WO2025065249A1 - 一种生物质基硬碳材料及其制备方法与用途 - Google Patents

一种生物质基硬碳材料及其制备方法与用途 Download PDF

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Publication number
WO2025065249A1
WO2025065249A1 PCT/CN2023/121592 CN2023121592W WO2025065249A1 WO 2025065249 A1 WO2025065249 A1 WO 2025065249A1 CN 2023121592 W CN2023121592 W CN 2023121592W WO 2025065249 A1 WO2025065249 A1 WO 2025065249A1
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biomass
hard carbon
precursor particles
preparation
temperature
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English (en)
French (fr)
Inventor
郑爽
阮丁山
李长东
毛林林
张苗
齐俊
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
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Priority to CN202380011439.1A priority Critical patent/CN117677582B/zh
Priority to PCT/CN2023/121592 priority patent/WO2025065249A1/zh
Publication of WO2025065249A1 publication Critical patent/WO2025065249A1/zh
Anticipated expiration legal-status Critical
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • 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
    • H01M4/58—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
    • 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 embodiments of the present application relate to the field of battery technology, for example, a biomass-based hard carbon material and a preparation method and use thereof.
  • sodium-ion batteries As a secondary battery, the electrochemical mechanism of sodium-ion batteries is similar to that of lithium batteries. However, compared with lithium-ion batteries, sodium-ion batteries have the following advantages: abundant reserves of raw materials and low prices; sodium-ion batteries are allowed to discharge to 0V; and the battery energy density is greater than 100Wh/kg, which is comparable to lithium iron phosphate batteries. It can be seen that its cost advantage is obvious.
  • hard carbon As a negative electrode material for sodium ion batteries, hard carbon has more outstanding capacity and stability than graphite commonly used in lithium batteries; because the radius of sodium ions (0.103nm) is much larger than the radius of lithium ions (0.071nm), the small spacing between graphite layers is not conducive to the deintercalation of sodium ions, while the long-range disordered structure of hard carbon has many defects and micropores that contribute to the adsorption and storage of sodium ions.
  • the raw materials of hard carbon are mainly divided into biomass, resin and coal-based.
  • resin-based hard carbon has good performance, but the cost is relatively high; the capacity of coal-based hard carbon is difficult to increase, and the raw materials rely on coal mining; in comparison, biomass-based hard carbon has more development and application advantages due to its wide source of raw materials, easy structure control and low cost.
  • CN115259136A discloses a method for preparing biomass-based hard carbon materials in large quantities using waste biomass, wherein lignin is extracted by destroying the biomass using a specific pretreatment solution, the obtained lignin is pre-carbonized and high-temperature carbonized, and after acid washing at 40 to 80°C, the target hard carbon material is obtained by drying.
  • CN113044827A discloses a method for preparing a nano-carbon composite biomass hard carbon electrode material.
  • the biomass raw material is cleaned and crushed, and then heated with an alkaline solution. After cleaning and drying, it is first heated and stirred in a 1-5 mol/L alkaline solution at 90-120°C, and then put into a 1-5 mol/L acid solution and heated and stirred at 90-120°C. After microwave hydrothermal reaction, pre-carbonization and high-temperature treatment, the target hard carbon material is obtained.
  • the method of preparing hard carbon from biomass raw materials is relatively complicated, and the disadvantage of preparing hard carbon from biomass raw materials is that there are too many impurities. Therefore, the commonly used impurity removal method in industry is also high-temperature alkali washing and acid washing as in the above scheme, but the impurity removal processing cost of this method is high and the equipment requirements are high. Therefore, it is still necessary to develop a new manufacturing scheme for biomass-based hard carbon materials.
  • the embodiment of the present application provides a biomass-based hard carbon material and its preparation method and use.
  • the preparation method sequentially performs anaerobic baking, impurity removal, oxidation modification and high-temperature carbonization on the biomass raw material to obtain the biomass-based hard carbon material.
  • the present application first sequentially performs anaerobic baking and impurity removal, so that the lignin and cellulose in the biomass raw material are destroyed, leaving pores and defects inside, so that the material is in a metastable structure to expose impurities, and then it can be selected to remove impurities at room temperature, and the impurity removal effect is excellent.
  • the impurity content of the obtained biomass-based hard carbon is low, and the ash content can be reduced to less than 0.5wt%, and it has a disordered interlayer structure, which is conducive to the insertion/extraction of sodium ions, and can show a higher reversible capacity and first-effect performance.
  • the present invention provides a method for preparing a biomass-based hard carbon material, the method comprising the following steps:
  • the biomass raw materials are subjected to oxygen-free baking, impurity removal, oxidation modification and high-temperature carbonization in sequence to obtain biomass-based hard carbon materials.
  • the present invention first performs anaerobic baking and impurity removal in sequence, so that the lignin and cellulose in the biomass raw materials are destroyed, leaving pores and defects inside, so that the material is in a metastable structure to expose impurities, and then the impurity removal can be achieved at room temperature, and the impurity removal effect is excellent.
  • the impurity content of the obtained biomass-based hard carbon is low, the ash content can be reduced to less than 0.5wt%, and it has a disordered interlayer structure, which is conducive to the embedding of sodium ions. In/out, it can show higher reversible capacity and first-effect performance.
  • biomass raw materials the main components that contribute to hard carbon in biomass raw materials are lignin and part of cellulose.
  • Biomass raw materials, especially fibrous biomass raw materials are composed of hemicellulose, cellulose, lignin and various impurities.
  • the impurities are all present in the structure of hemicellulose, cellulose and lignin. To remove these impurities, it is necessary to destroy the stable connection between hemicellulose, cellulose and lignin.
  • the present application first performs anaerobic baking to decompose hemicellulose, cellulose and lignin under certain temperature conditions, and the impurities can be exposed; therefore, subsequent impurity removal can be selected to be carried out under room temperature conditions, and further, the main impurities in the biomass can be analyzed by elements, so that the subsequent impurity removal is targeted.
  • biomass raw materials are mainly composed of three major components, namely hemicellulose, cellulose and lignin, and usually use cellulose as the skeleton, lignin and hemicellulose are tightly entangled on the skeleton, it is difficult to break the steady-state structure of biomass raw materials by directly removing impurities and oxidative modification without anaerobic baking; since the decomposition temperatures of hemicellulose, cellulose and lignin increase in sequence, hemicellulose and part of cellulose can be decomposed at a relatively low temperature, so anaerobic baking can provide natural pore sites for organic carbon sources on the one hand, and on the other hand, it can destroy the original steady-state structure of biomass, which is beneficial to subsequent impurity removal and oxidative modification;
  • the hard carbon precursor after impurity removal is mainly composed of a segment structure of C, H, and O, and is still in an organic state. In this state, oxygen-containing functional groups are directly introduced through oxidation modification as connecting bonds between organic segments. The strength is higher than that of hydrogen bonds, which is beneficial to the subsequent structural aromatic ring rearrangement.
  • the preparation method described in this application can realize the production of normalized hard carbon materials from different biomass raw materials. Normalization refers to the process of treating essentially different materials to obtain materials with similar structures and properties. As mentioned above, the components of biomass raw materials are hemicellulose, cellulose, wood Elements and impurities, the difference between different biomass raw materials lies in the impurity composition and the content of the three major elements.
  • the biomass-based hard carbon obtained by the preparation method described in this application has a similar structure and little difference in performance.
  • the biomass raw material includes any one of poplar sawdust, pine sawdust, litchi sawdust, coconut shell, bamboo sawdust, cotton or wheat straw, or a combination of at least two of them.
  • the anaerobic baking is carried out in an inert atmosphere, and the oxygen concentration is less than 1000ppm, for example, 990ppm, 900ppm, 800ppm, 700ppm, 600ppm, 500ppm, 400ppm, 300ppm, 200ppm, 100ppm, 50ppm, 10ppm or 0ppm, 0ppm means an oxygen-free atmosphere, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the inert atmosphere includes any one of nitrogen, argon or helium, or a combination of at least two of them.
  • Typical but non-limiting examples of the combination include a combination of nitrogen and argon, a combination of nitrogen and helium, or a combination of argon and helium.
  • the temperature of the oxygen-free baking is 200-1000°C, for example 200°C, 300°C, 400°C, 500°C, 600°C, 700°C, 800°C, 900°C or 1000°C, and the time is 15-48h, for example 15h, 18h, 21h, 24h, 27h, 30h, 33h, 36h, 39h, 42h, 45h or 48h, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the material is discharged and subjected to a first crushing to obtain first precursor particles, and the first precursor particles are subjected to impurity removal.
  • the median particle size of the first precursor particles is 0.5-1 mm, for example 0.5 mm, 0.55 mm, 0.6 mm, 0.65 mm, 0.7 mm, 0.75 mm, 0.8 mm, 0.85 mm, 0.9 mm, 0.95 mm or 1 mm, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the impurity removal is liquid phase impurity removal, and the biomass raw material after anaerobic baking is treated in a solution containing an impurity remover.
  • the impurity remover comprises any one of sodium hydroxide, potassium hydroxide, sulfuric acid, hydrochloric acid, phosphoric acid or hydrofluoric acid, or a combination of at least two thereof.
  • Typical but non-limiting examples of the combination include a combination of sodium hydroxide and potassium hydroxide, a combination of sulfuric acid and hydrochloric acid, a combination of hydrochloric acid and phosphoric acid, a combination of hydrochloric acid and hydrofluoric acid, a combination of phosphoric acid and hydrofluoric acid, or a combination of sulfuric acid and hydrofluoric acid.
  • the solution containing the impurity remover also contains additives.
  • the additive comprises any one of thiourea, urea, disodium edetate, citric acid, aqueous ammonia or sodium gluconate, or a combination of at least two thereof.
  • Typical but non-limiting examples of the combination include a combination of thiourea and urea, a combination of thiourea and disodium edetate, a combination of citric acid and disodium edetate, a combination of aqueous ammonia and urea, or a combination of sodium gluconate and citric acid.
  • the present application preferably uses a combination of an impurity remover and an additive to produce a synergistic effect, so that the pretreated precursor is further decomposed at room temperature, leaving abundant pores and defects inside the material after further decomposition.
  • the material is in a metastable structure, and a substitution reaction occurs between the impurities and the impurity remover, and the impurities are dissolved in the aqueous solution in a free state, thereby further improving the effect of room temperature impurity removal.
  • the role of the additive is to open the chain structure of the hard carbon precursor and promote the impurity removal effect of the impurity remover; the impurity remover is determined according to the type of impurity elements in the material.
  • the impurity elements can be divided into alkaline metal/non-metal elements and acidic metal/non-metal elements. After testing, the types of impurity metal/non-metal elements with higher content are obtained, so that the impurity remover can be used in a targeted manner.
  • the liquid phase impurity removal is carried out at a rotation speed of 100 to 500 rpm, for example, 100 rpm, 150 rpm, 200 rpm, 250 rpm, 300 rpm, 350 rpm, 400 rpm, 450 rpm or 500 rpm, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the treatment time of the liquid phase impurity removal is 3 to 24 hours, for example, 3 hours, 6 hours, 9 hours, 12 hours, 15 hours, 18h, 21h or 24h, etc., but are not limited to the listed values, and other values not listed within the above value range are also applicable.
  • washing is first performed until the pH value is 7, and then the second crushing is performed after drying.
  • the drying temperature is 80-120°C, for example 80°C, 90°C, 100°C, 110°C or 120°C
  • the time is 8-12h, for example 8h, 9h, 10h, 11h or 12h, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the second crushing obtains second precursor particles, and the second precursor particles are oxidatively modified, and the median particle size of the second precursor particles is 4 to 10 ⁇ m, for example, 4 ⁇ m, 4.5 ⁇ m, 5 ⁇ m, 5.5 ⁇ m, 6 ⁇ m, 6.5 ⁇ m, 7 ⁇ m, 7.5 ⁇ m, 8 ⁇ m, 8.5 ⁇ m, 9 ⁇ m, 9.5 ⁇ m or 10 ⁇ m, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the present application preferably performs coarse crushing (first crushing) after anaerobic baking, and performs fine crushing (second crushing) after impurities are removed.
  • first crushing coarse crushing
  • second crushing fine crushing
  • the pores and defects can be exposed to the greatest extent.
  • Oxidative modification introduces oxygen-containing functional groups into the material structure as connecting bonds between chain segments, which have a higher strength than hydrogen bonds and are beneficial to the subsequent structural aromatic ring rearrangement.
  • the subsequent high-temperature carbonization process as the temperature slowly rises, due to the existence of tension stress in the material itself, the material continues to shrink, achieving a "self-repairing” effect, "repairing" the pores on the surface, thereby forming a closed-cell structure.
  • the oxidation modification method includes oxygen-containing sintering and/or liquid phase oxidation.
  • One of the purposes of the oxidative modification carried out in the present application is to introduce oxygen-containing functional groups.
  • a part of the oxygen molecules react with carbon to form oxygen-containing functional groups as active sites, while another part of the oxygen reacts with part of the carbon to generate CO and/or CO2 , so that pores are further formed on the surface and inside of the material, which contribute to the storage of sodium ions and thus improve the electrochemical properties of the material.
  • the oxygen concentration of the oxygen-containing sintering is 10% to 15%, for example 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%, 13.5%, 14%, 14.5% or 15%, etc., but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the temperature of the oxygen-containing sintering is 400-600°C, for example 400°C, 420°C, 440°C, 460°C, 480°C, 500°C, 520°C, 540°C, 560°C, 580°C or 600°C, and the time is 1-5h, for example 1h, 1.5h, 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or 5h, etc., but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the liquid phase oxidation processes the impurity-removed biomass raw material in a solution containing an oxidant
  • the treatment time of the liquid phase oxidation is 6 to 12 h, for example 6 h, 6.5 h, 7 h, 7.5 h, 8 h, 8.5 h, 9 h, 9.5 h, 10 h, 10.5 h, 11 h, 11.5 h or 12 h, and the treatment temperature is -3 to 5 ° C, for example -3 ° C, -2 ° C, -1 ° C, 0 ° C, 1 ° C, 2 ° C, 3 ° C, 4 ° C or 5 ° C, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the temperature of the high-temperature carbonization is 1600-1800°C, for example, 1600°C, 1620°C, 1640°C, 1660°C, 1680°C, 1700°C, 1720°C, 1740°C, 1760°C, 1780°C or 1800°C, and the time is 3-20h, for example, 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h or 20h, but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the heating rate of the high-temperature carbonization is 0.5 to 3°C/min, for example, 0.5°C/min, 1°C/min, 1.5°C/min, 2°C/min, 2.5°C/min or 3°C/min, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the high-temperature carbonization is carried out under an inert atmosphere.
  • the preparation method comprises the following steps:
  • the second precursor particles are mixed with an aqueous solution containing an oxidant, stirred at -3 to 5° C. for 6 to 12 hours, and dried to obtain third precursor particles;
  • the temperature is increased at a rate of 0.5 to 3°C/min, and the third precursor particles are subjected to high-temperature carbonization treatment at 1600 to 1800°C for 3 to 20 hours. After cooling to room temperature, a biomass-based hard carbon material is obtained.
  • an embodiment of the present application provides a biomass-based hard carbon material obtained using the preparation method described in the first aspect.
  • the ash content of the hard carbon material is less than 0.5wt%, for example 0.45wt%, 0.40wt%, 0.35wt%, 0.30wt%, 0.25wt%, 0.20wt%, 0.15wt%, 0.10wt%, 0.05wt% or 0.01wt%, etc., but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the pore size of the hard carbon material is 0.5 to 20 nm, for example 0.5 nm, 1 nm, 3 nm, 5 nm, 7 nm, 9 nm, 10 nm, 12 nm, 14 nm, 16 nm, 18 nm or 20 nm, but is not limited to the listed values, and other unlisted values within the above numerical range are also applicable.
  • the true density of the hard carbon material is 1.3-2.0 g/cm 3 , for example 1.3 g/cm 3 , 1.4 g/cm 3 , 1.5 g/cm 3 , 1.6 g/cm 3 , 1.7 g/cm 3 , 1.8 g/cm 3 , 1.9 g/cm 3 or 2.0 g/cm 3 , but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • the specific surface area of the hard carbon material is less than 5 g/m 2 , for example 4.8 g/m 2 , 4.5 g/m 2 , 4 g/m 2 , 3.5 g/m 2 , 3 g/m 2 , 2.5 g/m 2 , 2 g/m 2 , 1.5 g/m 2 , 1 g/m 2 , 0.5 g/m 2 or 0.1 g/m 2 , but is not limited to the listed values, and other values not listed within the above numerical range are also applicable.
  • an embodiment of the present application provides a negative electrode plate comprising the biomass-based hard carbon material described in the second aspect.
  • an embodiment of the present application provides a battery comprising the negative electrode sheet described in the third aspect.
  • the embodiments of the present application have at least the following beneficial effects:
  • the embodiment of the present application first performs anaerobic baking and impurity removal in sequence, so that the lignin and cellulose in the biomass raw material are destroyed, leaving pores and defects inside, so that the material is in a metastable structure to expose impurities, and then the impurity removal can be achieved at room temperature, and the impurity removal effect is excellent.
  • the obtained biomass-based hard carbon has a low impurity content, the ash content can be reduced to less than 0.5wt%, and has a disordered interlayer structure, which is conducive to the insertion/extraction of sodium ions, and can show a higher reversible capacity and first-effect performance;
  • the embodiment of the present application uses a synergistic effect of an impurity remover and an additive, so that the pretreated precursor is further decomposed at room temperature, and after further decomposition, abundant pores and defects are left inside the material.
  • the material is in a metastable structure, and a substitution reaction occurs between the impurities and the impurity remover, and the impurities are dissolved in the aqueous solution in a free state, thereby further improving the effect of room temperature impurity removal;
  • oxygen-containing functional groups are introduced by oxidation modification.
  • a portion of the oxygen molecules react with the carbon to form oxygen-containing functional groups as active sites, while another portion of the oxygen reacts with a portion of the carbon to generate
  • the formation of CO and/or CO 2 further forms pores on the surface and inside of the material, which helps to store sodium ions and thus improve the electrochemical performance of the material;
  • FIG1 is a SEM image of the first precursor particles obtained in Example 1;
  • FIG2 is a SEM image of the biomass-based hard carbon material obtained in Example 1;
  • FIG3 is a charge and discharge curve diagram of the biomass-based hard carbon material obtained in Example 1;
  • FIG. 4 is an XRD diagram of the biomass-based hard carbon material obtained in Example 1.
  • This embodiment provides a biomass-based hard carbon material, which is prepared by the following method:
  • step (2) The first precursor particles obtained in step (1) were placed in a stirring vessel at a mass ratio of 22:4:74. Sodium hydroxide, sodium gluconate and water were added in order, stirred at room temperature for 3 hours, washed until neutral, dried, and crushed by air jet mill to a median particle size of 5 ⁇ m to obtain second precursor particles;
  • step (3) The second precursor particles of step (2) are placed in a nitrogen atmosphere with the oxygen concentration controlled at 8%, and the temperature is rapidly raised to 800°C within 5°C/min, and the treatment is carried out for 6 hours to introduce oxygen-containing functional groups to obtain third precursor particles.
  • step (3) Under argon conditions, the third precursor particles obtained in step (3) are subjected to high-temperature closed-pore treatment, the temperature is raised to 1700°C at 2°C/min, and the temperature is kept at this temperature for 8 hours, and the temperature is lowered to room temperature to obtain a biomass-based hard carbon material with an internal porous structure.
  • Figures 1 and 2 are SEM images of the first precursor particles obtained in Example 1 and the biomass-based hard carbon material obtained after sintering in the high-temperature stage, respectively. It can be seen from the figure that the surface of the first precursor particles contains a large amount of particulate impurities. The surface of the biomass-based hard carbon material obtained after impurity removal and carbonization is smooth, and the particle size is significantly reduced after carbonization.
  • Figure 3 is a charge and discharge curve of the biomass-based hard carbon material obtained in Example 1. It can be seen from the figure that the electrochemical properties of the biomass-based hard carbon: the first charge is 334.43mAh/g, and the first charge is 88.65%.
  • Figure 4 is the XRD diagram of the biomass-based hard carbon material obtained in Example 1. It can be seen from the figure that the hard carbon material has no impurities, and the lattice spacing is about 3.8nm through calculation.
  • This embodiment provides a biomass-based hard carbon material, which is prepared by the following method:
  • step (2) placing the first precursor particles obtained in step (1) in a stirred tank, adding sodium hydroxide, thiourea and water in a mass ratio of 12:7:81 in sequence, stirring at room temperature for 3 hours, washing until neutral, drying, and crushing by jet milling to a median particle size of 5 ⁇ m to obtain second precursor particles;
  • step (3) placing the second precursor particles in step (2) in a nitrogen atmosphere with the oxygen concentration controlled at 8%, Rapidly heat to 800°C within 5°C/min, treat for 6 hours, introduce oxygen-containing functional groups, and obtain third precursor particles (4); Under argon conditions, the third precursor particles obtained in step (3) are subjected to high-temperature closed-pore treatment, heated to 1700°C at 2°C/min, kept warm for 8 hours, and cooled to room temperature to obtain a biomass-based hard carbon material with an internal porous structure.
  • This embodiment provides a biomass-based hard carbon material, which is prepared by the following method:
  • step (2) placing the first precursor particles obtained in step (1) in a stirred tank containing 20% HF, stirring at room temperature for 3 h, washing until neutral, drying, and crushing by jet milling to a median particle size of 5 ⁇ m to obtain second precursor particles;
  • step (3) placing the second precursor particles of step (2) in 500 mL of a mixed solution of phosphoric acid and sulfuric acid in a molar ratio of 3:1, stirring with a stirrer at a temperature of 0 to 3° C., adding 3 g of potassium permanganate every two minutes, adding 60 g in batches, stirring for 6 h, and finally adding 100 mL of hydrogen peroxide, stirring for 12 h, washing to neutrality, introducing oxygen-containing functional groups, and drying to obtain third precursor particles;
  • step (3) Under argon conditions, the third precursor particles obtained in step (3) are subjected to high-temperature closed-pore treatment, the temperature is increased to 1600°C at 2°C/min, kept at this temperature for 8 hours, and then cooled to room temperature to obtain a biomass-based hard carbon material with an internal porous structure.
  • Step (3) of the method for preparing the biomass-based hard carbon material is:
  • the second precursor particles of step (2) were placed in 500 mL of a mixture of phosphoric acid and sulfuric acid with a molar ratio of 3:1. The mixture was stirred with a stirrer at a temperature of 0 to 3°C, 3 g of potassium permanganate was added every two minutes, 60 g was added in batches, and the mixture was stirred for 6 hours. Finally, 100 mL of hydrogen peroxide was added, and the mixture was stirred for 12 hours. The mixture was washed to neutrality, oxygen-containing functional groups were introduced, and the mixture was dried to obtain the third precursor particles.
  • This embodiment provides a biomass-based hard carbon material.
  • urea is used to replace thiourea in step (2).
  • other conditions are exactly the same as those in Example 2.
  • This embodiment provides a biomass-based hard carbon material.
  • disodium ethylenediaminetetraacetate is used in step (2) to replace thiourea.
  • other conditions are exactly the same as those in Example 2.
  • This embodiment provides a biomass-based hard carbon material.
  • ammonia water is used to replace thiourea in step (2).
  • other conditions are exactly the same as those in Example 2.
  • This embodiment provides a biomass-based hard carbon material.
  • sodium gluconate is used to replace thiourea in step (2).
  • other conditions are exactly the same as those in Example 2.
  • This comparative example provides a biomass-based hard carbon material, which is prepared by the following method:
  • step (2) The sample obtained in step (1) is subjected to a jet mill to reduce the median particle size to 5 ⁇ m, and the obtained to biomass-based hard carbon materials.
  • This comparative example provides a biomass-based hard carbon material.
  • the preparation method of the biomass-based hard carbon material does not perform step (2), and directly performs step (3) on the first precursor particles obtained in step (1). Apart from this, other conditions are exactly the same as those in Example 2.
  • This comparative example provides a biomass-based hard carbon material.
  • the preparation method of the biomass-based hard carbon material does not perform step (3), and directly performs step (4) on the second precursor particles obtained in step (2). Apart from this, other conditions are exactly the same as those in Example 2.
  • This comparative example provides a biomass-based hard carbon material.
  • the preparation method of the biomass hard carbon material is different from that of Example 2 in that anaerobic baking, oxidative modification, impurity removal and high-temperature carbonization are performed in sequence.
  • the preparation method is as follows:
  • step (2) placing the first precursor particles obtained in step (1) in a nitrogen atmosphere with an oxygen concentration controlled at 8%, rapidly heating to 800° C. within 5° C./min, treating for 6 h, introducing oxygen-containing functional groups, and crushing by air flow milling to a median particle size of 5 ⁇ m to obtain second precursor particles;
  • step (3) placing the second precursor particles of step (2) in a stirring kettle, adding sodium hydroxide, thiourea and water in a mass ratio of 12:7:81 in sequence, stirring at room temperature for 3 hours, washing to neutrality, and drying to obtain third precursor particles;
  • step (3) Under argon conditions, the third precursor particles obtained in step (3) are subjected to high temperature pore closing treatment. The temperature was raised to 1700°C at 2°C/min, kept at that temperature for 8h, and then cooled to room temperature to obtain the biomass-based hard carbon material.
  • This comparative example provides a biomass-based hard carbon material.
  • the preparation method of the biomass hard carbon material is different from that of Example 2 in that anaerobic baking, oxidative modification, high-temperature carbonization and impurity removal are performed in sequence.
  • the preparation method is as follows:
  • step (2) placing the first precursor particles obtained in step (1) in a nitrogen atmosphere with an oxygen concentration controlled at 8%, rapidly heating to 800° C. within 5° C./min, treating for 6 h, introducing oxygen-containing functional groups, and crushing by air flow milling to a median particle size of 5 ⁇ m to obtain second precursor particles;
  • step (3) Under argon conditions, the second precursor particles of step (2) were subjected to high-temperature closed-pore treatment, the temperature was raised to 1700° C. at 2° C./min, kept at that temperature for 8 h, and then cooled to room temperature to obtain third precursor particles;
  • step (3) The third precursor particles obtained in step (3) are placed in a stirring kettle, and sodium hydroxide, thiourea and water are added in a mass ratio of 12:7:81 in sequence, stirred at room temperature for 3 hours, washed until neutral, and dried to obtain a biomass-based hard carbon material.
  • the hard carbon material obtained in the examples and comparative examples was dissolved in deionized water with sodium carboxymethyl cellulose, super P conductive agent, and polymer binder at a ratio of 95:2:1:2 to form a slurry, which was then coated on copper foil.
  • the electrode was placed in a drying oven at 80°C for 4 to 10 hours to obtain a hard carbon negative electrode. Finally, the electrode was placed in an argon atmosphere. Button cells were assembled in a glove box.
  • the electrolyte used was NaClO 4 dissolved in ethylene carbonate and propylene carbonate in a volume ratio of 1:1.
  • Sodium metal foil was used as the counter electrode and reference electrode.
  • the electrochemical properties were tested by an electrochemical workstation and other equipment, and the results are recorded in Table 1.
  • the specific surface area of the biomass-based hard carbon sample prepared in the embodiment is smaller than that of comparative example 1, and the specific surface area of the sample after medium-temperature treatment in the embodiment is larger than the specific surface area after high-temperature carbonization. This is only because the temperature is rapidly raised to the medium-temperature stage, causing the structure in the material to rapidly rearrange. Due to the rapid temperature change, the molecular weight moves faster and faster, causing the connections between the structures to gradually become messy, exposing a large number of pores and defects. With the further slow increase in temperature and the presence of catalytic gas, impurity elements will be removed. Due to the change in temperature, the material itself has tension stress, causing the material to continuously shrink, achieving a "self-repairing" effect, "repairing" the surface pores without affecting the formation of the internal pore structure, thereby reducing the specific surface area.
  • the electrochemical performance of the hard carbon product prepared in the embodiment is better than that in the comparative example 1. This is because the high temperature catalytic carbonization process makes the impurities contained in the material volatilize and the material undergoes The structure is rearranged and the surface defects can be repaired by itself, so that the material forms closed pores, the specific surface area is reduced, and the sodium ions forming SEI are reduced, thereby improving the capacity and initial efficiency of the material.
  • Example 2 The electrochemical performance of Example 2 is better than that of Example 4. This is because in Example 4, liquid-phase oxidation is carried out in solution. In addition to the effect of the oxidant on the material, the aqueous solution also affects the structure of the material under the action of a strong oxidant, resulting in an excessively large specific surface area of the material and abundant internal pores, which makes it impossible for the material to shrink and close the pores through its own tension, resulting in performance differences from Example 2.
  • Example 2 The electrochemical performance of Example 2 is better than that of Comparative Examples 2 and 3. Since the material of Comparative Example 2 has not been impurized, the capacity and initial efficiency of the material are greatly affected. The presence of impurities leads to a low carbon content of the material. Untreated Si and other impurities react with carbon to form SiC, which causes the material structure to mutate, making it difficult to achieve excellent energy storage performance. The material of Comparative Example 3 has been impurity-free and has relatively excellent performance. Since the pores of Comparative Example 3 are all natural pores, the energy storage is limited, and the capacity is greatly different from that of Example 2.
  • Example 2 The electrochemical performance of Example 2 is better than that of Comparative Examples 4 and 5.
  • the comparative examples adjust the process sequence, so that the material cannot achieve the effect of impurity removal.
  • the presence of impurities leads to a low carbon content of the material.
  • Untreated Si and other impurities react with carbon to form SiC, causing the material structure to mutate, making it difficult to achieve excellent energy storage performance.

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Abstract

本申请提供了一种生物质基硬碳材料及其制备方法与用途，该制备方法将生物质原料依次进行无氧烘焙、除杂、氧化改性及高温炭化，得到生物质基硬碳材料。本申请通过先依次进行无氧烘焙与除杂，使得生物质原料中的木质素及纤维素等破坏，在内部留下孔隙及缺陷，使材料处于亚稳态结构，以暴露杂质，进而可以选择在常温下实现除杂，且除杂效果优异，所得生物质基硬碳的杂质含量低，灰分可降至0.5wt％以下，且具有无序的层间结构，有利于钠离子的嵌入/脱出，可表现出较高的可逆容量和首效性能。

Description

一种生物质基硬碳材料及其制备方法与用途 技术领域
本申请实施例涉及电池技术领域，例如一种生物质基硬碳材料及其制备方法与用途。
背景技术
钠离子电池作为二次电池，其电化学机理与锂电池类似，但是与锂离子电池相比，钠离子电池具有的优势有：原材料储量丰富，价格低廉；允许钠离子电池放电到0V；电池能量密度大于100Wh/kg，而可与磷酸铁锂电池相媲美，可见，其成本优势明显。
作为钠离子电池负极材料，相较于锂电池中常用的石墨而言，硬碳的容量及稳定性更为突出；因为钠离子的半径(0.103nm)远大于锂离子半径(0.071nm)，石墨层间距较小不利于钠离子的脱嵌，而硬碳结构长程无序，有许多的缺陷和微孔有助于钠离子的吸附和存储。
硬碳的原料主要分为生物质类、树脂类、煤基类。其中树脂基硬碳性能好，但成本较高；煤基硬碳容量难提升，原料依靠煤矿开采；相比而言，生物质基硬碳，因原料来源广，结构好调控，成本较低更具有开发和应用优势。
CN115259136A公开了一种使用废弃生物质大批量制备生物质基硬碳材料的方法，通过使用特定的预处理溶液破坏生物质中提取木质素，将得到的木质素进行预碳化及高温碳化，经过40～80℃的酸洗后，干燥得到目标硬碳材料。
CN113044827A公开了一种纳米碳材复合生物质硬碳电极材料的制备方法，将生物质原料清洗破碎后，用碱溶液加热处理，清洗干燥后，先在1～5mol/L的碱溶液中于90～120℃下加热搅拌，再投入到1～5mol/L的酸溶液中于90～120℃下加热搅拌，再进行微波水热反应、预碳化及高温处理后，得到目标硬碳材料。
目前，因利用的生物质类原料制备硬碳的方法较为繁琐，且生物质类原料制备硬碳的劣势在于杂质过多，因而工业上常用的除杂方式也是如上述方案一样进行高温碱洗酸洗，但通过此方法除杂加工成本高，对设备的要求高。因此，尚需要开发一种新的生物质基硬碳材料的制造方案。
发明内容
以下是对本文详细描述的主题的概述。本概述并非是为了限制权利要求的保护范围。
本申请实施例提供一种生物质基硬碳材料及其制备方法与用途，所述制备方法将生物质原料依次进行无氧烘焙、除杂、氧化改性及高温炭化，得到生物质基硬碳材料。本申请通过先依次进行无氧烘焙与除杂，使得生物质原料中的木质素及纤维素等破坏，在内部留下孔隙及缺陷，使材料处于亚稳态结构，以暴露杂质，进而可以选择在常温下实现除杂，且除杂效果优异，所得生物质基硬碳的杂质含量低，灰分可降至0.5wt％以下，且具有无序的层间结构，有利于钠离子的嵌入/脱出，可表现出较高的可逆容量和首效性能。
第一方面，本申请实施例提供了一种生物质基硬碳材料的制备方法，所述制备方法包括如下步骤：
将生物质原料依次进行无氧烘焙、除杂、氧化改性及高温炭化，得到生物质基硬碳材料。
本申请通过先依次进行无氧烘焙与除杂，使得生物质原料中的木质素及纤维素等破坏，在内部留下孔隙及缺陷，使材料处于亚稳态结构，以暴露杂质，进而可以选择在常温下实现除杂，且除杂效果优异，所得生物质基硬碳的杂质含量低，灰分可降至0.5wt％以下，且具有无序的层间结构，有利于钠离子的嵌 入/脱出，可表现出较高的可逆容量和首效性能。
具体地说，从原料成分上讲，生物质原料中对硬碳作出贡献的主要成分是木质素以及部分纤维素，生物质原料，尤其是纤维类生物质原料是由半纤维素、纤维素、木质素以及各类杂质组成，杂质均存在于半纤维素、纤维素、木质素的结构之中，要去除这些杂质，需要破坏半纤维素、纤维素、木质素之间的稳定的连接，因此，本申请先进行无氧烘焙，使得半纤维素、纤维素、木质素在一定温度条件下，发生分解，杂质可以暴露出来；因此，后续除杂可以选择在常温室温条件下进行，进一步可以通过元素分析生物质内的主要杂质，使得后续的除杂具有针对性。
由于生物质原料主要是由半纤维素、纤维素、木质素这三大组分组成，通常以纤维素为骨架，木质素与半纤维素紧密缠绕在骨架上，故不进行无氧烘焙而直接通过除杂以及氧化改性很难破碎生物质原料的稳态结构；由于半纤维素、纤维素、木质素的分解温度依次增加，故可在相对较低温度下分解半纤维素和部分纤维素，故无氧烘焙一方面可以为有机碳源提供天然的孔隙位点，另一方面可以破坏生物质原本的稳态结构，利于后续的除杂和氧化改性；
当进行完无氧烘焙后，对于此时的除杂工序和氧化改性工序来说，由于材料处于亚稳态结构，部分杂质暴露，进而可以常温下实现除杂，经过除杂的硬碳前驱体，主要是由C、H、O的链段结构，还处于有机物的状态，此状态下经过氧化改性直接引入含氧官能团作为有机链段间的连接键，强度比氢键强度高，有利于后续的结构芳环化重排。
综上，使用本申请所述制备方法可以实现不同生物质原料的归一化硬碳材料的生产，归一化是指把本质上不同的材料，经过处理得到结构类似性能类似的材料的过程。如上所述，生物质原料的组成成分是半纤维素、纤维素、木质 素以及杂质，不同的生物质原料的差异就是在杂质组成以及三大素的含量差异，经过本申请所述制备方法的处理而得到的生物质基硬碳的结构类似，性能相差不大。
以下作为本申请优选的技术方案，但不作为本申请提供的技术方案的限制，通过以下技术方案，可以更好地达到和实现本申请的技术目的和有益效果。
作为本申请优选的技术方案，所述生物质原料包括白杨木屑、松木屑、荔枝木屑、椰壳、竹屑、棉花或小麦秸秆中的任意一种或至少两种的组合。
作为本申请优选的技术方案，所述无氧烘焙在惰性气氛下进行，氧气浓度＜1000ppm，例如990ppm、900ppm、800ppm、700ppm、600ppm、500ppm、400ppm、300ppm、200ppm、100ppm、50ppm、10ppm或0ppm，0ppm即无氧气氛，但并不仅限于列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述惰性气氛包括氮气、氩气或氦气中的任意一种或至少两种的组合，所述组合典型但非限制性的实例包括氮气与氩气的组合、氮气与氦气的组合或氩气与氦气的组合。
优选地，所述无氧烘焙的温度为200～1000℃，例如200℃、300℃、400℃、500℃、600℃、700℃、800℃、900℃或1000℃等，时间为15～48h，例如15h、18h、21h、24h、27h、30h、33h、36h、39h、42h、45h或48h等，但并不仅限于列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述无氧烘焙后，所述除杂前，冷却至＜50℃时，出料并进行第一破碎，得到第一前驱体颗粒，对所述第一前驱体颗粒进行除杂。
优选地，所述第一前驱体颗粒的中位粒径为0.5～1mm，例如0.5mm、0.55mm、0.6mm、0.65mm、0.7mm、0.75mm、0.8mm、0.85mm、0.9mm、0.95mm或1mm等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
作为本申请优选的技术方案，所述除杂为液相除杂，将无氧烘焙后的生物质原料在含有除杂剂的溶液中处理。
优选地，所述除杂剂包括氢氧化钠、氢氧化钾、硫酸、盐酸、磷酸或氢氟酸中的任意一种或至少两种的组合，所述组合典型但非限制性的实例包括氢氧化钠与氢氧化钾的组合、硫酸与盐酸的组合、盐酸与磷酸的组合、盐酸与氢氟酸的组合、磷酸与氢氟酸的组合或硫酸与氢氟酸的组合。
优选地，所述含有除杂剂的溶液中还有添加剂。
优选地，所述添加剂包括硫脲、尿素、乙二胺四乙酸二钠、柠檬酸、氨水或葡萄糖酸钠中的任意一种或至少两种的组合，所述组合典型但非限制性的实例包括硫脲与尿素的组合、硫脲与乙二胺四乙酸二钠的组合、柠檬酸与乙二胺四乙酸二钠的组合、氨水与尿素的组合或葡萄糖酸钠与柠檬酸的组合。
本申请优选使用除杂剂和添加剂配合产生协同作用，使得预处理后的前驱体在室温条件进一步分解，进一步分解后在材料内部留下丰富的孔隙及缺陷，此时材料处于亚稳态的结构，杂质与除杂剂之间发生置换反应，杂质呈游离态溶于水溶液中，从而进一步提升常温除杂的效果。
需要说明的是，添加剂的作用是将硬炭前体的链段结构打开，促进除杂剂的除杂效果；除杂剂的是根据材料中杂质元素的类型确定适宜的除杂剂，杂质元素可以分为碱性金属/非金属元素和酸性金属/非金属元素，经过检测得出含量较高的杂质金属/非金属元素种类，从而针对性地使用除杂剂。
优选地，所述液相除杂在转速100～500rpm下进行，例如100rpm、150rpm、200rpm、250rpm、300rpm、350rpm、400rpm、450rpm或500rpm等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述液相除杂的处理时间为3～24h，例如3h、6h、9h、12h、15h、 18h、21h或24h等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述除杂后，所述氧化改性前，先进行洗涤直至pH＝7，烘干后再进行第二破碎。
优选地，所述烘干的温度为80～120℃，例如80℃、90℃、100℃、110℃或120℃等，时间为8～12h，例如8h、9h、10h、11h或12h等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述第二破碎得到第二前驱体颗粒，对所述第二前驱体颗粒进行氧化改性，所述第二前驱体颗粒的中位粒径为4～10μm，例如4μm、4.5μm、5μm、5.5μm、6μm、6.5μm、7μm、7.5μm、8μm、8.5μm、9μm、9.5μm或10μm等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
本申请优选在无氧烘焙之后进行粗破(第一破碎)，在除杂之后进行细碎(第二破碎)，通过减小粒径并配合结构固化(氧化改性)可以将孔隙以及缺陷最大程度的暴露出来，通过氧化改性往材料结构中引入含氧官能团作为链段间的连接键，强度比氢键强度高，有利于后续的结构芳环化重排；而在后续的高温炭化过程中，随着温度缓慢升高，由于材料本身张力应力存在，使得材料不断回缩，达到“自我修复”效果，“修复”表面的孔隙，从而形成闭孔的结构。
作为本申请优选的技术方案，所述氧化改性的方法包括含氧烧结和/或液相氧化。
本申请进行的氧化改性的目的之一在于引入含氧官能团，当充分反应时，一部分氧分子与碳反应形成含氧官能团作活性位点，同时另一部分氧与部分碳反应生成CO和/或CO2使得材料表面及内部进一步形成孔隙，该孔隙有助于钠离子的储存从而提升材料的电化学性能。
优选地，所述含氧烧结的氧浓度为10％～15％，例如10％、10.5％、11％、11.5％、12％、12.5％、13％、13.5％、14％、14.5％或15％等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述含氧烧结的温度为400～600℃，例如400℃、420℃、440℃、460℃、480℃、500℃、520℃、540℃、560℃、580℃或600℃，时间为1～5h，例如1h、1.5h、2h、2.5h、3h、3.5h、4h、4.5h或5h等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述液相氧化将除杂后的生物质原料在含有氧化剂的溶液中处理；
优选地，所述液相氧化的处理时间为6～12h，例如6h、6.5h、7h、7.5h、8h、8.5h、9h、9.5h、10h、10.5h、11h、11.5h或12h等，处理温度为-3～5℃，例如-3℃、-2℃、-1℃、0℃、1℃、2℃、3℃、4℃或5℃等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
作为本申请优选的技术方案，所述高温炭化的温度为1600～1800℃，例如1600℃、1620℃、1640℃、1660℃、1680℃、1700℃、1720℃、1740℃、1760℃、1780℃或1800℃等，时间为3～20h，例如3h、4h、5h、6h、7h、8h、9h、10h、11h、12h、13h、14h、15h、16h、17h、18h、19h或20h等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述高温炭化的升温速率为0.5～3℃/min，例如0.5℃/min、1℃/min、1.5℃/min、2℃/min、2.5℃/min或3℃/min，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述高温炭化在惰性气氛下进行。
作为本申请优选的技术方案，所述制备方法包括如下步骤：
(1)将生物质原料置于惰性气氛中，体系内无氧或氧气浓度＜1000ppm， 在200～1000℃下进行无氧烘焙15～48h，冷却至＜50℃时，出料并进行第一破碎，得到毫米级的第一前驱体颗粒，中位粒径为0.5～1mm；
(2)将第一前驱体颗粒与含有除杂剂和添加剂的水溶液混合，在100～500rpm下搅拌3～24h进行液相除杂，水洗至pH＝7后，在80～120℃烘干8～12h，进行第二破碎，得到微米级的第二前驱体颗粒，中位粒径为4～10μm；
(3)将第二前驱体颗粒置于惰性气氛中，体系内氧气浓度10％～15％，在400～600℃下进行含氧烧结15～48h，降温至室温后，得到第三前驱体颗粒；
或，将第二前驱体颗粒与含有氧化剂的水溶液混合，在-3～5℃下搅拌处理6～12h，干燥后得到第三前驱体颗粒；
(4)在惰性气体保护下，以0.5～3℃/min的速率升温，将第三前驱体颗粒于1600～1800℃下进行高温炭化处理3～20h，降温至室温后，得到生物质基硬碳材料。
第二方面，本申请实施例提供了一种生物质基硬碳材料，使用第一方面所述的制备方法得到。
优选地，所述硬碳材料的灰分含量＜0.5wt％，例如0.45wt％、0.40wt％、0.35wt％、0.30wt％、0.25wt％、0.20wt％、0.15wt％、0.10wt％、0.05wt％或0.01wt％等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述硬碳材料的孔径大小为0.5～20nm，例如0.5nm、1nm、3nm、5nm、7nm、9nm、10nm、12nm、14nm、16nm、18nm或20nm等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述硬碳材料的真密度为1.3～2.0g/cm3，例如1.3g/cm3、1.4g/cm3、1.5g/cm3、1.6g/cm3、1.7g/cm3、1.8g/cm3、1.9g/cm3或2.0g/cm3等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
优选地，所述硬碳材料的比表面积＜5g/m2，例如4.8g/m2、4.5g/m2、4g/m2、3.5g/m2、3g/m2、2.5g/m2、2g/m2、1.5g/m2、1g/m2、0.5g/m2或0.1g/m2等，但并不仅限于所列举的数值，上述数值范围内其他未列举的数值同样适用。
第三方面，本申请实施例提供了一种负极极片，含有第二方面所述的生物质基硬碳材料。
第四方面，本申请实施例提供了一种电池，含有第三方面所述的负极极片。
与相关技术方案相比，本申请实施例至少具有以下有益效果：
(1)本申请实施例通过先依次进行无氧烘焙与除杂，使得生物质原料中的木质素及纤维素等破坏，在内部留下孔隙及缺陷，使材料处于亚稳态结构，以暴露杂质，进而可以选择在常温下实现除杂，且除杂效果优异，所得生物质基硬碳的杂质含量低，灰分可降至0.5wt％以下，且具有无序的层间结构，有利于钠离子的嵌入/脱出，可表现出较高的可逆容量和首效性能；
(2)本申请实施例使用除杂剂和添加剂配合产生协同作用，使得预处理后的前驱体在室温条件进一步分解，进一步分解后在材料内部留下丰富的孔隙及缺陷，此时材料处于亚稳态的结构，杂质与除杂剂之间发生置换反应，杂质呈游离态溶于水溶液中，从而进一步提升常温除杂的效果；
(3)本申请实施例在无氧烘焙之后进行粗破(第一破碎)，在除杂之后进行细碎(第二破碎)，通过减小粒径并进行结构固化可以将孔隙以及缺陷最大程度地暴露出来，在后续的高温炭化过程中，随着温度缓慢升高，由于材料本身张力应力存在，使得材料不断回缩，达到“自我修复”效果，“修复”表面的孔隙，从而形成闭孔的结构；
(4)本申请实施例通过氧化改性引入含氧官能团，当充分反应时，一部分氧分子与碳反应形成含氧官能团作活性位点，同时另一部分氧与部分碳反应生 成CO和/或CO2使得材料表面及内部进一步形成孔隙，该孔隙有助于钠离子的储存从而提升材料的电化学性能；
(5)本申请实施例所述的制备方法对生物质原料的适用性十分广泛，成本低，对于硬碳负极材料在工业上的应用具有现实意义。
在阅读并理解了附图和详细描述后，可以明白其他方面。
附图说明
附图用来提供对本文技术方案的进一步理解，并且构成说明书的一部分，与本申请的实施例一起用于解释本文的技术方案，并不构成对本文技术方案的限制。
图1是实施例1所得第一前驱体颗粒的SEM图；
图2是实施例1所得生物质基硬碳材料的SEM图；
图3是实施例1所得生物质基硬碳材料的充放电曲线图；
图4是实施例1所得生物质基硬碳材料XRD图。
具体实施方式
下面通过具体实施方式来进一步说明本申请的技术方案。
本领域技术人员应该明了，所述实施例仅仅是帮助理解本申请，不应视为对本申请的具体限制。
实施例1
本实施例提供了一种生物质基硬碳材料，通过如下方法制得：
(1)将1kg的竹屑置于氮气气氛下，氧浓度低于200ppm，升温至400℃，处理12h，冷却至50℃以下出料，利用颚式破碎机，破碎至中位粒度为1mm，得到第一前驱体颗粒；
(2)将步骤(1)得到的第一前驱体颗粒，置于搅拌釜中，以22∶4∶74的质 量配比依次加入氢氧化钠、葡萄糖酸钠及水，室温搅拌3h，洗至中性，烘干，利用气流磨破碎至中位粒度为5μm，得到第二前驱体颗粒；
(3)将步骤(2)的第二前驱体颗粒置于氮气气氛中，氧浓度控制在8％，5℃/min内快速升温至800℃，处理6h，引入含氧官能团，得到第三前驱体颗粒(4)在氩气条件下，将步骤(3)得到的第三前驱体颗粒进行高温闭孔处理，2℃/min升温至1700℃，保温8h，降温至室温，即可得到内部带有孔隙结构的生物质基硬炭材料。
图1及图2分别是实施例1所得第一前驱体颗粒和高温段烧结后所得生物质基硬碳材料的SEM图，由图中可以看出第一前驱体颗粒表面含有大量的颗粒杂质存在，经除杂炭化后得到的生物质基硬碳材料表面光滑，炭化后颗粒尺寸明显减小；图3是实施例1所得生物质基硬碳材料的充放电曲线图，由图中可以看出生物质基硬碳的电化学性能：首充334.43mAh/g，首充88.65％，图4是实施例1所得生物质基硬碳材料XRD图，由图中可以看出硬碳材料无杂质，且通过计算晶格间距在3.8nm左右。
实施例2
本实施例提供了一种生物质基硬碳材料，通过如下方法制得：
(1)将1kg的松木屑置于氮气气氛下，氧浓度低于200ppm，升温至250℃，处理48h，冷却至50℃以下出料，利用颚式破碎机，破碎至中位粒度为1mm，得到第一前驱体颗粒；
(2)将步骤(1)得到的第一前驱体颗粒，置于搅拌釜中，以12∶7∶81的质量配比依次加入氢氧化钠、硫脲及水，室温搅拌3h，洗至中性，烘干，利用气流磨破碎至中位粒度为5μm，得到第二前驱体颗粒；
(3)将步骤(2)的第二前驱体颗粒置于氮气气氛中，氧浓度控制在8％， 5℃/min内快速升温至800℃，处理6h，引入含氧官能团，得到第三前驱体颗粒(4)在氩气条件下，将步骤(3)得到的第三前驱体颗粒进行高温闭孔处理，2℃/min升温至1700℃，保温8h，降温至室温，即可得到内部带有孔隙结构的生物质基硬炭材料。
实施例3
本实施例提供了一种生物质基硬碳材料，通过如下方法制得：
(1)将1kg的白杨木屑置于氮气气氛下，氧浓度低于200ppm，升温至600℃，处理28h，冷却至50℃以下出料，利用颚式破碎机，破碎至中位粒度为1mm，得到第一前驱体颗粒；
(2)将步骤(1)得到的第一前驱体颗粒，置于含有20％HF的搅拌釜中，室温搅拌3h，洗至中性，烘干，利用气流磨破碎至中位粒度为5μm，得到第二前驱体颗粒；
(3)将步骤(2)的第二前驱体颗粒置于500mL的磷酸∶硫酸摩尔比为3∶1的混合溶液中，在0～3℃温度下，用搅拌器搅拌，隔两分钟加入3g高锰酸钾，分批共加入60g，搅拌处理6h，最后加入100mL的过氧化氢，搅拌处理12h，洗至中性，引入含氧官能团，干燥后，得到第三前驱体颗粒；
(4)在氩气条件下，将步骤(3)得到的第三前驱体颗粒进行高温闭孔处理，2℃/min升温至1600℃，保温8h，降温至室温，即可得到内部带有孔隙结构的生物质基硬炭材料。
实施例4
本实施例提供了一种生物质基硬碳材料，所述生物质基硬碳材料的制备方法的步骤(3)为：
将步骤(2)的第二前驱体颗粒置于500mL的磷酸∶硫酸摩尔比为3∶1的混 合溶液中，在0～3℃温度下，用搅拌器搅拌，隔两分钟加入3g高锰酸钾，分批共加入60g，搅拌处理6h，最后加入100mL的过氧化氢，搅拌处理12h，洗至中性，引入含氧官能团，干燥后，得到第三前驱体颗粒；
除此之外，其他条件与实施例2完全相同。
实施例5
本实施例提供了一种生物质基硬碳材料，所述生物质基硬碳材料的制备方法步骤(2)中使用尿素替换硫脲，除此之外，其他条件与实施例2完全相同。
实施例6
本实施例提供了一种生物质基硬碳材料，所述生物质基硬碳材料的制备方法步骤(2)中使用乙二胺四乙酸二钠替换硫脲，除此之外，其他条件与实施例2完全相同。
实施例7
本实施例提供了一种生物质基硬碳材料，所述生物质基硬碳材料的制备方法步骤(2)中使用氨水替换硫脲，除此之外，其他条件与实施例2完全相同。
实施例8
本实施例提供了一种生物质基硬碳材料，所述生物质基硬碳材料的制备方法步骤(2)中使用葡萄糖酸钠替换硫脲，除此之外，其他条件与实施例2完全相同。
对比例1
本对比例提供了一种生物质基硬碳材料，通过如下方法制得：
(1)将1kg的竹屑置于氩气气氛下，氧浓度低于200ppm，5℃/min升温至1600℃，保温10h，降温至室温，冷却需冷却至50℃以下出料；
(2)将步骤(1)得到的样品利用气流磨将的中位粒度将至5μm，即可得 到生物质基硬碳材料。
对比例2
本对比例提供了一种生物质基硬碳材料，所述生物质基硬碳材料的制备方法不进行步骤(2)，直接使步骤(1)中得到的第一前驱体颗粒进行步骤(3)，除此之外，其他条件与实施例2完全相同。
对比例3
本对比例提供了一种生物质基硬碳材料，所述生物质基硬碳材料的制备方法不进行步骤(3)，直接使步骤(2)中得到的第二前驱体颗粒进行步骤(4)，除此之外，其他条件与实施例2完全相同。
对比例4
本对比例提供了一种生物质基硬碳材料，所述生物质硬碳材料的制备方法与实施例2的区别为，依次进行无氧烘焙、氧化改性、除杂及高温碳化，所述制备方法如下：
(1)将1kg的椰壳置于氮气气氛下，氧浓度低于200ppm，升温至250℃，处理48h，冷却至50℃以下出料，利用颚式破碎机，破碎至中位粒度为1mm，得到第一前驱体颗粒；
(2)将步骤(1)得到的第一前驱体颗粒置于氮气气氛中，氧浓度控制在8％，5℃/min内快速升温至800℃，处理6h，引入含氧官能团，利用气流磨破碎至中位粒度为5μm，得到第二前驱体颗粒；
(3)将步骤(2)的第二前驱体颗粒置于搅拌釜中，以12∶7∶81的质量配比依次加入氢氧化钠、硫脲及水，室温搅拌3h，洗至中性，烘干，得到第三前驱体颗粒；
(4)在氩气条件下，将步骤(3)得到的第三前驱体颗粒进行高温闭孔处 理，2℃/min升温至1700℃，保温8h，降温至室温，即可得到生物质基硬炭材料。
对比例5
本对比例提供了一种生物质基硬碳材料，所述生物质硬碳材料的制备方法与实施例2的区别为，依次进行无氧烘焙、氧化改性、高温碳化及除杂，所述制备方法如下：
(1)将1kg的椰壳置于氮气气氛下，氧浓度低于200ppm，升温至250℃，处理48h，冷却至50℃以下出料，利用颚式破碎机，破碎至中位粒度为1mm，得到第一前驱体颗粒；
(2)将步骤(1)得到的第一前驱体颗粒置于氮气气氛中，氧浓度控制在8％，5℃/min内快速升温至800℃，处理6h，引入含氧官能团，利用气流磨破碎至中位粒度为5μm，得到第二前驱体颗粒；
(3)在氩气条件下，将步骤(2)的第二前驱体颗粒进行高温闭孔处理，2℃/min升温至1700℃，保温8h，降温至室温，得到第三前驱体颗粒；
(4)将步骤(3)得到的第三前驱体颗粒置于搅拌釜中，以12∶7∶81的质量配比依次加入氢氧化钠、硫脲及水，室温搅拌3h，洗至中性，烘干，即可得到生物质基硬炭材料。
通过国标方法GB/T 17664-1999测试实施例与对比例所得硬碳材料的灰分含量，结果记录于表1；
将实施例与对比例所得硬碳材料，与羧甲基纤维素钠、super P导电剂、聚合物粘接剂以95∶2∶1∶2的配比溶于去离子水中配成浆料，然后涂布在铜箔上，极片放于干燥箱中在80℃下干燥4～10h得到硬碳负极极片。最后在充满氩气气氛 的手套箱中组装扣式电池，所用电解液为NaClO4溶于体积比为1∶1的碳酸乙烯酯和碳酸丙烯酯制成；钠金属箔作为对电极和参比电极；通过电化学工作站等设备测试电化学性能，结果记录于表1。
表1
由表1可知：
实施例中制备的生物质基硬碳样品的比表面积较对比例1要小，实施例的中温处理后样品的比表面积比高温炭化后的比表面积要大，只是因为将温度迅速提高至中温阶段，使材料中的结构快速重排，由于温度变化较快，分子量运动越来越快，使得结构间的连接逐渐凌乱，大量的孔隙和缺陷暴露出来；随着进一步温度缓慢升高，以及催化气体的存在，杂质元素会被去除，由于温度的变化，材料本身张力应力存在，使得材料不断回缩，达到“自我修复”效果，“修复”表面的孔隙，而不影响内部孔隙结构的形成，缩小了比表面积。
实施例中制备得到硬炭产品的电化学性能比对比例1要好，这是由于高温催化炭化过程中一方面使材料内部含有的杂质被催化挥发，另一方面材料进行 了结构重排，可自行修复了表面的缺陷，使材料形成闭孔，比表面积缩小，形成SEI的钠离子减少，从而提升了材料的容量和首效。
实施例2的电化学性能优于实施例4的电化学性能，这是实施例4因为液相氧化是在溶液中进行的，除了氧化剂对材料的作用以外，在强氧化剂的作用下，水溶液对材料的结构也有影响，导致物料比表面积过大，内部孔隙丰富，导致材料无法通过自身张力回缩闭孔，导致性能与实施例2有差异。
实施例2的电化学性能优于对比例2、3，由于对比例2物料没有除杂对物料的容量以及首效的影响很大，杂质的存在导致材料的含碳率低，未处理的Si等杂质与碳发生反应生成SiC，使材料结构发生异变，很难实现优异的储能性能；对比例3的物料经过除杂，性能相对优异，由于对比例3的孔隙均为天然孔隙，储能有限，相对于实施例2容量存在较大差异。
实施例2的电化学性能优于对比例4、5，对比例调整工序顺序，使材料达不到除杂的效果，杂质的存在导致材料的含碳率低，未处理的Si等杂质与碳发生反应生成SiC，使材料结构发生异变，很难实现优异的储能性能。
本申请通过上述实施例来说明本申请的详细结构特征，但本申请并不局限于上述详细结构特征，即不意味着本申请必须依赖上述详细结构特征才能实施。所属技术领域的技术人员应该明了，对本申请的任何改进，对本申请所选用部件的等效替换以及辅助部件的增加、具体方式的选择等，均落在本申请的保护范围和公开范围之内。
以上详细描述了本申请的优选实施方式，但是，本申请并不限于上述实施方式中的具体细节，在本申请的技术构思范围内，可以对本申请的技术方案进行多种简单变型，这些简单变型均属于本申请的保护范围。
另外需要说明的是，在上述具体实施方式中所描述的各个具体技术特征， 在不矛盾的情况下，可以通过任何合适的方式进行组合，为了避免不必要的重复，本申请对各种可能的组合方式不再另行说明。
此外，本申请的各种不同的实施方式之间也可以进行任意组合，只要其不违背本申请的思想，其同样应当视为本申请所公开的内容。

Claims (15)

  1. 一种生物质基硬碳材料的制备方法，其包括如下步骤：
    将生物质原料依次进行无氧烘焙、除杂、氧化改性及高温炭化，得到生物质基硬碳材料。
  2. 根据权利要求1所述的制备方法，其中，所述生物质原料包括白杨木屑、松木屑、荔枝木屑、椰壳、竹屑、棉花或小麦秸秆中的任意一种或至少两种的组合。
  3. 根据权利要求1或2所述的制备方法，其中，所述无氧烘焙在惰性气氛下进行，氧气浓度＜1000ppm。
  4. 根据权利要求1-3任一项所述的制备方法，其中，所述惰性气氛包括氮气、氩气或氦气中的任意一种或至少两种的组合。
  5. 根据权利要求1-4任一项所述的制备方法，其中，所述无氧烘焙的温度为200～1000℃，时间为15～48h；
    优选地，所述无氧烘焙后，所述除杂前，冷却至＜50℃时，出料并进行第一破碎，得到第一前驱体颗粒，对所述第一前驱体颗粒进行除杂；
    优选地，所述第一前驱体颗粒的中位粒径为0.5～1mm。
  6. 根据权利要求1-5任意一项所述的制备方法，其中，所述除杂为液相除杂，将无氧烘焙后的生物质原料在含有除杂剂的溶液中处理。
  7. 根据权利要求6所述的制备方法，其中，所述除杂剂包括氢氧化钠、氢氧化钾、硫酸、盐酸、磷酸或氢氟酸中的任意一种或至少两种的组合；
    优选地，所述含有除杂剂的溶液中还有添加剂；
    优选地，所述添加剂包括硫脲、尿素、乙二胺四乙酸二钠、柠檬酸、氨水或葡萄糖酸钠中的任意一种或至少两种的组合。
  8. 根据权利要求6或7所述的制备方法，其中，所述液相除杂在转速 100～500rpm下进行；
    优选地，所述液相除杂的处理时间为3～24h。
  9. 根据权利要求1-8任意一项所述的制备方法，其中，所述除杂后，所述氧化改性前，先进行洗涤直至pH＝7，烘干后再进行第二破碎；
    优选地，所述烘干的温度为80～120℃，时间为8～12h；
    优选地，所述第二破碎得到第二前驱体颗粒，对所述第二前驱体颗粒进行氧化改性，所述第二前驱体颗粒的中位粒径为4～10μm。
  10. 根据权利要求1-9任意一项所述的制备方法，其中，所述氧化改性的方法包括含氧烧结和/或液相氧化；
    优选地，所述含氧烧结的氧浓度为10％～15％；
    优选地，所述含氧烧结的温度为400～600℃，时间为1～5h；
    优选地，所述液相氧化将除杂后的生物质原料在含有氧化剂的溶液中处理；
    优选地，所述液相氧化的处理时间为6～12h，处理温度为-3～5℃。
  11. 根据权利要求1-10任意一项所述的制备方法，其中，所述高温炭化的温度为1600～1800℃，时间为3～20h；
    优选地，所述高温炭化的升温速率为0.5～3℃/min；
    优选地，所述高温炭化在惰性气氛下进行。
  12. 根据权利要求1-11任意一项所述的制备方法，其包括如下步骤：
    (1)将生物质原料置于惰性气氛中，体系内无氧或氧气浓度＜1000ppm，在200～1000℃下进行无氧烘焙15～48h，冷却至＜50℃时，出料并进行第一破碎，得到毫米级的第一前驱体颗粒，中位粒径为0.5～1mm；
    (2)将第一前驱体颗粒与含有除杂剂和添加剂的水溶液混合，在100～500rpm下搅拌3～24h进行液相除杂，水洗至pH＝7后，在80～120℃烘干 8～12h，进行第二破碎，得到微米级的第二前驱体颗粒，中位粒径为4～10μm；
    (3)将第二前驱体颗粒置于惰性气氛中，体系内氧气浓度10％～15％，在400～600℃下进行含氧烧结15～48h，降温至室温后，得到第三前驱体颗粒；
    或，将第二前驱体颗粒与含有氧化剂的水溶液混合，在-3～5℃下搅拌处理6～12h，干燥后得到第三前驱体颗粒；
    (4)在惰性气体保护下，以0.5～3℃/min的速率升温，将第三前驱体颗粒于1600～1800℃下进行高温炭化处理3～20h，降温至室温后，得到生物质基硬碳材料。
  13. 一种生物质基硬碳材料，其使用权利要求1-12任意一项所述的制备方法得到；
    优选地，所述硬碳材料的灰分含量＜0.5wt％；
    优选地，所述硬碳材料的孔径大小为0.5～20nm；
    优选地，所述硬碳材料的真密度为1.3～2.0g/cm3；
    优选地，所述硬碳材料的比表面积＜5g/m2。
  14. 一种负极极片，其含有权利要求13所述的生物质基硬碳材料。
  15. 一种电池，其含有权利要求14所述的负极极片。
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