WO2022056951A1 - 一种硬碳的制备方法及应用 - Google Patents

一种硬碳的制备方法及应用 Download PDF

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WO2022056951A1
WO2022056951A1 PCT/CN2020/117973 CN2020117973W WO2022056951A1 WO 2022056951 A1 WO2022056951 A1 WO 2022056951A1 CN 2020117973 W CN2020117973 W CN 2020117973W WO 2022056951 A1 WO2022056951 A1 WO 2022056951A1
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carbonization
preparation
salt
hard carbon
biomass waste
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PCT/CN2020/117973
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English (en)
French (fr)
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邢伟
邱智健
李彬
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山东昭文新能源科技有限公司
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • 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 relates to the technical field of battery materials, in particular to a preparation method and application of hard carbon.
  • Lithium (Li) is the lightest metal element with a small ionic radius and has many electrochemical properties. Advantages such as high energy density, high power density as well as a wide range of operating temperatures and good operating life. Therefore, lithium-ion-based electrical energy storage systems have broad application prospects.
  • lithium-ion-based electric energy storage system lithium-ion battery, lithium-ion capacitor, etc.
  • it will rely on the storage of lithium ions on the negative electrode material to achieve the purpose of storing electric charge, thereby realizing the storage of electric energy.
  • the most commonly used anode material is graphite, but graphite has the disadvantages of low voltage platform, low theoretical capacity and poor rate performance, and the traditional graphite preparation method is cumbersome, high cost and high technical requirements.
  • hard carbon materials make up for the shortcomings of graphite's low voltage platform, low theoretical capacity and poor rate performance to a certain extent, so it has great research potential.
  • the cycle specific capacity and rate performance of currently commercially available hard carbon materials are still unsatisfactory, and the cost is relatively high.
  • the purpose of the present invention is to provide a preparation method and application of hard carbon, the preparation method is low in cost, and the prepared hard carbon has excellent electrochemical performance.
  • the technical scheme adopted in the present invention is:
  • a preparation method of hard carbon comprising the following steps:
  • the biomass waste powder is subjected to salt leaching to obtain the biomass waste powder after the salt leaching;
  • the hard carbon is obtained by sequentially performing first carbonization, ball milling and second carbonization on the salt-leached biomass waste powder.
  • the biomass waste of the biomass waste powder is nut shell and/or waste wood.
  • the nut shell is one of walnut shell, coconut shell, macadamia nut shell, pistachio nut shell, almond shell, hazelnut shell, pine nut shell, cashew nut shell, ginkgo shell, pecan shell and almond shell or several.
  • the waste wood is one or more of birch, boxwood, willow, hard maple and peach.
  • the salt concentration in the salt solution used for the salt leaching is (0-1.5) mol/L, and the salt concentration in the salt solution is not 0.
  • the salt solution includes potassium carbonate solution, potassium chloride solution, zinc chloride solution, cobalt nitrate solution or nickel nitrate solution.
  • the temperature of the first carbonization is 350-600°C, and the time is 60-180min;
  • the heating rate to the temperature of the first carbonization is 5 to 15° C./min.
  • the rotational speed of the ball mill is 400-900 rpm, and the time of the ball-milling is 30-180 min.
  • the grinding balls used in the ball milling include grinding balls with a diameter of 3 mm and grinding balls with a diameter of 10 mm;
  • the number ratio of the grinding balls with a diameter of 3 mm and the grinding balls with a diameter of 10 mm is (1-5):1.
  • the temperature of the second carbonization is 800-1200°C, and the time is 30-120min;
  • the heating rate to the temperature of the second carbonization is 5 to 15° C./min.
  • acid washing of the obtained product is also included.
  • the acid solution used in the pickling is hydrochloric acid with a concentration of 0.01-0.5 mol/L.
  • the particle size of the biomass waste powder is 10-900 ⁇ m.
  • the present invention also provides the application of the hard carbon prepared by the preparation method described in the above technical solution in the field of batteries.
  • the invention provides a method for preparing hard carbon, which comprises the following steps: salt leaching biomass waste powder to obtain the biomass waste powder after salt leaching; sequentially performing the first step on the salt leaching biomass waste powder Carbonization, ball milling, and second carbonization yield the hard carbon.
  • the biomass waste powder is subjected to salt leaching so that the biomass waste powder contains salt ions, and the salt ions will change the microstructure of carbon in the subsequent second carbonization process, thereby affecting the performance of hard carbon
  • the two-step carbonization process is used to ensure that a preliminary carbon structure can be formed and tar substances in the biomass can be removed through the first carbonization, so as to facilitate the relative controllability of the biomass waste powder size in the subsequent ball milling process. Dicarbonization ensures the formation of a more stable carbon structure.
  • the present invention adopts a simple process and low-cost raw materials to prepare hard carbon, which is a low-consumption and high-efficiency preparation method, and is suitable for large-scale commercial applications;
  • the present invention adopts biomass waste as raw material to prepare hard carbon material, and realizes waste utilization and virtuous cycle;
  • the present invention adopts a two-step carbonization method. Through the first carbonization, a pre-carbonized structure is obtained and tar substances are removed, so that the effect of ball milling is better played. structural stability;
  • the hard carbon prepared by the present invention has excellent rate performance, high cycle stability capacity and good cycle life.
  • Fig. 1 is the charge-discharge curve of the hard carbon prepared in Example 1;
  • Fig. 2 is the charge-discharge cycle curve of the hard carbon prepared in Example 1;
  • Fig. 3 is the charge-discharge cycle curve of hard carbon and commercial hard carbon prepared in Example 1;
  • Fig. 4 is the SEM image of the hard carbon prepared in Example 1;
  • Example 5 is a Raman characterization diagram of the hard carbon prepared in Example 1;
  • Fig. 6 is the charge-discharge cycle curve of the hard carbon prepared in Examples 2-4;
  • Fig. 7 is the charge-discharge curve of the hard carbon prepared in Example 2.
  • FIG. 9 is the charge-discharge curve of the hard carbon prepared in Example 4.
  • the invention provides a preparation method of hard carbon, comprising the following steps:
  • the biomass waste powder is subjected to salt leaching to obtain the biomass waste powder after the salt leaching;
  • the hard carbon is obtained by sequentially performing first carbonization, ball milling and second carbonization on the salt-leached biomass waste powder.
  • the biomass waste powder is subjected to salt leaching to obtain the biomass waste powder after the salt leaching.
  • the biomass waste powder is preferably prepared; the preparation method of the biomass waste powder is preferably: ultrasonically, cleaning, drying and crushing the biomass waste in sequence to obtain the biomass waste powder.
  • the biomass waste is preferably nut shells and/or waste wood;
  • the nut shells are preferably walnut shells, coconut shells, macadamia nut shells, pistachio nut shells, almond shells, hazelnut shells, pine nut shells, cashew nuts
  • the limit of can be mixed according to any ratio.
  • the waste wood is preferably one or more of birch, boxwood, willow, hard maple and peach; when the waste wood is two or more of the above specific choices, The present invention does not have any special limitation on the proportion of the above-mentioned specific substances, and the mixture can be mixed according to any proportion.
  • the biological waste is nut shell and waste wood
  • the present invention does not have any special limitation on the ratio of the nut shell and waste wood, and it can be mixed according to any ratio.
  • the ultrasonication is preferably carried out in distilled water.
  • the present invention does not have any special limitation on the conditions of the ultrasonication, and the ultrasonication can be carried out under conditions well known to those skilled in the art.
  • the present invention does not have any special limitation on the cleaning solution, and the cleaning can be performed by a process well known to those skilled in the art.
  • the drying temperature is preferably 60-100° C., more preferably 70-90° C., and most preferably 75-85° C. A time well known to the skilled person is sufficient to ensure adequate drying.
  • the drying is preferably carried out in a forced air drying oven.
  • the grinding time is preferably 10-60 minutes, more preferably 20-50 minutes, and most preferably 30-40 minutes.
  • the pulverization is preferably performed in a pulverizer.
  • the particle size of the biomass waste powder is preferably 10 to 900 ⁇ m, more preferably 100 to 500 ⁇ m.
  • the salt concentration in the salt solution used in the salt leaching is preferably (0-1.5) mol/L, and the salt concentration in the salt solution is not 0; more preferably (0.5-1.0) mol /L.
  • the salt solution preferably includes potassium carbonate solution, potassium chloride solution, zinc chloride solution, cobalt nitrate solution or nickel nitrate solution.
  • the mass ratio of the biomass waste powder to the salt solution is preferably 10g:(50-200)mL, more preferably 10g:(100-150)mL.
  • the salt leaching time is preferably 6-12 hours, more preferably 8-10 hours.
  • the purpose of the salt leaching is to make the salt particles adhere to the biomass waste, so that the salt particles can change the microstructure of carbon in the subsequent carbonization process and improve the performance of hard carbon.
  • the salt leaching after the salt leaching is completed, it also preferably includes drying; in the present invention, the drying temperature is preferably 60-100°C, more preferably 70-80°C; the present invention controls the drying time There are no special restrictions, as long as sufficient drying is ensured.
  • the temperature of the first carbonization is preferably 350-600°C, more preferably 400-550°C, most preferably 450-500°C; the time is preferably 60-180min, more preferably 90-150min, and the most It is preferably 100-120 min; the heating rate to the temperature of the first carbonization is preferably 5-15°C/min, more preferably 8-12°C/min.
  • the first carbonization is preferably performed in an inert atmosphere; the present invention does not have any special limitation on the inert atmosphere.
  • the present invention also preferably includes cooling, and the cooling method is preferably natural cooling or quenching.
  • the rotational speed of the ball mill is preferably 400-900 rpm, more preferably 500-800 rpm, and most preferably 600-700 rpm; the ball-milling time is preferably 30-180 min, more preferably 50-150 min, most preferably For 80 ⁇ 120min.
  • the grinding balls used in the ball milling preferably include grinding balls with a diameter of 3 mm and grinding balls with a diameter of 10 mm; the number ratio of the grinding balls with a diameter of 3 mm to the grinding balls with a diameter of 10 mm is preferably ( 1 to 5): 1, more preferably (2 to 4): 1.
  • the ball-to-charge ratio is preferably 1:(15-30), more preferably 1:(20-30).
  • the temperature of the second carbonization is preferably 800-1200°C, more preferably 900-1100°C, most preferably 950-1050°C; the time is preferably 30-120min, more preferably 50-100min, and most preferably Preferably, it is 60-80 min; the heating rate to the temperature of the second carbonization is preferably 5-15°C/min, more preferably 8-12°C/min.
  • the second carbonization is preferably performed in an inert atmosphere; the present invention does not have any special limitation on the inert atmosphere
  • the present invention also preferably includes cooling, and the cooling method is preferably natural cooling or quenching.
  • the present invention also preferably includes pickling the obtained product;
  • the acid solution used in the pickling is preferably hydrochloric acid with a concentration of 0.01-0.5 mol/L;
  • the number of times of the pickling is preferably 3 ⁇ 15 times, more preferably 5 ⁇ 10 times;
  • the drying temperature is preferably 60-100°C, more preferably 70-80°C;
  • the drying is preferably carried out in a forced air drying oven.
  • the present invention also provides the application of the hard carbon prepared by the preparation method described in the above technical solution in the field of batteries.
  • the hard carbon is preferably used as an electrode material in the battery field; the present invention does not have any special limitation on the application method, and the application method well known to those skilled in the art can be used.
  • the coconut shells are placed in distilled water for ultrasonication and cleaning, dried at a temperature of 60 ° C, and pulverized with a pulverizer for 30 min to obtain coconut shell powder (particle size is 100-500 ⁇ m);
  • the coconut husk powder after the salt leaching is heated to 350°C with a heating rate of 5°C/min and kept for 120min to carry out the first carbonization, and after being naturally cooled to room temperature, ball milling (a diameter of 3mm is carried out)
  • the number ratio of the balls to the grinding balls with a diameter of 10 mm is 3, the ball milling speed is 400 rpm, the time is 90 min, and the ball-to-material ratio is 1:20), followed by the second carbonization (nitrogen atmosphere, with a heating rate of 5 °C/min).
  • the hard carbon is tested by scanning electron microscope, and the test result is shown in Figure 4. It can be seen from Figure 4 that the surface of the obtained hard carbon material is relatively smooth, and the macroporous structure is less;
  • the hard carbon was tested by Raman spectroscopy, and the test result was shown in FIG. 5 . It can be seen from FIG. 5 that the obtained hard carbon material has a high degree of disorder.
  • the coconut shells are placed in distilled water for ultrasonication and cleaning, dried at a temperature of 60 ° C, and pulverized with a pulverizer for 30 min to obtain coconut shell powder (particle size is 100-500 ⁇ m);
  • the coconut husk powder after the salt leaching is heated to 400°C with a heating rate of 5°C/min and kept for 120min to carry out the first carbonization, after being naturally cooled to room temperature, ball milling (a mill with a diameter of 3mm) is carried out.
  • the number ratio of the balls to the grinding balls with a diameter of 10 mm is 1, the ball milling speed is 600 rpm, the time is 90 min, and the ball-to-material ratio is 1:30), followed by the second carbonization (nitrogen atmosphere, with a heating rate of 5 °C/min).
  • the temperature was raised to 900° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • the coconut shells are placed in distilled water for ultrasonication and cleaning, dried at a temperature of 60 ° C, and pulverized with a pulverizer for 30 min to obtain coconut shell powder (particle size is 100-500 ⁇ m);
  • the coconut shell powder after the salt leaching is heated to 550°C with a heating rate of 5°C/min and kept for 120min to carry out the first carbonization, after being naturally cooled to room temperature, ball milling (a mill with a diameter of 3mm) is carried out.
  • the number ratio of the balls to the grinding balls with a diameter of 10 mm is 0.5, the ball milling speed is 600 rpm, the time is 90 min, and the ball-to-material ratio is 1:30), followed by the second carbonization (nitrogen atmosphere, with a heating rate of 5°C/min).
  • the temperature was raised to 1100° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • the coconut shells are placed in distilled water for ultrasonication and cleaning, dried at a temperature of 60 ° C, and pulverized with a pulverizer for 30 min to obtain coconut shell powder (particle size is 100-500 ⁇ m);
  • the coconut husk powder after the salt leaching is heated to 350°C with a heating rate of 5°C/min and kept for 120min to carry out the first carbonization, and after being naturally cooled to room temperature, ball milling (a diameter of 3mm is carried out)
  • the number ratio of the balls to the grinding balls with a diameter of 10 mm is 1.5, the ball milling speed is 600 rpm, the time is 90 min, and the ball-to-material ratio is 1:30), followed by the second carbonization (nitrogen atmosphere, with a heating rate of 5°C/min).
  • the temperature was raised to 1100° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • the walnut shells are placed in distilled water for ultrasonication, cleaning, drying at a temperature of 60 ° C, and pulverizing with a pulverizer for 30 minutes to obtain walnut shell powder (particle size is 150-500 ⁇ m);
  • the walnut shell powder after the salt leaching was heated to 350°C at a heating rate of 5°C/min and kept for 120min for the first carbonization, and after being naturally cooled to room temperature, ball milling (a mill with a diameter of 3mm The number ratio of the balls to the grinding balls with a diameter of 10 mm is 3, the ball milling speed is 400 rpm, the time is 90 min, and the ball-to-material ratio is 1:30), followed by the second carbonization (nitrogen atmosphere, with a heating rate of 5°C/min). The temperature was raised to 1000° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • macadamia nut shells put the macadamia nut shells in distilled water for ultrasonication, cleaning, drying at a temperature of 60 ° C, and pulverizing with a pulverizer for 30 minutes to obtain macadamia nut shell powder (particle size is 150-500 ⁇ m);
  • the macadamia nut shell powder after the salt leaching was heated to 350°C at a heating rate of 5°C/min and kept for 120min to carry out the first carbonization, after being naturally cooled to room temperature, ball milling (with a diameter of 3mm) was carried out.
  • the number ratio of grinding balls to those with a diameter of 10 mm is 3, the ball milling speed is 400 rpm, the time is 90 min, and the ball-to-material ratio is 1:30).
  • the temperature was raised to 1000° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • the pistachio shells are placed in distilled water for ultrasonication, cleaning, drying at a temperature of 60 ° C, and pulverizing with a pulverizer for 30 minutes to obtain pistachio shell powder (particle size is 200-500 ⁇ m);
  • the pistachio nut shell powder after the salt leaching was heated to 350°C at a heating rate of 5°C/min and kept for 120min to carry out the first carbonization, and after being naturally cooled to room temperature, ball milling (with a diameter of 3mm) was carried out.
  • the number ratio of grinding balls to those with a diameter of 10 mm is 3, the ball milling speed is 400 rpm, the time is 90 min, and the ball-to-material ratio is 1:30).
  • the temperature was raised to 1000° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • the almond shells are placed in distilled water for ultrasonication, cleaning, drying at a temperature of 60° C., and pulverizing with a pulverizer for 30 minutes to obtain almond shell powder (particle size is 200-500 ⁇ m);
  • the salted almond shell powder was heated to 350°C at a heating rate of 5°C/min and kept for 120min for the first carbonization, and after being naturally cooled to room temperature, ball milling (a mill with a diameter of 3mm) was performed.
  • the number ratio of the balls to the grinding balls with a diameter of 10 mm is 3, the ball milling speed is 400 rpm, the time is 90 min, and the ball-to-material ratio is 1:30), followed by the second carbonization (nitrogen atmosphere, with a heating rate of 5°C/min).
  • the temperature was raised to 1000° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • hazelnut shells are placed in distilled water for ultrasonication, cleaning, drying at a temperature of 60 ° C, and pulverizing with a pulverizer for 30 minutes to obtain hazelnut shell powder (particle size is 150-500 ⁇ m);
  • the hazelnut shell powder after the salt leaching was heated to 350°C at a heating rate of 5°C/min and kept for 120min to carry out the first carbonization, and after being naturally cooled to room temperature, ball milling (a mill with a diameter of 3 mm was carried out).
  • the number ratio of the balls to the grinding balls with a diameter of 10 mm is 3, the ball milling speed is 400 rpm, the time is 90 min, and the ball-to-material ratio is 1:30), followed by the second carbonization (nitrogen atmosphere, with a heating rate of 5°C/min).
  • the temperature was raised to 1000° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • boxwood is placed in distilled water for ultrasonication and cleaning, dried at a temperature of 60° C., and pulverized with a pulverizer for 30 minutes to obtain boxwood powder (particle size is 200-500 ⁇ m);
  • the boxwood powder after the salt leaching was heated to 350°C with a heating rate of 5°C/min and kept for 120min to carry out the first carbonization.
  • the number ratio of the balls to the grinding balls with a diameter of 10 mm is 3, the ball milling speed is 400 rpm, the time is 90 min, and the ball-to-material ratio is 1:20), followed by the second carbonization (nitrogen atmosphere, with a heating rate of 5 °C/min).
  • the temperature was raised to 1000° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • the hard maple trees are placed in distilled water for ultrasonication, cleaning, drying at a temperature of 60 ° C, and pulverizing with a pulverizer for 30 minutes to obtain hard maple powder (particle size is 200-500 ⁇ m);
  • the hard maple powder after the salt leaching was heated to 350°C at a heating rate of 5°C/min and kept for 120min to carry out the first carbonization, after being naturally cooled to room temperature, ball milled (with a diameter of 3mm
  • the number ratio of the grinding balls to the grinding balls with a diameter of 10 mm is 3, the ball milling speed is 400 rpm, the time is 90 min, and the ball-to-material ratio is 1:20), followed by the second carbonization (nitrogen atmosphere, with a temperature rise of 5°C/min).
  • the temperature was raised to 1000° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • peach trees are placed in distilled water for ultrasonication and cleaning, dried at a temperature of 60 ° C, and pulverized with a pulverizer for 30 min to obtain peach tree powder (particle size is 200 to 500 ⁇ m);
  • the peach tree powder after the salt leaching was heated to 350°C with a temperature increase rate of 5°C/min and kept for 120min to carry out the first carbonization, after being naturally cooled to room temperature, ball milling (a 3mm diameter mill was carried out).
  • the number ratio of the balls to the grinding balls with a diameter of 10 mm is 3, the ball milling speed is 400 rpm, the time is 90 min, and the ball-to-material ratio is 1:20), followed by the second carbonization (nitrogen atmosphere, with a heating rate of 5°C/min).
  • the temperature was raised to 1000° C. and kept for 90 min), naturally cooled to room temperature, washed three times with 0.01 mol/L hydrochloric acid, and dried to obtain hard carbon.
  • the hard carbons prepared in Examples 1-12 and commercially available hard carbons (LBV-1001 (Sumitomo Bakelite, Japan), Kuraray type-1 (Kuraray Co., Ltd.) and Kuraray type-2 (Kuraray Co., Ltd.)) Mix evenly with acetylene black and PVDF in a mass ratio of 8:1:1, and disperse with N-methylpyrrolidone solvent to obtain a mixed slurry;
  • the mixed slurry was evenly coated on the copper foil, dried at 60°C for 12 hours, cut into a 16mm diameter disc, and then a button battery was formed using a lithium sheet as a counter electrode in a nitrogen-filled glove box. , and then perform constant current charge-discharge test at a current density of 0.05A/g;
  • Cycle test and rate performance test first charge and discharge for 500 cycles at a current density of 0.5A/g, and then cycle for 500 cycles at a current density of 1A/g.
  • Figure 1 is the charge-discharge curve of the hard carbon prepared in Example 1, and it can be seen from Figure 1 that the specific capacity of the hard carbon prepared in Example 1 is 601.8 mA h/g;
  • Figure 2 is the charge-discharge cycle curve of the hard carbon prepared in Example 1. It can be seen from Figure 2 that the hard carbon prepared in Example 1 has a high capacity retention rate and a high cycle capacity, and the current is 1A/g. The specific capacity remains at 440mA h/g under density;
  • Figure 3 shows the charge-discharge cycle curves of the hard carbon prepared in Example 1 and commercial hard carbon. It can be seen from Figure 3 that the hard carbon prepared in Example 1 has better capacity retention and higher cycle time than commercial hard carbon.
  • Capacity (LBV-1001 maintains a specific capacity of 150.8 mA h/g at a current density of 1A/g; Kuraray type-1 maintains a specific capacity of 164.4 mA h/g at a current density of 1 A/g and Kuraray type- 2 The specific capacity remains at 59.2 mA h/g at a current density of 1 A/g);
  • Figure 6 shows the charge-discharge cycle curves of the hard carbons prepared in Examples 2 to 4. It can be seen from Figure 6 that the hard carbon prepared in Example 2 has a high capacity retention rate and a high cycle capacity, at 1A/g The specific capacity remains at 128.8 mA h/g at a current density of 1 A/g; the hard carbon prepared in Example 3 has high capacity retention and cycle capacity, and the specific capacity remains at 210.5 at a current density of 1 A/g mA h/g; the hard carbon prepared in Example 4 has high capacity retention and cycle capacity, and the specific capacity remains at 122.5 mA h/g at a current density of 1 A/g;
  • Figure 7 is the charge-discharge curve of the hard carbon prepared in Example 2; it can be seen from Figure 7 that the specific capacity of the hard carbon prepared in Example 2 is 205.6 mA h/g;
  • Figure 8 is the charge-discharge curve of the hard carbon prepared in Example 3; it can be seen from Figure 8 that the specific capacity of the hard carbon prepared in Example 3 is 448.3 mA h/g;
  • Figure 9 is the charge-discharge curve of the hard carbon prepared in Example 4; it can be seen from Figure 9 that the specific capacity of the hard carbon prepared in Example 4 is 338.2 mA h/g;
  • Table 1 The specific capacity (mA ⁇ h/g) of the hard carbons prepared in Examples 5-12 at a current density of 0.05A/g and the specific capacity (mA ⁇ h) of 500 cycles at a current density of 1A/g /g)

Abstract

本发明涉及电池材料技术领域，尤其涉及一种硬碳的制备方法及应用。本发明提供的制备方法，包括以下步骤：将生物质废料粉末进行盐浸，得到盐浸后的生物质废料粉末；将所述盐浸后的生物质废料粉末依次进行第一碳化、球磨和第二碳化，得到所述硬碳。本发明先将生物质废料粉末进行盐浸使所述生物质废料粉末中带有盐离子，且所述盐离子在后续的第二碳化过程中会改变碳的微观结构，进而影响硬碳的性能，通过两步碳化过程是为了保证经过第一碳化可以形成初步的碳结构和去除所述生物质中的焦油类物质，便于后续的球磨过程中对生物质废料粉末尺寸的相对可控性，经过第二碳化可以保证形成更加稳定的碳结构。

Description

一种硬碳的制备方法及应用
本申请要求于2020年09月18日提交中国专利局、申请号为202010986133.6、发明名称为“一种硬碳的制备方法及应用”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明涉及电池材料技术领域，尤其涉及一种硬碳的制备方法及应用。
背景技术
地球上存在各种能源，包括化石能源、地热能、风能、水能和太阳能等。我们可以从这些资源中产生可供人类使用的能量，但是为了更加方便地使用这些能量，就需要高效的电能储存***、锂(Li)是最轻的金属元素，离子半径小，具有许多电化学优势，例如高能量密度、高功率密度以及宽范围的工作温度和良好的工作寿命。因此，基于锂离子的电能储存***具有广阔的应用前景。
无论何种基于锂离子的电能储存***(锂离子电池、锂离子电容器等)都会在负极材料上依靠锂离子的储存达到储存电荷的目的，从而实现电能的储存。目前，最常用的负极材料是石墨，但石墨存在着电压平台低、理论容量低、倍率性能差的缺点，并且传统的石墨的制备方法繁琐，成本高和技术要求含量高。而硬碳材料在一定程度上弥补了石墨的电压平台低、理论容量低和倍率性能差的缺点，因此具有很大的研究潜力。但是，目前市售的硬碳材料的循环比容量和倍率性能仍然不太理想，并且成本较高。
发明内容
本发明的目的在于提供一种硬碳的制备方法及应用，所述制备方法成本低，且制备得到的硬碳具有优异的电化学性能。
为了解决上述技术问题，本发明采用的技术方案是：
一种硬碳的制备方法，包括以下步骤：
将生物质废料粉末进行盐浸，得到盐浸后的生物质废料粉末；
将所述盐浸后的生物质废料粉末依次进行第一碳化、球磨和第二碳化，得到所述硬碳。
优选的，所述生物质废料粉末的生物质废料为果壳和/或废木材。
优选的，所述果壳为核桃壳、椰壳、夏威夷果壳、开心果壳、杏仁壳、榛子壳、松子壳、腰果壳、白果壳、碧根果壳和巴旦木壳中的一种或几种。
优选的，所述废木材为桦树木、黄杨树木、柳树木、硬枫树木和桃树木中的一种或几种。
优选的，所述盐浸采用的盐溶液中盐的浓度为(0～1.5)mol/L，且所述盐溶液中盐的浓度不为0。
优选的，所述盐溶液包括碳酸钾溶液、氯化钾溶液、氯化锌溶液、硝酸钴溶液或硝酸镍溶液。
优选的，所述第一碳化的温度为350～600℃，时间为60～180min；
升温至所述第一碳化的温度的升温速度为5～15℃/min。
优选的，所述球磨的转速为400～900rpm，所述球磨的时间为30～180min。
优选的，所述球磨采用的磨球包括直径为3mm的磨球和直径为10mm的磨球；
所述直径为3mm的磨球和直径为10mm的磨球的个数比为(1～5)：1。
优选的，所述第二碳化的温度为800～1200℃，时间为30～120min；
升温至所述第二碳化的温度的升温速度为5～15℃/min。
优选的，所述第二碳化完成后，还包括将所得产物进行酸洗。
优选的，所述酸洗采用的酸液为浓度为0.01～0.5mol/L的盐酸。
优选的，所述生物质废料粉末的粒径为10～900μm。
本发明还提供了上述技术方案所述的制备方法制备得到的硬碳在电池领域中的应用。
本发明提供了一种硬碳的制备方法，包括以下步骤：将生物质废料粉末进行盐浸，得到盐浸后的生物质废料粉末；将所述盐浸后的生物质废料粉末依次进行第一碳化、球磨和第二碳化，得到所述硬碳。本发明将生物质废料粉末进行盐浸使所述生物质废料粉末中带有盐离子，且所述盐离子在后续的第二碳化过程中会改变碳的微观结构，进而影响硬碳的性能，通过两步碳化过程是为了保证经过第一碳化可以形成初步的碳结构和去除 所述生物质中的焦油类物质，便于后续的球磨过程中对生物质废料粉末尺寸的相对可控性，经过第二碳化可以保证形成更加稳定的碳结构。
与现有技术相比，本发明所述技术方案的具有以下有益效果：
1、本发明采用了简单的工艺和低成本的原料制备得到了硬碳，是一种低耗高效的制备方法，适合于大规模的商业应用；
2、本发明采用生物质废料作为原料制备得到硬碳材料，实现了废物利用和良性循环；
3、本发明采用了两步碳化法，通过第一碳化得到了预碳化结构并去除了焦油类的物质，更好的发挥了球磨的作用，球磨后的第二碳化又使硬碳具有良好的结构稳定性；
4、本发明制备得到的硬碳具有优异的倍率性能和较高的循环稳定容量以及良好的循环寿命。
附图说明
图1为实施例1制备得到的硬碳的充放电曲线；
图2为实施例1制备得到的硬碳的充放电循环曲线；
图3为实施例1制备得到的硬碳和商业硬碳的充放电循环曲线；
图4为实施例1制备得到的硬碳的SEM图；
图5为实施例1制备得到的硬碳的拉曼表征图；
图6为实施例2～4制备得到的硬碳的充放电循环曲线；
图7为实施例2制备得到的硬碳的充放电曲线；
图8为实施例3制备得到的硬碳的充放电曲线；
图9为实施例4制备得到的硬碳的充放电曲线。
具体实施方式
下面结合实施例对本发明进一步说明。
本发明提供了一种硬碳的制备方法，包括以下步骤：
将生物质废料粉末进行盐浸，得到盐浸后的生物质废料粉末；
将所述盐浸后的生物质废料粉末依次进行第一碳化、球磨和第二碳化，得到所述硬碳。
在本发明中，若无特殊说明，所有原料均为本领域技术人员熟知的市售产品。
本发明将生物质废料粉末进行盐浸，得到盐浸后的生物质废料粉末。
在本发明中，所述生物质废料粉末优选通过制备得到；所述生物质废料粉末的制备方法优选为：将生物质废料依次进行超声、清洗、干燥和破碎，得到所述生物质废料粉末。
在本发明中，所述生物质废料优选为果壳和/或废木材；所述果壳优选为核桃壳、椰壳、夏威夷果壳、开心果壳、杏仁壳、榛子壳、松子壳、腰果壳、白果壳、碧根果壳和巴旦木壳中的一种或几种；当所述果壳为上述具体物质中的两种以上时，本发明对上述具体物质的配比没有任何特殊的限定，按任意配比进行混合即可。在本发明中，所述废木材优选为桦树木、黄杨树木、柳树木、硬枫树木和桃树木中的一种或几种；当所述废木材为上述具体选择中的两种以上时，本发明对上述具体物质的配比没有任何特殊的限定，按任意配比进行混合即可。当所述生物废料为果壳和废木材时，本发明对所述果壳和废木材的配比没有任何特殊的限定，按任意配比进行混合即可。
在本发明中，所述超声优选在蒸馏水中进行，本发明对所述超声的条件没有任何特殊的限定，采用本领域技术人员熟知的条件进行即可。本发明对所述清洗液没有任何特殊的限定，采用本领域技术人员熟知的过程进行清洗即可。
在本发明中，所述干燥的温度优选为60～100℃，更优选为70～90℃，最优选为75～85℃；本发明对所述干燥的时间没有任何特殊的限定，采用本领域技术人员熟知的时间并保证能够使其充分干燥即可。在本发明中，所述干燥优选在鼓风干燥箱中进行。
在本发明中，所述粉碎的时间优选为10～60min，更优选为20～50min，最优选为30～40min。本发明中，所述粉碎优选在粉碎机中进行。
在本发明中，所述生物质废料粉末的粒径优选为10～900μm，更优选为100～500μm。
在本发明中，所述盐浸采用的盐溶液中盐的浓度优选为(0～1.5)mol/L，且所述盐溶液中盐的浓度不为0；更优选为(0.5～1.0)mol/L。在本发明中，所述盐溶液优选包括碳酸钾溶液、氯化钾溶液、氯化锌溶液、硝酸钴溶液或硝酸镍溶液。在本发明中，所述生物质废料粉料的质量与所 述盐溶液的体积比优选为10g:(50～200)mL，更优选为10g:(100～150)mL。
在本发明中，所述盐浸的时间优选为6～12h，更优选为8～10h。
在本发明中，所述盐浸的目的是使盐粒子附着在所述生物质废料中，以利于所述盐粒子在后续的碳化过程中改变碳的微观结构，提高硬碳的性能。
在本发明中，所述盐浸完成后，还优选包括干燥；在本发明中，所述干燥的温度优选为60～100℃，更优选为70～80℃；本发明对所述干燥的时间没有任何特殊的限定，能够保证充分干燥即可。
在本发明中，所述第一碳化的温度优选为350～600℃，更优选为400～550℃，最优选为450～500℃；时间优选为60～180min，更优选为90～150min，最优选为100～120min；升温至所述第一碳化的温度的升温速度优选为5～15℃/min，更优选为8～12℃/min。在本发明中，所述第一碳化优选在惰性气氛中进行；本发明对所述惰性气氛没有任何特殊的限定。
所述第一碳化完成后，本发明还优选包括冷却，所述冷却的方式优选为自然冷却或骤冷。
在本发明中，所述球磨的转速优选为400～900rpm，更优选为500～800rpm，最优选为600～700rpm；所述球磨的时间优选为30～180min，更优选为50～150min，最优选为80～120min。在本发明中，所述球磨采用的磨球优选包括直径为3mm的磨球和直径为10mm的磨球；所述直径为3mm的磨球和直径为10mm的磨球的个数比优选为(1～5)：1，更优选为(2～4)：1。在本发明中，所述球料比优选为1：(15～30)，更优选为1：(20～30)。
在本发明中，所述第二碳化的温度优选为800～1200℃，更优选为900～1100℃，最优选为950～1050℃；时间优选为30～120min，更优选为50～100min，最优选为60～80min；升温至所述第二碳化的温度的升温速度优选为5～15℃/min，更优选为8～12℃/min。在本发明中，所述第二碳化优选在惰性气氛中进行；本发明对所述惰性气氛没有任何特殊的限定
所述第二碳化完成后，本发明还优选包括冷却，所述冷却的方式优选为自然冷却或骤冷。
所述第二碳化完成后，本发明还优选包括将所得产物进行酸洗；所述酸洗采用的酸液优选为浓度为0.01～0.5mol/L的盐酸；所述酸洗的次数优选为3～15次，更优选为5～10次；所述清洗完成后，还优选包括干燥；所述干燥的温度优选为60～100℃，更优选为70～80℃；本发明对所述干燥的时间没有任何特殊的限定，能够保证充分干燥即可。在本发明中，所述干燥优选在鼓风干燥箱中进行。
本发明还提供了上述技术方案所述的制备方法制备得到的硬碳在电池领域中的应用。在本发明中，所述硬碳优选作为电极材料应用在所述电池领域；本发明对所述应用的方法没有任何特殊的限定，采用本领域技术人员熟知的应用方法进行即可。
下面结合实施例对本发明提供的硬碳的制备方法及应用进行详细的说明，但是不能把它们理解为对本发明保护范围的限定。
实施例1
将椰壳置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到椰壳粉末(粒径为100～500μm)；
将10g所述椰壳粉末在0.1L浓度为0.1mol/L的碳酸钾溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的椰壳粉末；
在氮气气氛下，将所述盐浸后的椰壳粉末，以5℃/min的升温速度升温至350℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为3，球磨转速为400rpm，时间为90min，球料比为1:20)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1000℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳；
将所述硬碳进行扫描电子显微镜测试，测试结果如图4所示，由图4可知，得到的硬碳材料表面相对光滑，大孔结构较少；
将所述硬碳进行拉曼光谱测试，测试结果如图5所示，由图5可知，得到的硬碳材料具有较高的无序程度。
实施例2
将椰壳置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到椰壳粉末(粒径为100～500μm)；
将10g所述椰壳粉末在0.05L浓度为0.5mol/L的氯化钾溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的椰壳粉末；
在氮气气氛下，将所述盐浸后的椰壳粉末，以5℃/min的升温速度升温至400℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为1，球磨转速为600rpm，时间为90min，球料比为1:30)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至900℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
实施例3
将椰壳置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到椰壳粉末(粒径为100～500μm)；
将10g所述椰壳粉末在0.05L浓度为0.75mol/L的氯化锌溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的椰壳粉末；
在氮气气氛下，将所述盐浸后的椰壳粉末，以5℃/min的升温速度升温至550℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为0.5，球磨转速为600rpm，时间为90min，球料比为1:30)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1100℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
实施例4
将椰壳置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到椰壳粉末(粒径为100～500μm)；
将10g所述椰壳粉末在0.05L浓度为1mol/L的硝酸钴溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的椰壳粉末；
在氮气气氛下，将所述盐浸后的椰壳粉末，以5℃/min的升温速度升温至350℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为1.5，球磨转速为600rpm，时间为90min，球料比为1:30)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1100℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
实施例5
将核桃壳置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到核桃壳粉末(粒径为150～500μm)；
将10g所述核桃壳粉末在0.05L浓度为0.1mol/L的碳酸钾溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的核桃壳粉末；
在氮气气氛下，将所述盐浸后的核桃壳粉末，以5℃/min的升温速度升温至350℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为3，球磨转速为400rpm，时间为90min，球料比为1:30)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1000℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
实施例6
将夏威夷果壳置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到夏威夷果壳粉末(粒径为150～500μm)；
将10g所述夏威夷果壳粉末在0.05L浓度为0.1mol/L的碳酸钾溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的夏威夷果壳粉末；
在氮气气氛下，将所述盐浸后的夏威夷果壳粉末，以5℃/min的升温速度升温至350℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为3，球磨转速为400rpm，时间为90min，球料比为1:30)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1000℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
实施例7
将开心果壳置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到开心果壳粉末(粒径为200～500μm)；
将10g所述开心果壳粉末在0.05L浓度为0.1mol/L的碳酸钾溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的开心果壳粉末；
在氮气气氛下，将所述盐浸后的开心果壳粉末，以5℃/min的升温速度升温至350℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为3，球磨转 速为400rpm，时间为90min，球料比为1:30)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1000℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
实施例8
将杏仁壳置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到杏仁壳粉末(粒径为200～500μm)；
将10g所述杏仁壳粉末在0.05L浓度为0.1mol/L的碳酸钾溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的杏仁壳粉末；
在氮气气氛下，将所述盐浸后的杏仁壳粉末，以5℃/min的升温速度升温至350℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为3，球磨转速为400rpm，时间为90min，球料比为1:30)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1000℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
实施例9
将榛子壳置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到榛子壳粉末(粒径为150～500μm)；
将10g所述榛子壳粉末在0.05L浓度为0.1mol/L的碳酸钾溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的榛子壳粉末；
在氮气气氛下，将所述盐浸后的榛子壳粉末，以5℃/min的升温速度升温至350℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为3，球磨转速为400rpm，时间为90min，球料比为1:30)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1000℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
实施例10
将黄杨树木置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到黄杨树木粉末(粒径为200～500μm)；
将10g所述黄杨树木粉末在0.1L浓度为0.1mol/L的碳酸钾溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的黄杨树木粉末；
在氮气气氛下，将所述盐浸后的黄杨树木粉末，以5℃/min的升温速度升温至350℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为3，球磨转速为400rpm，时间为90min，球料比为1:20)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1000℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
实施例11
将硬枫树木置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到硬枫树木粉末(粒径为200～500μm)；
将10g所述硬枫树木粉末在0.1L浓度为0.1mol/L的碳酸钾溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的硬枫树木粉末；
在氮气气氛下，将所述盐浸后的硬枫树木粉末，以5℃/min的升温速度升温至350℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为3，球磨转速为400rpm，时间为90min，球料比为1:20)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1000℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
实施例12
将桃树木置于蒸馏水中进行超声、清洗，在60℃的温度下干燥，用粉碎机粉碎30min，得到桃树木粉末(粒径为200～500μm)；
将10g所述桃树木粉末在0.1L浓度为0.1mol/L的碳酸钾溶液中浸泡12h，在60℃的温度下干燥，得到盐浸后的桃树木粉末；
在氮气气氛下，将所述盐浸后的桃树木粉末，以5℃/min的升温速度升温至350℃并保温120min进行第一碳化，自然冷却至室温后，进行球磨(直径为3mm的磨球和直径为10mm的磨球的个数比为3，球磨转速为400rpm，时间为90min，球料比为1:20)后，进行第二碳化(氮气气氛，以5℃/min的升温速度升温至1000℃并保温90min)，自然冷却至室温，用0.01mol/L的盐酸清洗3次后干燥，得到硬碳。
测试例
将实施例1～12制备得到的硬碳和市售的硬碳(LBV-1001(日本住友 电木)、Kuraray type-1(可乐丽株式会社)和Kuraray type-2(可乐丽株式会社))分别与乙炔黑和PVDF按照8:1:1的质量比混合均匀，用N-甲基吡咯烷酮溶剂分散，得到混合浆料；
将所述混合浆料均匀涂在铜箔上，在60℃的温度下干燥12h后，剪裁成直径为16mm的圆片，然后再充满氮气的手套箱中用锂片作为对电极组成纽扣式电池，然后在0.05A/g的电流密度下进行恒流充放电测试；
循环测试和倍率性能测试：先在0.5A/g的电流密度下充放电循环500圈后，再在1A/g的电流密度下循环500圈。
其中，图1为实施例1制备得到的硬碳的充放电曲线，由图1可知，实施例1制备的得到的硬碳的比容量为601.8mA·h/g；
图2为实施例1制备得到的硬碳的充放电循环曲线，由图2可知，实施例1制备得到的硬碳具有很高的容量保持率和很高的循环容量，在1A/g的电流密度下比容量保持在440mA·h/g；
图3为实施例1制备得到的硬碳和商业硬碳的充放电循环曲线，由图3可知，实施例1制备得到的硬碳较商业硬碳具有更好的容量保持率和更高的循环容量(LBV-1001在1A/g的电流密度下比容量保持在150.8mA·h/g；Kuraray type-1在1A/g的电流密度下比容量保持在164.4mA·h/g和Kuraray type-2在1A/g的电流密度下比容量保持在59.2mA·h/g)；
图6为实施例2～4制备得到的硬碳的充放电循环曲线，由图6可知，实施例2制备得到的硬碳具有很高的容量保持率和很高的循环容量，在1A/g的电流密度下比容量保持在128.8mA·h/g；实施例3制备得到的硬碳具有很高的容量保持率和很高的循环容量，在1A/g的电流密度下比容量保持在210.5mA·h/g；实施例4制备得到的硬碳具有很高的容量保持率和很高的循环容量，在1A/g的电流密度下比容量保持在122.5mA·h/g；
图7为实施例2制备得到的硬碳的充放电曲线；由图7可知，实施例2制备的得到的硬碳的比容量为205.6mA·h/g；
图8为实施例3制备得到的硬碳的充放电曲线；由图8可知，实施例3制备的得到的硬碳的比容量为448.3mA·h/g；
图9为实施例4制备得到的硬碳的充放电曲线；由图9可知，实施例 4制备的得到的硬碳的比容量为338.2mA·h/g；
其中实施例5～12制备得到的硬碳在0.05A/g的电流密度下的比容量和在1A/g的容量保持率，如表1所示：
表1 实施例5～12制备得到的硬碳在0.05A/g的电流密度下的比容量(mA·h/g)和在1A/g的电流密度下循环500圈的比容量(mA·h/g)
Figure PCTCN2020117973-appb-000001
以上实施例的说明只是用于帮助理解本发明的方法及其核心思想。应当指出，对于本技术领域的普通技术人员来说，在不脱离本发明原理的前提下，还可以对本发明进行若干改进和修饰，这些改进和修饰也落入本发明权利要求的保护范围内。对这些实施例的多种修改对本领域的专业技术人员来说是显而易见的，本文中所定义的一般原理可以在不脱离本发明的精神或范围的情况下在其它实施例中实现。因此，本发明将不会被限制于本文所示的这些实施例，而是要符合与本文所公开的原理和新颖特点相一致的最宽的范围。

Claims (14)

  1. 一种硬碳的制备方法，其特征在于，包括以下步骤：
    将生物质废料粉末进行盐浸，得到盐浸后的生物质废料粉末；
    将所述盐浸后的生物质废料粉末依次进行第一碳化、球磨和第二碳化，得到所述硬碳。
  2. 如权利要求1所述的制备方法，其特征在于，所述生物质废料粉末的生物质废料为果壳和/或废木材。
  3. 如权利要求2所述的制备方法，其特征在于，所述果壳为核桃壳、椰壳、夏威夷果壳、开心果壳、杏仁壳、榛子壳、松子壳、腰果壳、白果壳、碧根果壳和巴旦木壳中的一种或几种。
  4. 如权利要求2所述的制备方法，其特征在于，所述废木材为桦树木、黄杨树木、柳树木、硬枫树木和桃树木中的一种或几种。
  5. 如权利要求1所述的制备方法，其特征在于，所述盐浸采用的盐溶液中盐的浓度为(0～1.5)mol/L，且所述盐溶液中盐的浓度不为0。
  6. 如权利要求5所述的制备方法，其特征在于，所述盐溶液包括碳酸钾溶液、氯化钾溶液、氯化锌溶液、硝酸钴溶液或硝酸镍溶液。
  7. 如权利要求1所述的制备方法，其特征在于，所述第一碳化的温度为350～600℃，时间为60～180min；
    升温至所述第一碳化的温度的升温速度为5～15℃/min。
  8. 如权利要求1所述的制备方法，其特征在于，所述球磨的转速为400～900rpm，所述球磨的时间为30～180min。
  9. 如权利要求1或8所述的制备方法，其特征在于，所述球磨采用的磨球包括直径为3mm的磨球和直径为10mm的磨球；
    所述直径为3mm的磨球和直径为10mm的磨球的个数比为(1～5)：1。
  10. 如权利要求1所述的制备方法，其特征在于，所述第二碳化的温度为800～1200℃，时间为30～120min；
    升温至所述第二碳化的温度的升温速度为5～15℃/min。
  11. 如权利要求1或10所述的制备方法，其特征在于，所述第二碳 化完成后，还包括将所得产物进行酸洗。
  12. 如权利要求11所述的制备方法，其特征在于，所述酸洗采用的酸液为浓度为0.01～0.5mol/L的盐酸。
  13. 如权利要求1所述的制备方法，其特征在于，所述生物质废料粉末的粒径为10～900μm。
  14. 权利要求1～13任一项所述的制备方法制备得到的硬碳在电池领域中的应用。
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CN108258216A (zh) * 2018-01-11 2018-07-06 电子科技大学 生物质碳-锡储能材料及其制备方法
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