction of K 2 CO 3 are the same as the activated
  • the generated N 2 O, NO and bound water overflow, making the material porosity; metal potassium is embedded in the carbon, and the lattice expands.
  • the intercalated potassium is removed leaving a lot of vacancies, and these micropores and mesopores in the interconnected fiber network facilitate the penetration of the electrolyte through hierarchical assembly, providing for the transport of lithium ions and electrons.
  • the core-shell structure adapts to the volume change caused by the lithium ion deintercalation process, and has excellent cycle stability at high rates.
  • Fig. 1 is the XRD figure of embodiment 5 step A2b composite material 1200 °C of carbonization 2h;
  • Fig. 2 is the XRD figure of the composite material of embodiment 5;
  • Fig. 3 is the XPS analysis high-resolution N1s figure of the composite material of embodiment 5;
  • Fig. 4 is the pore size distribution figure of the composite material of embodiment 5;
  • Example 5 is a SEM image of the composite material of Example 5.
  • This embodiment has prepared a kind of composite material, and specific preparation method is:
  • A1a Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
  • A1b Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
  • Glucose specification D-(+)-glucose, GC, ⁇ 99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ⁇ 99%, purchased from Aladdin.
  • A2a Mix the washed cellulose, aniline, and ammonium persulfate into 0.8mol/L H 2 SO 4 and stir at room temperature for 24 hours, wherein the volume ratio of the mass of cellulose to aniline (i.e. solid-to-liquid ratio) is 1g : 10ml, the mol ratio of aniline and ammonium persulfate is 1:1.5, thereby the composite material of synthesizing cellulose and polyaniline, the composite material of cellulose and polyaniline is washed 5 times with deionized water, and then placed in a drying box Dry at 80°C for 15 hours;
  • step A2b Place the mixture obtained in step A2a in a nitrogen atmosphere, calcinate at 300°C for 5h, and then further raise the temperature to 1200°C for carbonization for 2h;
  • A3b Mix the mixture obtained in A2b with KOH at a mass ratio of 1:4, calcinate at 700°C for 2 hours and cool, then wash with 0.5mol/L HCl at 25-50°C for 1-6 hours, then deionize The composite material was obtained by washing several times until the pH was close to 7, and drying at 80° C. for 15 hours.
  • B1b 75% of the composite material prepared in Example 1 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, placed at room temperature and dried for 24h, and then After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading capacity of the active material was 1.5 mg/cm 2 .
  • This embodiment has prepared a kind of composite material, and specific preparation method is:
  • A1a Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
  • A1b Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
  • Glucose specification D-(+)-glucose, GC, ⁇ 99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ⁇ 99%, purchased from Aladdin.
  • A2a Mix the washed cellulose, aniline, and ammonium persulfate into 0.8mol/L H 2 SO 4 and stir at room temperature for 24 hours, wherein the volume ratio of the mass of cellulose to aniline (i.e. solid-liquid ratio) is 1 : 10g/ml, the mol ratio of aniline and ammonium persulfate is 1:1.5, thereby the composite material of synthesizing cellulose and polyaniline, the composite material of cellulose and polyaniline is cleaned 5 times with deionized water, then placed in drying Dry in the oven at 80°C for 15 hours;
  • step A2b Place the mixture obtained in step A2a in a nitrogen atmosphere, calcinate at 300°C for 5h, and then further raise the temperature to 1200°C for carbonization for 2h;
  • A3b Mix the mixture obtained in A2b with KOH at a mass ratio of 1:5, calcinate at 700°C for 2 hours and cool, then wash with 0.5mol/L HCl at 25-50°C for 1-6 hours, then use deionized Wash it several times until the pH is close to 7, and dry it at 80°C for 15 hours.
  • B1b 75% of the composite material prepared in Example 3 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, placed at room temperature and dried for 24h, and then After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading capacity of the active material was 1.5 mg/cm 2 .
  • This embodiment has prepared a kind of composite material, and specific preparation method is:
  • A1a Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
  • A1b Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
  • Glucose specification D-(+)-glucose, GC, ⁇ 99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ⁇ 99%, purchased from Aladdin.
  • A2a Mix the washed cellulose, aniline, and ammonium persulfate into 0.8mol/L H 2 SO 4 and stir at room temperature for 24 hours, wherein the volume ratio of the mass of cellulose to aniline (i.e. solid-liquid ratio) is 1 : 10g/ml, the mol ratio of aniline and ammonium persulfate is 1:1.5, thereby the composite material of synthesizing cellulose and polyaniline, the composite material of cellulose and polyaniline is cleaned 5 times with deionized water, then placed in drying Dry in the oven at 80°C for 15 hours;
  • step A2b Place the mixture obtained in step A2a in a nitrogen atmosphere, calcinate at 300°C for 5h, and then further raise the temperature to 1200°C for carbonization for 2h;
  • A3b Mix the mixture obtained in A2b with KOH at a mass ratio of 1:6, calcinate at 700°C for 2 hours and cool, then wash with 0.5mol/L HCl at 25-50°C for 1-6 hours, then deionize It was washed several times until the pH was close to 7, and dried at 80°C for 15 hours.
  • Figure 1 is the XRD pattern of the composite material carbonized at 1200°C for 2 hours in step A2b of Example 5. It can be seen from the figure that the 002 peak is very sharp, which shows that the crystallinity and graphitization degree of the material have been improved.
  • Fig. 2 is the XRD figure of embodiment 5 gained composite material, can find out from the figure that the broad peak corresponding graphite crystallite (002) plane at about 25 °, interlayer distance is 0.36nm, has proved the amorphous carbon exists, and the (100) peak at 45° indicates that the degree of graphitization of the material is low, and the diffraction angle corresponding to the (002) peak is 24.9°, which is smaller than the 26.2° of the graphite (002) peak, and according to the Bragg equation It can be seen that the smaller the diffraction angle corresponds to the larger interlayer spacing, so it can prove the lattice expansion of the activated carbon material.
  • Fig. 3 is the XPS analysis high-resolution N1s diagram of the composite material of Example 5, and the binding energies 403.2, 400.2 and 398.3eV respectively correspond to nitrogen oxide (24%), pyrrole nitrogen (66%) and pyridine nitrogen (10%). Defects generated by pyrrole nitrogen and pyridinium nitrogen can provide additional lithium ion storage sites.
  • Figure 4 is the pore size distribution diagram of the composite material of Example 5. It can be seen from the figure that the pore size distribution of the activated material is concentrated at 3-4nm and below 2nm, and the average pore volume is about 0.75cm 3 /g.
  • Fig. 5 is the SEM image of the composite material obtained in Example 5, as can be seen from the figure with a complex network of one-dimensional fibers with a granular structure, the diameter is 85 ⁇ 105nm, the structure is a core-shell structure, and this structure is based on Carbon fiber is the core, and a large number of polyaniline particles attached to the surface are the shell.
  • B1b 75% of the composite material prepared in Example 5 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, placed at room temperature and dried for 24h, and then placed in After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading amount of the active material was 1.5 mg/cm 2 .
  • This embodiment has prepared a kind of composite material, and specific preparation method is:
  • A1a Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
  • A1b Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
  • Glucose specification D-(+)-glucose, GC, ⁇ 99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ⁇ 99%, purchased from Aladdin.
  • A2a Mix the washed cellulose, aniline, and ammonium persulfate into 0.8mol/L H 2 SO 4 and stir at room temperature for 24 hours, wherein the volume ratio of the mass of cellulose to aniline (i.e. solid-liquid ratio) is 1 : 10g/ml, the molar ratio of aniline to ammonium persulfate is 1:1.5, thereby synthesizing the composite material of cellulose and polyaniline, the composite material is washed 5 times with deionized water, and then placed in a drying oven at 80°C for 15h ;
  • step A2b Place the mixture obtained in step A2a in a nitrogen atmosphere, calcinate at 300°C for 5h, and then further raise the temperature to 1200°C for carbonization for 2h;
  • A3b Mix the mixture obtained in A2b with KOH at a mass ratio of 1:7, calcinate at 700°C for 2 hours and cool, then wash with 0.5mol/L HCl at 25-50°C for 1-6 hours, then deionize It was washed several times until the pH was close to 7, and dried at 80°C for 15 hours.
  • B1b 75% of the composite material prepared in Example 7 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, placed at room temperature and dried for 24h, and then After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading capacity of the active material was 1.5 mg/cm 2 .
  • This comparative example has prepared a kind of composite material, and concrete preparation method is:
  • A1a Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
  • A1b Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
  • Glucose specification D-(+)-glucose, GC, ⁇ 99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ⁇ 99%, purchased from Aladdin.
  • A2a Mix the washed cellulose, aniline, and ammonium persulfate into 0.8mol/L H 2 SO 4 and stir at room temperature for 24 hours, wherein the volume ratio of the mass of cellulose to aniline (i.e. solid-liquid ratio) is 1 : 10g/ml, the molar ratio of aniline to ammonium persulfate is 1:1.5, thereby synthesizing the composite material of cellulose and polyaniline, the composite material is washed 5 times with deionized water, and then placed in a drying oven at 80°C for 15h ;
  • step A2b The mixture obtained in step A2a is placed in a nitrogen atmosphere, calcined at 300°C for 5h, and then the temperature is further raised to 1200°C for carbonization for 2h.
  • B1b 75% of the composite material prepared in Comparative Example 1 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, placed at room temperature and dried for 24h, and then placed in After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading capacity of the active material was 1.5 mg/cm 2 .
  • This comparative example has prepared a kind of composite material, and concrete preparation method is:
  • A1a Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
  • A1b Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
  • Glucose specification D-(+)-glucose, GC, ⁇ 99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ⁇ 99%, purchased from Aladdin.
  • A2a Put the cleaned cellulose in a nitrogen atmosphere and calcinate at 300°C for 5 hours, the hydroxyl groups on the cellulose will form ether bonds, and crosslinks will occur between the single chains, thereby stabilizing the material, and then further increase the temperature to 1200°C Carry out carbonization for 2h;
  • A2b Mix the carbonized material with KOH at a mass ratio of 1:7, and activate it by calcination at 700°C for 2h, and wash the cooled material with 0.5mol/L HCl at 25-50°C for 1-6h, and then use Deionized and washed several times until the pH is close to 7, and dried at 80°C for 15 hours.
  • B1b 75% of the composite material prepared in Comparative Example 2 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, dried at room temperature for 24h, and then After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading amount of the active material was 1.5 mg/cm 2 .
  • Calculation method of specific surface area The specific surface area is tested by Mike 2020, calculated by BET theory according to the adsorption amount of nitrogen, and obtained by direct test with equipment for sending powder samples.
  • Table 1 compares the specific surface area of the samples prepared in Examples 1, 3, 5, 7 and Comparative Examples 1 and 3. It is found that the specific surface area of the material can be effectively increased by doping and activation, and the specific surface area of Example 7 is the largest.
  • Table 2 is the comparison of the electrochemical properties of the samples prepared in Examples 2, 4, 6, 8 and Comparative Examples 2 and 4, and it is found that the specific capacity of the prepared activated nitrogen-doped bacterial cellulose is higher than that of Comparative Examples 2 and 4, and with With the increase of the magnification, the performance of the material in the examples is more prominent, especially the electrochemical performance of the example 6 is obviously excellent.
  • Table 3 shows the 200-cycle capacity retention of samples prepared in Examples 2, 4, 6, and 8 and Comparative Examples 2 and 4. Examples 2, 4, 6, and 8 show excellent cycle stability at high rates.

Abstract

A composite material, and a preparation method therefor and the use thereof. The composite material comprises carbon fibers and carbonated polyaniline particles attached to the carbon fibers. Pores are present in the composite material, and the pore diameter of the pores is less than or equal to 4 nm. By introducing a hierarchical structure and a nitrogen-containing structure (pyridine nitrogen, pyrrole nitrogen, nitric oxide, etc.), the electrochemical performance of the material can be effectively improved; and the nitrogen-doped composite material is carbonized and activated to synthesize a porous carbon material containing the hierarchical pore structure, such that the migration and storage of lithium ions are facilitated, and the capacity of the material is improved.

Description

一种复合材料及其制备方法和应用A kind of composite material and its preparation method and application 技术领域technical field
本发明属于无机非金属材料技术领域，具体涉及一种复合材料及其制备方法和应用。The invention belongs to the technical field of inorganic non-metallic materials, and in particular relates to a composite material and its preparation method and application.
背景技术Background technique
碳导电材料自从被发现起就具有广阔的发展潜力，它作为一种新型的导电材料既有良好的导电性，又具有较高的可逆容量。同时碳材料因为其低嵌入电压，高稳定性，可调的微观结构而被广泛用于制备锂电池。随着开发高效能、高储量的储能电池材料需求的日益增长，研究新型电池体系代替锂离子电池受到了广泛的关注。Carbon conductive materials have broad development potential since they were discovered. As a new type of conductive material, it has both good conductivity and high reversible capacity. At the same time, carbon materials are widely used in the preparation of lithium batteries because of their low insertion voltage, high stability, and tunable microstructure. With the increasing demand for the development of high-efficiency and high-storage energy storage battery materials, research on new battery systems to replace lithium-ion batteries has received extensive attention.
碳基材料凭借高导电性、成本低以及化学稳定性成为电池负极材料的研究热点，但一些碳材料也存在着容量低、倍率性能差的问题。例如石墨在电池中理论容量仅有279mA h g -1，同时钾离子嵌入/脱出过程中发生巨大的体积膨胀以及低扩散动力学限制了其应用。为解决这些问题，人们在优化碳负极材料上做出了许多努力，例如增加缺陷来提高活性位点、增加比表面积以提高储钾能力等。然而，现有技术中对增加比表面，提升材料的容量，提升碳材料的电化学性能作用有限。 Carbon-based materials have become a research hotspot for battery anode materials due to their high conductivity, low cost and chemical stability, but some carbon materials also have problems of low capacity and poor rate performance. For example, the theoretical capacity of graphite in batteries is only 279mA h g -1 , while the huge volume expansion and low diffusion kinetics of potassium ion intercalation/extraction limit its application. To solve these problems, many efforts have been made to optimize carbon anode materials, such as increasing defects to improve active sites, increasing specific surface area to improve potassium storage capacity, etc. However, the existing technology has limited effects on increasing the specific surface area, increasing the capacity of the material, and improving the electrochemical performance of the carbon material.
因此需要研究一种适合规模化生产，同时具有高电化学性能的碳基复合材料。Therefore, it is necessary to study a carbon-based composite material that is suitable for large-scale production and has high electrochemical performance.
发明内容Contents of the invention
本发明至少解决现有技术问题中存在的上述问题之一，为此本发明提供了一种复合材料，本发明提供的复合材料，通过引入等级结构和含氮结构(吡啶氮、吡咯氮、氧化氮等)，可以有效提升材料的电化学性能；掺氮后的复合材料通过碳化活化，合成含有等级孔结构的多孔碳材料，有助于锂离子的迁移，储存，提升材料的容量，同时形成核壳结构，缓解了锂离子脱嵌过程中产生的体积变化。The present invention at least solves one of the above-mentioned problems existing in the prior art problems, for this reason the present invention provides a kind of composite material, the composite material provided by the present invention, by introducing hierarchical structure and nitrogen-containing structure (pyridine nitrogen, pyrrole nitrogen, oxidation Nitrogen, etc.), can effectively improve the electrochemical performance of the material; the composite material after nitrogen doping is activated by carbonization, and a porous carbon material with a hierarchical pore structure is synthesized, which is helpful for the migration and storage of lithium ions, and improves the capacity of the material. The core-shell structure alleviates the volume change during the lithium ion deintercalation process.
本发明还提供了一种上述复合材料的制备方法。The present invention also provides a preparation method of the composite material.
本发明还提供了一种包括上述复合材料的储能装置。The present invention also provides an energy storage device comprising the above-mentioned composite material.
根据本发明的一个方面，提供了一种复合材料，包括碳纤维和附着在所述碳纤维上 的聚苯胺颗粒；According to one aspect of the present invention, a kind of composite material is provided, comprise carbon fiber and the polyaniline particle that is attached on the described carbon fiber;
所述复合材料上存在孔；Pores are present in the composite material;
所述孔的孔径≤4nm。The diameter of the pores is ≤4nm.
本发明的复合材料至少具有以下有益效果：The composite material of the present invention has at least the following beneficial effects:
1、本发明通过引入等级结构和含氮结构(吡啶氮、吡咯氮、氧化氮等)，可以有效提升材料的电化学性能。1. The present invention can effectively improve the electrochemical performance of the material by introducing a hierarchical structure and a nitrogen-containing structure (pyridine nitrogen, pyrrole nitrogen, nitrogen oxide, etc.).
2、本发明将掺氮后的复合材料通过碳化活化，合成含有等级孔结构的多孔碳材料，有助于锂离子的迁移，储存，提升材料的容量。2. The present invention activates the nitrogen-doped composite material through carbonization to synthesize a porous carbon material containing a hierarchical pore structure, which is helpful for the migration and storage of lithium ions, and improves the capacity of the material.
在本发明的一些实施方式中，所述复合材料的孔径集中分布在3～4nm和2nm以下，平均孔体积约为0.75cm 3/g。 In some embodiments of the present invention, the composite material has a concentrated distribution of pore sizes between 3-4 nm and below 2 nm, and an average pore volume of about 0.75 cm 3 /g.
在本发明的一些实施方式中，所述碳纤维的直径为85～105nm。In some embodiments of the present invention, the carbon fiber has a diameter of 85-105 nm.
在本发明的一些实施方式中，所述纤维素的制备原料包括细菌纤维素。In some embodiments of the present invention, the raw material for the preparation of the cellulose includes bacterial cellulose.
在本发明的一些实施方式中，所述细菌纤维素的制备原料包括汉氏驹形杆菌。In some embodiments of the present invention, the raw material for the preparation of bacterial cellulose includes Bacillus hansenii.
本发明以细菌纤维素纳米纤维为核，以聚苯胺为壳，形成核壳结构，从而缓解锂离子脱嵌过程中产生的体积变化。The invention uses bacterial cellulose nanofibers as the core and polyaniline as the shell to form a core-shell structure, thereby alleviating the volume change generated during the deintercalation process of lithium ions.
本发明以细菌纤维素为基底合成聚苯胺，减少了聚合物的团聚程度，提高了分散均匀性，增强了聚合物与细菌纤维素的接触。The invention synthesizes polyaniline with bacterial cellulose as the base, reduces the aggregation degree of the polymer, improves the uniformity of dispersion, and strengthens the contact between the polymer and the bacterial cellulose.
本发明的另一个方面提出了所述的复合材料的制备方法，包括以下步骤：Another aspect of the present invention proposes the preparation method of described composite material, comprises the following steps:
S1：将所述纤维素、苯胺、引发剂和掺杂剂混合后除杂，干燥；S1: After mixing the cellulose, aniline, initiator and dopant, removing impurities and drying;
S2：将步骤S1所得混合物在氮气气氛下热处理；S2: heat treating the mixture obtained in step S1 under nitrogen atmosphere;
S3：将步骤S2所得混合物和致孔剂混合，热处理，除杂，干燥，即得到所述复合材料。S3: Mix the mixture obtained in step S2 with the porogen, heat treat, remove impurities, and dry to obtain the composite material.
在本发明的一些实施方式中，所述纤维素的制备方法包括以下步骤：In some embodiments of the present invention, the preparation method of the cellulose comprises the following steps:
A1：向培养基中加入柠檬酸，混合，以所述汉氏驹形杆菌为菌种发酵，形成细菌纤维素；A1: Add citric acid to the culture medium, mix, and ferment with the Bacillus hansenii as the strain to form bacterial cellulose;
A2：将所述细菌纤维素以碱性溶液洗涤，除杂，即得到所述纤维素。A2: washing the bacterial cellulose with an alkaline solution to remove impurities to obtain the cellulose.
在本发明的一些实施方式中，步骤A1中，所述培养基为葡萄糖、酵母精、蛋白胨、磷酸二氢钠组成的混合物。In some embodiments of the present invention, in step A1, the medium is a mixture composed of glucose, yeast extract, peptone, and sodium dihydrogen phosphate.
在本发明的一些实施方式中，所述葡萄糖、所述酵母精、所述蛋白胨、所述磷酸二氢钠的质量比为1:(0.2～0.3)：(0.2～0.3)：(0.1～0.2)。In some embodiments of the present invention, the mass ratio of the glucose, the yeast extract, the peptone, and the sodium dihydrogen phosphate is 1:(0.2～0.3):(0.2～0.3):(0.1～0.2 ).
在本发明的一些实施方式中，步骤A1中，所述柠檬酸的浓度为1～5g/L。In some embodiments of the present invention, in step A1, the concentration of the citric acid is 1-5 g/L.
在本发明的一些实施方式中，步骤A1中，所述汉氏驹形杆菌发酵的时间为15～30d。In some embodiments of the present invention, in step A1, the fermentation time of the Bacillus hansiformis is 15-30 days.
在本发明的一些实施方式中，步骤A1中，所述汉氏驹形杆菌发酵的温度为25～50℃。In some embodiments of the present invention, in step A1, the fermentation temperature of the Bacillus hansiformis is 25-50°C.
在本发明的一些实施方式中，步骤A2中，所述碱性溶液包括KOH溶液或NaOH溶液中的一种。In some embodiments of the present invention, in step A2, the alkaline solution includes one of KOH solution or NaOH solution.
在本发明的一些实施方式中，步骤A2中，所述碱性溶液的浓度为0.1～3mol/L。In some embodiments of the present invention, in step A2, the concentration of the alkaline solution is 0.1-3 mol/L.
在本发明的一些实施方式中，步骤A2中，所述除杂过程为在碱性溶液中搅拌10～30h。In some embodiments of the present invention, in step A2, the impurity removal process is stirring in an alkaline solution for 10-30 hours.
在本发明的一些实施方式中，步骤A2中，在碱性溶液中搅拌后再用去离子水多次清洗至pH接近7。In some embodiments of the present invention, in step A2, after stirring in an alkaline solution, wash with deionized water several times until the pH is close to 7.
根据《产纤维素菌株的分离鉴定及产量相关性》一文中对比了5个不同菌属，包括醋酸杆菌属、驹形杆菌属、葡糖醋杆菌属、沙雷氏菌属和乳酸杆菌属，其中高产菌株集中分布于汉氏驹形杆菌和中间驹形杆菌，因此所述汉氏驹形杆菌获得的细菌纤维素具有产量高、遗传代谢稳定的优点，从而降低了生产成本。According to the article "Isolation, Identification and Yield Correlation of Cellulose-producing Strains", five different genera were compared, including Acetobacter, Oomaformis, Gluconacetobacter, Serratia and Lactobacillus, Among them, the high-yield strains are concentrated in Bacillus hansenii and Bacterium hansenii. Therefore, the bacterial cellulose obtained by the bacterium hansenii has the advantages of high yield and stable genetic metabolism, thereby reducing the production cost.
在本发明的一些实施方式中，步骤S1中，所述纤维素的质量和所述苯胺原液的体积比(即固液比)为1g:5～20ml，苯胺原液AR纯度≥99.5％。In some embodiments of the present invention, in step S1, the mass ratio of the cellulose to the volume ratio of the aniline stock solution (ie solid-to-liquid ratio) is 1g:5-20ml, and the purity AR of the aniline stock solution is ≥99.5%.
在本发明的一些实施方式中，步骤S1中，所述引发剂包括过硫酸盐、过氧化氢、重铬酸盐和氯化铁中的一种。In some embodiments of the present invention, in step S1, the initiator includes one of persulfate, hydrogen peroxide, dichromate and ferric chloride.
在本发明的一些优选的实施方式中，步骤S1中，所述引发剂包括过硫酸盐。In some preferred embodiments of the present invention, in step S1, the initiator includes persulfate.
在本发明的一些更优选的实施方式中，步骤S1中，所述引发剂包括过硫酸铵。In some more preferred embodiments of the present invention, in step S1, the initiator includes ammonium persulfate.
在本发明的一些实施方式中，步骤S1中，所述苯胺与所述引发剂的摩尔比为1:(1～2)。In some embodiments of the present invention, in step S1, the molar ratio of the aniline to the initiator is 1:(1-2).
在本发明的一些实施方式中，步骤S1中，所述掺杂剂包括HCl溶液或H 2SO 4溶液中的至少一种。 In some embodiments of the present invention, in step S1, the dopant includes at least one of HCl solution or H 2 SO 4 solution.
在本发明的一些优选的实施方式中，所述HCl溶液或H 2SO 4溶液的浓度为0.1～2mol/L。 In some preferred embodiments of the present invention, the concentration of the HCl solution or the H 2 SO 4 solution is 0.1-2 mol/L.
在本发明的一些实施方式中，步骤S1中，所述混合的温度为0～30℃。In some embodiments of the present invention, in step S1, the mixing temperature is 0-30°C.
在本发明的一些实施方式中，步骤S1中，所述混合的时间为24～50h。In some embodiments of the present invention, in step S1, the mixing time is 24-50 hours.
纤维素中的大量的羟基与苯胺中的胺官能团形成氢键，起到桥接配体的作用，有助于苯胺单体吸附在它的表面上，而过硫酸铵作为聚合反应的引发剂，酸作为掺杂剂，使整个纤维网发生均匀的聚合反应，从而合成纤维素与聚苯胺的复合材料。A large number of hydroxyl groups in cellulose form hydrogen bonds with the amine functional groups in aniline, which act as bridging ligands and help the aniline monomer to adsorb on its surface, while ammonium persulfate acts as the initiator of the polymerization reaction, and the acid As a dopant, the entire fiber network undergoes a uniform polymerization reaction, thereby synthesizing a composite material of cellulose and polyaniline.
在本发明的一些实施方式中，步骤S1中，所述除杂为以去离子水清洗步骤S1所得混合物3～7次。In some embodiments of the present invention, in step S1, the impurity removal is washing the mixture obtained in step S1 with deionized water for 3-7 times.
在本发明的一些实施方式中，步骤S1中，所述干燥的时间为5～24h。In some embodiments of the present invention, in step S1, the drying time is 5-24 hours.
在本发明的一些实施方式中，步骤S1中，所述干燥的温度为50～120℃。In some embodiments of the present invention, in step S1, the drying temperature is 50-120°C.
在本发明的一些实施方式中，步骤S2中，所述热处理包括第一次热处理和第二次热处理。In some embodiments of the present invention, in step S2, the heat treatment includes a first heat treatment and a second heat treatment.
在本发明的一些优选的实施方式中，所述第一次热处理的温度为200～400℃。In some preferred embodiments of the present invention, the temperature of the first heat treatment is 200-400°C.
在本发明的一些优选的实施方式中，所述第一次热处理的时间为0.5～14h。In some preferred embodiments of the present invention, the time for the first heat treatment is 0.5-14 hours.
第一次热处理时，纤维素上的羟基会形成醚键，单链间产生交联，从而使材料稳定化。During the first heat treatment, the hydroxyl groups on the cellulose will form ether bonds, and cross-links will occur between the single chains, thereby stabilizing the material.
在本发明的一些优选的实施方式中，所述第二次热处理的温度为900～1200℃。In some preferred embodiments of the present invention, the temperature of the second heat treatment is 900-1200°C.
在本发明的一些优选的实施方式中，所述第二次热处理的时间为1～5h。In some preferred embodiments of the present invention, the time of the second heat treatment is 1-5 hours.
所述第二次热处理，可去除杂质分子同时修复小部分缺陷提高石墨化度，另外所述热处理后的材料中，氮以掺杂物的形式存在，可提升所得材料与电解液的润湿性，形成的吡咯氮、吡啶氮和氧化氮造成片层边缘弯曲和空位等缺陷将会作为活性位点储存锂离子。The second heat treatment can remove impurity molecules while repairing a small number of defects to increase the degree of graphitization. In addition, in the heat-treated material, nitrogen exists in the form of dopants, which can improve the wettability of the obtained material and the electrolyte , the formed pyrrole nitrogen, pyridinium nitrogen, and nitrogen oxide cause defects such as sheet edge bending and vacancies that will serve as active sites to store lithium ions.
在本发明的一些实施方式中，步骤S3中，所述致孔剂包括KOH和NaOH中的一种。In some embodiments of the present invention, in step S3, the porogen includes one of KOH and NaOH.
在本发明的一些优选的实施方式中，步骤S3中，所述致孔剂为KOH。In some preferred embodiments of the present invention, in step S3, the porogen is KOH.
在本发明的一些实施方式中，步骤S3中，所述步骤S2所得混合物和所述致孔剂的质量比为1:(2～10)。In some embodiments of the present invention, in step S3, the mass ratio of the mixture obtained in step S2 to the porogen is 1:(2-10).
在本发明的一些实施方式中，步骤S3中，所述热处理的温度为700～900℃。In some embodiments of the present invention, in step S3, the temperature of the heat treatment is 700-900°C.
在本发明的一些实施方式中，步骤S3中，所述热处理的时间为1～4h。In some embodiments of the present invention, in step S3, the time of the heat treatment is 1-4 hours.
在本发明的一些实施方式中，步骤S3中，所述除杂包括酸洗。In some embodiments of the present invention, in step S3, the impurity removal includes pickling.
在本发明的一些实施方式中，步骤S3中，所述酸洗过程中使用的酸为HCl或H 2SO 4中的一种。 In some embodiments of the present invention, in step S3, the acid used in the pickling process is one of HCl or H 2 SO 4 .
在本发明的一些实施方式中，步骤S3中，所述酸洗的温度为在25～50℃。In some embodiments of the present invention, in step S3, the temperature of the pickling is 25-50°C.
在本发明的一些实施方式中，步骤S3中，所述酸洗的时间为1～6h。In some embodiments of the present invention, in step S3, the acid washing time is 1-6 hours.
步骤S2所得混合物和所述KOH进行活化时，得到钾及其化合物，钾及其化合物包括K、K 2CO 3和K 2O，其中K 2CO 3继续反应产生的CO 2、CO，同活化产生的N 2O，NO和结合水溢出，使材料产生孔隙；金属钾嵌入到碳中，晶格膨胀。冷却酸洗后，嵌入的钾被移除后留下很多的空位，这些在相互连接的纤维网络中的微孔和介孔通过等级组装有助于电解液的渗透，为锂离子和电子的传输提供了连续的通道，也减少锂离子传输路径长度，还可作为额外的活性位点储存锂离子。同时，核壳结构适应锂离子脱嵌过程中造成的体积变化，在高倍率下具有优异的循环稳定性。 When the mixture obtained in step S2 and the KOH are activated, potassium and its compounds are obtained. Potassium and its compounds include K, K 2 CO 3 and K 2 O, wherein CO 2 and CO produced by the continuous reaction of K 2 CO 3 are the same as the activated The generated N 2 O, NO and bound water overflow, making the material porosity; metal potassium is embedded in the carbon, and the lattice expands. After cooling and pickling, the intercalated potassium is removed leaving a lot of vacancies, and these micropores and mesopores in the interconnected fiber network facilitate the penetration of the electrolyte through hierarchical assembly, providing for the transport of lithium ions and electrons. Provides a continuous channel, also reduces the length of the lithium ion transport path, and can also be used as an additional active site to store lithium ions. At the same time, the core-shell structure adapts to the volume change caused by the lithium ion deintercalation process, and has excellent cycle stability at high rates.
附图说明Description of drawings
下面结合附图和实施例对本发明做进一步的说明，其中：The present invention will be further described below in conjunction with accompanying drawing and embodiment, wherein:
图1为实施例5步骤A2b复合材料1200℃进行碳化2h的XRD图；Fig. 1 is the XRD figure of embodiment 5 step A2b composite material 1200 ℃ of carbonization 2h;
图2为实施例5的复合材料的XRD图；Fig. 2 is the XRD figure of the composite material of embodiment 5;
图3为实施例5的复合材料的XPS分析高分辨N1s图；Fig. 3 is the XPS analysis high-resolution N1s figure of the composite material of embodiment 5;
图4为实施例5的复合材料的孔径分布图；Fig. 4 is the pore size distribution figure of the composite material of embodiment 5;
图5为实施例5的复合材料的SEM图。5 is a SEM image of the composite material of Example 5.
具体实施方式Detailed ways
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。The conception and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments, so as to fully understand the purpose, features and effects of the present invention. Apparently, the described embodiments are only some of the embodiments of the present invention, rather than all of them. Based on the embodiments of the present invention, other embodiments obtained by those skilled in the art without creative efforts belong to The protection scope of the present invention.
实施例1Example 1
本实施例制备了一种复合材料，具体制备方法为：This embodiment has prepared a kind of composite material, and specific preparation method is:
A1.制备纤维素A1. Preparation of cellulose
A1a：将葡萄糖、酵母精、蛋白胨、磷酸二氢钠混合，混合质量比为4:1:1:0.6，向混合物中加入柠檬酸，柠檬酸的浓度为1.2g/L，搅拌均匀，以汉氏驹形杆菌为菌种在30℃发酵15天，形成细菌纤维素；A1a: Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
A1b：将细菌纤维素放入到2mol/L的NaOH溶液中，搅拌20h，去除杂质剥离出纯净的纤维素，再用去离子水多次清洗至pH接近7。A1b: Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
葡萄糖规格：D-(+)-葡萄糖，GC，≥99.5％，购买于阿拉丁；酵母精(酵母浸出粉)：超级纯，用于微生物，购买于阿拉丁；蛋白胨：酵母蛋白胨，购买于阿拉丁；磷酸二氢钠：用于分子生物学，≥99％，购买于阿拉丁。Glucose specification: D-(+)-glucose, GC, ≥99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ≥99%, purchased from Aladdin.
A2.制备复合材料A2. Preparation of composite materials
A2a：将清洗后的纤维素、苯胺、过硫酸铵混合放入到0.8mol/L的H 2SO 4中室温搅拌24h，其中纤维素的质量与苯胺的体积比(即固液比)为1g:10ml，苯胺与过硫酸铵的摩尔比为1:1.5，从而合成纤维素与聚苯胺的复合材料，将纤维素与聚苯胺的复合材料用去离子水清洗5次，之后置于干燥箱中80℃干燥15h； A2a: Mix the washed cellulose, aniline, and ammonium persulfate into 0.8mol/L H 2 SO 4 and stir at room temperature for 24 hours, wherein the volume ratio of the mass of cellulose to aniline (i.e. solid-to-liquid ratio) is 1g : 10ml, the mol ratio of aniline and ammonium persulfate is 1:1.5, thereby the composite material of synthesizing cellulose and polyaniline, the composite material of cellulose and polyaniline is washed 5 times with deionized water, and then placed in a drying box Dry at 80°C for 15 hours;
A2b：将A2a步骤所得的混合物置于氮气气氛中，在300℃下煅烧5h，再进一步将温度提升到1200℃进行碳化2h；A2b: Place the mixture obtained in step A2a in a nitrogen atmosphere, calcinate at 300°C for 5h, and then further raise the temperature to 1200°C for carbonization for 2h;
A3b：将A2b中所得到的混合物与KOH混合，质量比为1:4，在700℃下煅烧2h冷却后，用0.5mol/L的HCl在25～50℃清洗1～6h，接着用去离子多次清洗至pH接近7， 在80℃干燥15h，即得到所述复合材料。A3b: Mix the mixture obtained in A2b with KOH at a mass ratio of 1:4, calcinate at 700°C for 2 hours and cool, then wash with 0.5mol/L HCl at 25-50°C for 1-6 hours, then deionize The composite material was obtained by washing several times until the pH was close to 7, and drying at 80° C. for 15 hours.
实施例2Example 2
本实施例制备了一种电极材料，具体制备方法为：In this embodiment, a kind of electrode material is prepared, and the specific preparation method is as follows:
B1.电极材料B1. Electrode material
B1b：将75％的实施例1制备的复合材料(用作活性材料)，15％炭黑和10％PVDF在NMP中均匀混合，之后涂布在铜箔上，置于室温干燥24h，再在80℃下干燥24h，将干燥后的电极材料裁剪成圆片，活性材料的负载量为1.5mg/cm 2。 B1b: 75% of the composite material prepared in Example 1 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, placed at room temperature and dried for 24h, and then After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading capacity of the active material was 1.5 mg/cm 2 .
实施例3Example 3
本实施例制备了一种复合材料，具体制备方法为：This embodiment has prepared a kind of composite material, and specific preparation method is:
A1.制备纤维素A1. Preparation of cellulose
A1a：将葡萄糖、酵母精、蛋白胨、磷酸二氢钠混合，混合质量比为4:1:1:0.6，向混合物中加入柠檬酸，柠檬酸的浓度为1.2g/L，搅拌均匀，以汉氏驹形杆菌为菌种在30℃下发酵15天，形成细菌纤维素；A1a: Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
A1b：将细菌纤维素放入到2mol/L的NaOH溶液中，搅拌20h，去除杂质剥离出纯净的纤维素，再用去离子水多次清洗至pH接近7。A1b: Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
葡萄糖规格：D-(+)-葡萄糖，GC，≥99.5％，购买于阿拉丁；酵母精(酵母浸出粉)：超级纯，用于微生物，购买于阿拉丁；蛋白胨：酵母蛋白胨，购买于阿拉丁；磷酸二氢钠：用于分子生物学，≥99％，购买于阿拉丁。Glucose specification: D-(+)-glucose, GC, ≥99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ≥99%, purchased from Aladdin.
A2.制备复合材料A2. Preparation of composite materials
A2a：将清洗后的纤维素、苯胺、过硫酸铵混合放入到0.8mol/L的H 2SO 4中室温搅拌24h，其中纤维素的质量与苯胺的体积比(即固液比)为1:10g/ml，苯胺与过硫酸铵的摩尔比为1:1.5，从而合成纤维素与聚苯胺的复合材料，将纤维素与聚苯胺的复合材料用去离子水清洗5次，之后置于干燥箱中80℃干燥15h； A2a: Mix the washed cellulose, aniline, and ammonium persulfate into 0.8mol/L H 2 SO 4 and stir at room temperature for 24 hours, wherein the volume ratio of the mass of cellulose to aniline (i.e. solid-liquid ratio) is 1 : 10g/ml, the mol ratio of aniline and ammonium persulfate is 1:1.5, thereby the composite material of synthesizing cellulose and polyaniline, the composite material of cellulose and polyaniline is cleaned 5 times with deionized water, then placed in drying Dry in the oven at 80°C for 15 hours;
A2b：将A2a步骤所得的混合物置于氮气气氛中，在300℃下煅烧5h，再进一步将温度提升到1200℃进行碳化2h；A2b: Place the mixture obtained in step A2a in a nitrogen atmosphere, calcinate at 300°C for 5h, and then further raise the temperature to 1200°C for carbonization for 2h;
A3b：将A2b中所得到的混合物与KOH混合，质量比为1:5，在700℃下煅烧2h冷却后，用0.5mol/L的HCl在25～50℃清洗1～6h，接着用去离子多次清洗至pH接近7，在80℃干燥15h即得。A3b: Mix the mixture obtained in A2b with KOH at a mass ratio of 1:5, calcinate at 700°C for 2 hours and cool, then wash with 0.5mol/L HCl at 25-50°C for 1-6 hours, then use deionized Wash it several times until the pH is close to 7, and dry it at 80°C for 15 hours.
实施例4Example 4
本实施例制备了一种电极材料，具体制备方法为：In this embodiment, a kind of electrode material is prepared, and the specific preparation method is as follows:
B1.电极材料B1. Electrode material
B1b：将75％的实施例3制备的复合材料(用作活性材料)，15％炭黑和10％PVDF在NMP中均匀混合，之后涂布在铜箔上，置于室温干燥24h，再在80℃下干燥24h，将干燥后的电极材料裁剪成圆片，活性材料的负载量为1.5mg/cm 2。 B1b: 75% of the composite material prepared in Example 3 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, placed at room temperature and dried for 24h, and then After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading capacity of the active material was 1.5 mg/cm 2 .
实施例5Example 5
本实施例制备了一种复合材料，具体制备方法为：This embodiment has prepared a kind of composite material, and specific preparation method is:
A1.制备纤维素A1. Preparation of cellulose
A1a：将葡萄糖、酵母精、蛋白胨、磷酸二氢钠混合，混合质量比为4:1:1:0.6，向混合物中加入柠檬酸，柠檬酸的浓度为1.2g/L，搅拌均匀，以汉氏驹形杆菌为菌种在30℃发酵15天，形成细菌纤维素；A1a: Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
A1b：将细菌纤维素放入到2mol/L的NaOH溶液中，搅拌20h，去除杂质剥离出纯净的纤维素，再用去离子水多次清洗至pH接近7。A1b: Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
葡萄糖规格：D-(+)-葡萄糖，GC，≥99.5％，购买于阿拉丁；酵母精(酵母浸出粉)：超级纯，用于微生物，购买于阿拉丁；蛋白胨：酵母蛋白胨，购买于阿拉丁；磷酸二氢钠：用于分子生物学，≥99％，购买于阿拉丁。Glucose specification: D-(+)-glucose, GC, ≥99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ≥99%, purchased from Aladdin.
A2.制备复合材料A2. Preparation of composite materials
A2a：将清洗后的纤维素、苯胺、过硫酸铵混合放入到0.8mol/L的H 2SO 4中室温搅拌24h，其中纤维素的质量与苯胺的体积比(即固液比)为1:10g/ml，苯胺与过硫酸铵的摩尔比为1:1.5，从而合成纤维素与聚苯胺的复合材料，将纤维素与聚苯胺的复合材料用去离子水清洗5次，之后置于干燥箱中80℃干燥15h； A2a: Mix the washed cellulose, aniline, and ammonium persulfate into 0.8mol/L H 2 SO 4 and stir at room temperature for 24 hours, wherein the volume ratio of the mass of cellulose to aniline (i.e. solid-liquid ratio) is 1 : 10g/ml, the mol ratio of aniline and ammonium persulfate is 1:1.5, thereby the composite material of synthesizing cellulose and polyaniline, the composite material of cellulose and polyaniline is cleaned 5 times with deionized water, then placed in drying Dry in the oven at 80°C for 15 hours;
A2b：将A2a步骤所得的混合物置于氮气气氛中，300℃煅烧5h，再进一步将温度提升到1200℃进行碳化2h；A2b: Place the mixture obtained in step A2a in a nitrogen atmosphere, calcinate at 300°C for 5h, and then further raise the temperature to 1200°C for carbonization for 2h;
A3b：将A2b中所得到的混合物与KOH混合，质量比为1:6，在700℃下煅烧2h冷却后，用0.5mol/L的HCl在25～50℃清洗1～6h，接着用去离子多次清洗至pH接近7，在80℃干燥15h。A3b: Mix the mixture obtained in A2b with KOH at a mass ratio of 1:6, calcinate at 700°C for 2 hours and cool, then wash with 0.5mol/L HCl at 25-50°C for 1-6 hours, then deionize It was washed several times until the pH was close to 7, and dried at 80°C for 15 hours.
图1为实施例5步骤A2b复合材料1200℃进行碳化2h的XRD图，由图中可以看出002峰十分尖锐，由此可知材料结晶度和石墨化度得到了提高。Figure 1 is the XRD pattern of the composite material carbonized at 1200°C for 2 hours in step A2b of Example 5. It can be seen from the figure that the 002 peak is very sharp, which shows that the crystallinity and graphitization degree of the material have been improved.
图2为实施例5所得复合材料的XRD图，从图中可以看出在25°左右的较宽的峰对应石墨微晶(002)晶面，层间距为0.36nm，证明了无定形碳的存在，而45°的(100)峰则说明材料的石墨化度较低，同时其中(002)峰对应的衍射角度在24.9°，较石墨(002)峰的26.2°偏小，而根据布拉格方程可知越小的衍射角度对应更大的层间距，因此可证明活化后的碳材的晶格膨胀。Fig. 2 is the XRD figure of embodiment 5 gained composite material, can find out from the figure that the broad peak corresponding graphite crystallite (002) plane at about 25 °, interlayer distance is 0.36nm, has proved the amorphous carbon exists, and the (100) peak at 45° indicates that the degree of graphitization of the material is low, and the diffraction angle corresponding to the (002) peak is 24.9°, which is smaller than the 26.2° of the graphite (002) peak, and according to the Bragg equation It can be seen that the smaller the diffraction angle corresponds to the larger interlayer spacing, so it can prove the lattice expansion of the activated carbon material.
图3为实施例5的复合材料的XPS分析高分辨N1s图，结合能403.2,400.2和398.3eV分别对应氧化氮(24％)、吡咯氮(66％)和吡啶氮(10％)。吡咯氮和吡啶氮产生的缺陷可以提供额外的锂离子储存位点。Fig. 3 is the XPS analysis high-resolution N1s diagram of the composite material of Example 5, and the binding energies 403.2, 400.2 and 398.3eV respectively correspond to nitrogen oxide (24%), pyrrole nitrogen (66%) and pyridine nitrogen (10%). Defects generated by pyrrole nitrogen and pyridinium nitrogen can provide additional lithium ion storage sites.
图4为实施例5的复合材料的孔径分布图，由图可知，活化后的材料孔径集中分布在3～4nm和2nm以下，而平均孔体积则在0.75cm 3/g左右。 Figure 4 is the pore size distribution diagram of the composite material of Example 5. It can be seen from the figure that the pore size distribution of the activated material is concentrated at 3-4nm and below 2nm, and the average pore volume is about 0.75cm 3 /g.
图5为实施例5所得复合材料的SEM图，从图中可以看出带有颗粒状结构的一维纤维构成的复杂网状，直径为85～105nm，结构为核壳结构，此结构则以碳纤维为核，表面附着的大量聚苯胺颗粒为壳。Fig. 5 is the SEM image of the composite material obtained in Example 5, as can be seen from the figure with a complex network of one-dimensional fibers with a granular structure, the diameter is 85 ~ 105nm, the structure is a core-shell structure, and this structure is based on Carbon fiber is the core, and a large number of polyaniline particles attached to the surface are the shell.
实施例6Example 6
本实施例制备了一种电极材料，具体制备方法为：In this embodiment, a kind of electrode material is prepared, and the specific preparation method is as follows:
B1.电极材料B1. Electrode material
B1b：将75％的实施例5制备的复合材料(用作活性材料)，15％炭黑和10％PVDF在NMP中均匀混合，之后涂布在铜箔上，置于室温干燥24h，再在80℃下干燥24h， 将干燥后的电极材料裁剪成圆片，活性材料的负载量为1.5mg/cm 2。 B1b: 75% of the composite material prepared in Example 5 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, placed at room temperature and dried for 24h, and then placed in After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading amount of the active material was 1.5 mg/cm 2 .
实施例7Example 7
本实施例制备了一种复合材料，具体制备方法为：This embodiment has prepared a kind of composite material, and specific preparation method is:
A1.制备纤维素A1. Preparation of cellulose
A1a：将葡萄糖、酵母精、蛋白胨、磷酸二氢钠混合，混合质量比为4:1:1:0.6，向混合物中加入柠檬酸，柠檬酸的浓度为1.2g/L，搅拌均匀，以汉氏驹形杆菌为菌种在30℃发酵15天，形成细菌纤维素；A1a: Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
A1b：将细菌纤维素放入到2mol/L的NaOH溶液中，搅拌20h，去除杂质剥离出纯净的纤维素，再用去离子水多次清洗至pH接近7。A1b: Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
葡萄糖规格：D-(+)-葡萄糖，GC，≥99.5％，购买于阿拉丁；酵母精(酵母浸出粉)：超级纯，用于微生物，购买于阿拉丁；蛋白胨：酵母蛋白胨，购买于阿拉丁；磷酸二氢钠：用于分子生物学，≥99％，购买于阿拉丁。Glucose specification: D-(+)-glucose, GC, ≥99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ≥99%, purchased from Aladdin.
A2.制备复合材料A2. Preparation of composite materials
A2a：将清洗后的纤维素、苯胺、过硫酸铵混合放入到0.8mol/L的H 2SO 4中室温搅拌24h，其中纤维素的质量与苯胺的体积比(即固液比)为1:10g/ml，苯胺与过硫酸铵的摩尔比为1:1.5，从而合成纤维素与聚苯胺的复合材料，将复合材料用去离子水清洗5次，之后置于干燥箱中80℃干燥15h； A2a: Mix the washed cellulose, aniline, and ammonium persulfate into 0.8mol/L H 2 SO 4 and stir at room temperature for 24 hours, wherein the volume ratio of the mass of cellulose to aniline (i.e. solid-liquid ratio) is 1 : 10g/ml, the molar ratio of aniline to ammonium persulfate is 1:1.5, thereby synthesizing the composite material of cellulose and polyaniline, the composite material is washed 5 times with deionized water, and then placed in a drying oven at 80°C for 15h ;
A2b：将A2a步骤所得的混合物置于氮气气氛中，300℃煅烧5h，再进一步将温度提升到1200℃进行碳化2h；A2b: Place the mixture obtained in step A2a in a nitrogen atmosphere, calcinate at 300°C for 5h, and then further raise the temperature to 1200°C for carbonization for 2h;
A3b：将A2b中所得到的混合物与KOH混合，质量比为1:7，在700℃下煅烧2h冷却后，用0.5mol/L的HCl在25～50℃清洗1～6h，接着用去离子多次清洗至pH接近7，在80℃干燥15h。A3b: Mix the mixture obtained in A2b with KOH at a mass ratio of 1:7, calcinate at 700°C for 2 hours and cool, then wash with 0.5mol/L HCl at 25-50°C for 1-6 hours, then deionize It was washed several times until the pH was close to 7, and dried at 80°C for 15 hours.
实施例8Example 8
本实施例制备了一种电极材料，具体制备方法为：In this embodiment, a kind of electrode material is prepared, and the specific preparation method is as follows:
B1.电极材料B1. Electrode material
B1b：将75％的实施例7制备的复合材料(用作活性材料)，15％炭黑和10％PVDF在NMP中均匀混合，之后涂布在铜箔上，置于室温干燥24h，再在80℃下干燥24h，将干燥后的电极材料裁剪成圆片，活性材料的负载量为1.5mg/cm 2。 B1b: 75% of the composite material prepared in Example 7 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, placed at room temperature and dried for 24h, and then After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading capacity of the active material was 1.5 mg/cm 2 .
对比例1Comparative example 1
本对比例制备了一种复合材料，具体制备方法为：This comparative example has prepared a kind of composite material, and concrete preparation method is:
A1.制备纤维素A1. Preparation of cellulose
A1a：将葡萄糖、酵母精、蛋白胨、磷酸二氢钠混合，混合质量比为4:1:1:0.6，向混合物中加入柠檬酸，柠檬酸的浓度为1.2g/L，搅拌均匀，以汉氏驹形杆菌为菌种在30℃发酵15天，形成细菌纤维素；A1a: Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
A1b：将细菌纤维素放入到2mol/L的NaOH溶液中，搅拌20h，去除杂质剥离出纯净的纤维素，再用去离子水多次清洗至pH接近7。A1b: Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
葡萄糖规格：D-(+)-葡萄糖，GC，≥99.5％，购买于阿拉丁；酵母精(酵母浸出粉)：超级纯，用于微生物，购买于阿拉丁；蛋白胨：酵母蛋白胨，购买于阿拉丁；磷酸二氢钠：用于分子生物学，≥99％，购买于阿拉丁。Glucose specification: D-(+)-glucose, GC, ≥99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ≥99%, purchased from Aladdin.
A2.制备复合材料A2. Preparation of composite materials
A2a：将清洗后的纤维素、苯胺、过硫酸铵混合放入到0.8mol/L的H 2SO 4中室温搅拌24h，其中纤维素的质量与苯胺的体积比(即固液比)为1:10g/ml，苯胺与过硫酸铵的摩尔比为1:1.5，从而合成纤维素与聚苯胺的复合材料，将复合材料用去离子水清洗5次，之后置于干燥箱中80℃干燥15h； A2a: Mix the washed cellulose, aniline, and ammonium persulfate into 0.8mol/L H 2 SO 4 and stir at room temperature for 24 hours, wherein the volume ratio of the mass of cellulose to aniline (i.e. solid-liquid ratio) is 1 : 10g/ml, the molar ratio of aniline to ammonium persulfate is 1:1.5, thereby synthesizing the composite material of cellulose and polyaniline, the composite material is washed 5 times with deionized water, and then placed in a drying oven at 80°C for 15h ;
A2b：将A2a步骤所得的混合物置于氮气气氛中，300℃煅烧5h，再进一步将温度提升到1200℃进行碳化2h。A2b: The mixture obtained in step A2a is placed in a nitrogen atmosphere, calcined at 300°C for 5h, and then the temperature is further raised to 1200°C for carbonization for 2h.
对比例2Comparative example 2
本实施例制备了一种电极材料，具体制备方法为：In this embodiment, a kind of electrode material is prepared, and the specific preparation method is as follows:
B1.电极材料B1. Electrode material
B1b：将75％的对比例1制备的复合材料(用作活性材料)，15％炭黑和10％PVDF 在NMP中均匀混合，之后涂布在铜箔上，置于室温干燥24h，再在80℃下干燥24h，将干燥后的电极材料裁剪成圆片，活性材料的负载量为1.5mg/cm 2。 B1b: 75% of the composite material prepared in Comparative Example 1 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, placed at room temperature and dried for 24h, and then placed in After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading capacity of the active material was 1.5 mg/cm 2 .
对比例3Comparative example 3
本对比例制备了一种复合材料，具体制备方法为：This comparative example has prepared a kind of composite material, and concrete preparation method is:
A1.制备纤维素A1. Preparation of cellulose
A1a：将葡萄糖、酵母精、蛋白胨、磷酸二氢钠混合，混合质量比为4:1:1:0.6，向混合物中加入柠檬酸，柠檬酸的浓度为1.2g/L，搅拌均匀，以汉氏驹形杆菌为菌种在30℃发酵15天，形成细菌纤维素；A1a: Mix glucose, yeast extract, peptone, and sodium dihydrogen phosphate, the mixing mass ratio is 4:1:1:0.6, add citric acid to the mixture, the concentration of citric acid is 1.2g/L, stir well, and Bacillus colliformis is fermented at 30°C for 15 days to form bacterial cellulose;
A1b：将细菌纤维素放入到2mol/L的NaOH溶液中，搅拌20h，去除杂质剥离出纯净的纤维素，再用去离子水多次清洗至pH接近7。A1b: Put bacterial cellulose into 2mol/L NaOH solution, stir for 20 hours, remove impurities and peel off pure cellulose, and then wash with deionized water several times until the pH is close to 7.
葡萄糖规格：D-(+)-葡萄糖，GC，≥99.5％，购买于阿拉丁；酵母精(酵母浸出粉)：超级纯，用于微生物，购买于阿拉丁；蛋白胨：酵母蛋白胨，购买于阿拉丁；磷酸二氢钠：用于分子生物学，≥99％，购买于阿拉丁。Glucose specification: D-(+)-glucose, GC, ≥99.5%, purchased from Aladdin; yeast essence (yeast extract powder): super pure, used for microorganisms, purchased from Aladdin; peptone: yeast peptone, purchased from Aladdin Latin; sodium dihydrogen phosphate: used in molecular biology, ≥99%, purchased from Aladdin.
A2.制备复合材料A2. Preparation of composite materials
A2a：将清洗后的纤维素置于氮气气氛中，300℃煅烧5h，纤维素上的羟基会形成醚键，单链间产生交联，从而使材料稳定化，再进一步将温度提升到1200℃进行碳化2h；A2a: Put the cleaned cellulose in a nitrogen atmosphere and calcinate at 300°C for 5 hours, the hydroxyl groups on the cellulose will form ether bonds, and crosslinks will occur between the single chains, thereby stabilizing the material, and then further increase the temperature to 1200°C Carry out carbonization for 2h;
A2b：将碳化后的材料与KOH混合，质量比为1:7，在700℃下煅烧2h进行活化，冷却后的材料用0.5mol/L的HCl在25～50℃清洗1～6h，再用去离子多次清洗至pH接近7，在80℃干燥15h。A2b: Mix the carbonized material with KOH at a mass ratio of 1:7, and activate it by calcination at 700°C for 2h, and wash the cooled material with 0.5mol/L HCl at 25-50°C for 1-6h, and then use Deionized and washed several times until the pH is close to 7, and dried at 80°C for 15 hours.
对比例4Comparative example 4
本实施例制备了一种电极材料，具体制备方法为：In this embodiment, a kind of electrode material is prepared, and the specific preparation method is as follows:
B1.电极材料B1. Electrode material
B1b：将75％的对比例2制备的复合材料(用作活性材料)，15％炭黑和10％PVDF在NMP中均匀混合，之后涂布在铜箔上，置于室温干燥24h，再在80℃下干燥24h， 将干燥后的电极材料裁剪成圆片，活性材料的负载量为1.5mg/cm 2。 B1b: 75% of the composite material prepared in Comparative Example 2 (used as an active material), 15% carbon black and 10% PVDF were uniformly mixed in NMP, then coated on copper foil, dried at room temperature for 24h, and then After drying at 80° C. for 24 hours, the dried electrode material was cut into discs, and the loading amount of the active material was 1.5 mg/cm 2 .
试验例Test case
试验例1Test example 1
本试验例测试了实施例和对比例所得复合材料的比表面积，如表1所示：This test example has tested the specific surface area of the composite material of embodiment and comparative example gained, as shown in table 1:
表1复合材料与对比样品的比表面积The specific surface area of table 1 composite material and comparative sample
Figure PCTCN2022109233-appb-000001
Figure PCTCN2022109233-appb-000001
比表面积的计算方法：比表面积是通过麦克2020测试，根据氮气的吸附量利用BET理论计算得出，为送粉末样品用设备直接测试得到。Calculation method of specific surface area: The specific surface area is tested by Mike 2020, calculated by BET theory according to the adsorption amount of nitrogen, and obtained by direct test with equipment for sending powder samples.
表1为实施例1、3、5、7与对比例1、3制备的样品的比表面积对比，发现通过掺杂和活化可有效增加材料的比表面积，其中实施例7的比表面积最大。Table 1 compares the specific surface area of the samples prepared in Examples 1, 3, 5, 7 and Comparative Examples 1 and 3. It is found that the specific surface area of the material can be effectively increased by doping and activation, and the specific surface area of Example 7 is the largest.
试验例2Test example 2
以锂金属作为对电极和参比电极与实施例2、4、6、8与对比例2、4制备的工作电极一起组装成扣电池，其中隔膜用聚丙烯膜，电解液为溶解在1:1的碳酸乙烯酯和碳酸二甲酯的1mol/L的LiPF 6，电性能测试电压窗口为0.01～3V，电流密度为0.2～10C，测试结果如表2所示。 Use lithium metal as counter electrode and reference electrode and the working electrode that embodiment 2,4,6,8 and comparative example 2,4 prepare are assembled into button battery together, and wherein separator uses polypropylene film, and electrolytic solution is dissolved in 1: 1 ethylene carbonate and dimethyl carbonate 1mol/L LiPF 6 , the voltage window of the electrical performance test is 0.01-3V, and the current density is 0.2-10C. The test results are shown in Table 2.
表2复合材料与对比样品的电化学性能测试数据Table 2 The electrochemical performance test data of the composite material and the comparative sample
Figure PCTCN2022109233-appb-000002
Figure PCTCN2022109233-appb-000002
Figure PCTCN2022109233-appb-000003
Figure PCTCN2022109233-appb-000003
表2为实施例2、4、6、8与对比例2、4制备的样品的电化学性能对比，发现所制备的活化掺氮细菌纤维素的比容量高于对比例2和4，且随着倍率的增加，实施例中的材料性能越突出，尤其实施例6的电化学性能明显较为优异。Table 2 is the comparison of the electrochemical properties of the samples prepared in Examples 2, 4, 6, 8 and Comparative Examples 2 and 4, and it is found that the specific capacity of the prepared activated nitrogen-doped bacterial cellulose is higher than that of Comparative Examples 2 and 4, and with With the increase of the magnification, the performance of the material in the examples is more prominent, especially the electrochemical performance of the example 6 is obviously excellent.
试验例3Test example 3
表3活化掺氮细菌纤维素与对比样品循环200圈容量保持率Table 3 Capacity retention rate of activated nitrogen-doped bacterial cellulose and comparison sample after 200 cycles
Figure PCTCN2022109233-appb-000004
Figure PCTCN2022109233-appb-000004
表3为实施例2、4、6、8与对比例2、4制备的样品循环200圈容量保持率，实施例2、4、6、8表现了高倍率下优异的循环稳定性。Table 3 shows the 200-cycle capacity retention of samples prepared in Examples 2, 4, 6, and 8 and Comparative Examples 2 and 4. Examples 2, 4, 6, and 8 show excellent cycle stability at high rates.
上面结合附图对本发明实施例作了详细说明，但是本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。The embodiments of the present invention have been described in detail above in conjunction with the accompanying drawings, but the present invention is not limited to the above-mentioned embodiments, and within the scope of knowledge of those of ordinary skill in the art, various modifications can be made without departing from the spirit of the present invention. Variety. In addition, the embodiments of the present invention and the features in the embodiments can be combined with each other if there is no conflict.

Claims (10)

  1. 一种复合材料，其特征在于，包括碳纤维和附着在所述碳纤维上的聚苯胺颗粒；A composite material, characterized in that it includes carbon fibers and polyaniline particles attached to the carbon fibers;
    所述复合材料上存在孔；Pores are present in the composite material;
    所述孔的孔径≤4nm。The diameter of the pores is ≤4nm.
  2. 根据权利要求1所述的复合材料，其特征在于，所述碳纤维的制备原料包括细菌纤维素；优选的，所述细菌纤维素的制备原料包括汉氏驹形杆菌。The composite material according to claim 1, wherein the raw material for preparing the carbon fiber includes bacterial cellulose; preferably, the raw material for preparing the bacterial cellulose includes Bacillus hansenii.
  3. 一种如权利要求1或2所述的复合材料的制备方法，其特征在于，包括以下步骤：A preparation method of composite material as claimed in claim 1 or 2, is characterized in that, comprises the following steps:
    S1：将纤维素、苯胺、引发剂和掺杂剂混合后除杂，干燥；S1: Mix cellulose, aniline, initiator and dopant, remove impurities, and dry;
    S2：将步骤S1所得混合物在氮气气氛下热处理；S2: heat treating the mixture obtained in step S1 under nitrogen atmosphere;
    S3：将步骤S2所得混合物和致孔剂混合，热处理，除杂，干燥，即得到所述复合材料。S3: Mix the mixture obtained in step S2 with the porogen, heat treat, remove impurities, and dry to obtain the composite material.
  4. 根据权利要求3所述的复合材料的制备方法，其特征在于，步骤S1中，所述纤维素的质量和所述苯胺的体积比为1g:5～20ml。The preparation method of the composite material according to claim 3, characterized in that, in step S1, the volume ratio of the mass of the cellulose to the aniline is 1g:5-20ml.
  5. 根据权利要求3所述的复合材料的制备方法，其特征在于，步骤S1中，所述引发剂包括过硫酸盐、过氧化氢、重铬酸盐和氯化铁中至少一种；优选的，所述引发剂包括过硫酸盐，优选的，所述引发剂包括过硫酸铵，优选的，步骤S1中，所述苯胺与过硫酸铵的摩尔比为1:1～2；优选的，步骤S1中，所述掺杂剂包括HCl或H 2SO 4中的至少一种；优选的，步骤S1中，所述混合的温度为0～30℃；优选的，步骤S1中，所述混合的时间为24～50h。 The preparation method of composite material according to claim 3, is characterized in that, in step S1, described initiator comprises at least one in persulfate, hydrogen peroxide, dichromate and ferric chloride; Preferably, The initiator includes persulfate, preferably, the initiator includes ammonium persulfate, preferably, in step S1, the molar ratio of aniline to ammonium persulfate is 1:1-2; preferably, step S1 wherein, the dopant includes at least one of HCl or H2SO4 ; preferably, in step S1 , the mixing temperature is 0-30°C; preferably, in step S1, the mixing time For 24 ~ 50h.
  6. 根据权利要求3所述的复合材料的制备方法，其特征在于，步骤S2中，所述热处理包括第一次热处理和第二次热处理，优选的，第一次热处理的温度为200～400℃；优选的，第一次热处理的时间为0.5～14h；优选的，第二次热处理的温度为900～1200℃，优选的，第二次热处理的时间为1～5h。The preparation method of the composite material according to claim 3, characterized in that, in step S2, the heat treatment includes the first heat treatment and the second heat treatment, preferably, the temperature of the first heat treatment is 200-400°C; Preferably, the time for the first heat treatment is 0.5-14 hours; preferably, the temperature for the second heat treatment is 900-1200° C., preferably, the time for the second heat treatment is 1-5 hours.
  7. 根据权利要求3所述的复合材料的制备方法，其特征在于，步骤S3中，所述致 孔剂包括KOH和NaOH中至少一种，优选的，步骤S3中，所述步骤S2所得混合物和所述致孔剂的质量比为1:2～10。The preparation method of composite material according to claim 3, characterized in that, in step S3, the porogen includes at least one of KOH and NaOH, preferably, in step S3, the mixture obtained in step S2 and the The mass ratio of the porogen is 1:2-10.
  8. 根据权利要求3所述的复合材料的制备方法，其特征在于，步骤S3中，所述热处理的温度为700～900℃。The preparation method of the composite material according to claim 3, characterized in that, in step S3, the temperature of the heat treatment is 700-900°C.
  9. 根据权利要求3所述的复合材料的制备方法，其特征在于，步骤S3中，所述热处理的时间为1～4h。The preparation method of the composite material according to claim 3, characterized in that, in step S3, the time for the heat treatment is 1-4 hours.
  10. 一种储能装置，其特征在于，制备原料包括权利要求1或2所述的复合材料或权利要求3～8任一项所述的制备方法制备的复合材料。An energy storage device, characterized in that the preparation raw materials include the composite material according to claim 1 or 2 or the composite material prepared by the preparation method according to any one of claims 3-8.
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