WO2024007461A1 - 一种硬碳材料及其制备方法与应用 - Google Patents

一种硬碳材料及其制备方法与应用 Download PDF

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WO2024007461A1
WO2024007461A1 PCT/CN2022/122920 CN2022122920W WO2024007461A1 WO 2024007461 A1 WO2024007461 A1 WO 2024007461A1 CN 2022122920 W CN2022122920 W CN 2022122920W WO 2024007461 A1 WO2024007461 A1 WO 2024007461A1
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nano
hard carbon
starch
carbon material
template material
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French (fr)
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郑爽
李长东
阮丁山
毛林林
张苗
侯远飞
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
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Publication of WO2024007461A1 publication Critical patent/WO2024007461A1/zh

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • 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
    • H01M10/054—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/10—Solid density
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/16—Pore diameter
    • 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 present invention specifically relates to a hard carbon material and its preparation method and application.
  • Sodium and lithium belong to the same family of elements, have similar physical and chemical properties to lithium, and are rich in resources, environmentally friendly and low-priced (30 to 40 times cheaper than lithium carbonate, the raw material of lithium).
  • the electrode potential of sodium ions (Na + /Na) is 0.3V higher than that of lithium ions (Li + /Li), which has more stable electrochemical performance and safety performance.
  • Partial pyrolysis of hard carbon can obtain a reversible sodium insertion capacity of nearly 280 mAh/g, but the initial irreversible capacity is high and the kinetic properties are poor.
  • the irreversible capacity problem of sodium embedded in hard carbon materials can be improved by optimizing the structure and reducing the specific surface area, but the improvement of the current existing technology is still not impressive enough.
  • the purpose of the present invention is to provide a hard carbon material and a preparation method thereof.
  • the preparation method uses starch and nano-framework template materials as raw materials to smelt a precursor, and then pre-carbonizes and removes the precursor in sequence. Through a series of steps such as templating and high-temperature carbonization, high-performance hard carbon materials can be finally obtained without introducing additional processing equipment or secondary processing carbon sources.
  • This product has a rich and stable pore structure and a small specific surface area, which can effectively improve
  • hard carbon materials are used as negative electrode materials for sodium-ion batteries, they have a bottleneck problem of high initial irreversible capacity, and at the same time, they provide sufficient reversible sites for the sodium ion deintercalation process.
  • a kind of hard carbon material the pore diameter of the hard carbon material is 0.5-20nm, the true density is 1.3-2.26g/cm 3 , and the specific surface area is ⁇ 5m 2 /g.
  • the product prepared by the preparation method of the hard carbon material of the present invention has a rich pore structure, a stable carbon frame structure, and a small specific surface area.
  • the amount of irreversible sodium ions consumed by the SEI film generated by the initial sodium deintercalation process is reduced. , effectively improving the initial reversible specific capacity and initial Coulomb efficiency.
  • Another object of the present invention is to provide a sodium-ion battery in which the negative electrode material is prepared from the hard carbon material of the present invention.
  • Another object of the present invention is to provide a preparation method of the hard carbon material, which includes the following steps:
  • precursor A (1) Mix and smelt the nanoframe template material and starch under a protective atmosphere until uniform, and cool to obtain precursor A; the mass ratio of the nanoframe template material to starch is 1: (5-20); the nanoframework The particle size of the template material is 1 ⁇ 80nm;
  • the nano-framework template material and starch are first compounded and smelted.
  • the gelatinized starch is wrapped around the nano-framework template material and supported by the nano-framework template material to form a three-dimensional composite structure.
  • the precursor is pre-carbonized at a specific temperature, its microstructure further forms a new carbon segment structure and is macroscopically transformed into a stable three-dimensional aromatic cyclized cubic network structure.
  • the uniformly distributed nanoskeleton template material is pickled in situ, After removal, a certain amount of pore structure is left in the carbon cubic network structure.
  • the particle size of the nanoframework template material will also affect the morphology of the final prepared hard carbon material. If the particle size is too large, it will directly cause the initially generated pore structure to be too large, resulting in subsequent Self-healing at high temperatures is limited.
  • the inventor found through many experiments that if the precursor is not pre-carbonized before high-temperature carbonization, the segment structure generated in the material will directly break during the high-temperature pyrolysis process, causing the structure to collapse and presenting an undesirable sheet structure. , it is difficult to apply to the deintercalation of sodium ions; even if pre-carbonization is performed, in the subsequent high-temperature carbonization process, the degree of self-repair of the pore structure is related to the carbonization temperature and heating rate. If the carbonization conditions are improperly selected, it will also be difficult to achieve Ideal pore structure tension retraction.
  • the nano-framework template material is at least one of nano-metal oxide, nano-non-metal oxide, nano-halide, nano-metal element, and nano-non-metal element.
  • the nano-framework template material is nano-magnesium oxide, nano-zinc oxide, nano-alumina, nano-molybdenum dioxide, nano-titanium dioxide, nano-iron oxide, nano-silica, nano-selenium dioxide, nano-magnesium chloride, nano-chlorine At least one of zinc oxide, nano-iron chloride, nano-iron element, nano-copper element, nano-silver element, nano-gold element, nano-silicon element, nano-selenium element, nano-antimony element, and nano-sulfur element.
  • the mass ratio of the nano-framework template material and starch is 1: (10-20).
  • the above-mentioned preferred nano-framework template material has high stability when mixed with starch and will not undergo obvious reactions. It can be fully used as a skeleton template to compound with starch and become a precursor.
  • the particle size of the nano-framework template material is 10-40 nm.
  • the starch is at least one of potato starch, corn starch, wheat starch, sweet potato starch, tapioca starch, rice starch, and purple potato starch.
  • the protective atmosphere in step (1) is any one of nitrogen, argon, and helium, the temperature during mixing and smelting is 200-235°C, the time is 4-20h, and the mixing rate is 100-500rpm. .
  • the nano-framework template material can be fully wrapped into the gelatinized starch and evenly dispersed.
  • the temperature rising rate in step (2) is 5-10°C/min.
  • the carbon molecular chains in starch rearrange to form a new segment structure after a series of reactions such as dehydration and deoxygenation, and then transform into a stable cubic network structure.
  • the pickling solution used in the pickling treatment in step (3) is at least one of a hydrochloric acid solution, a sulfuric acid solution, a nitric acid solution, a phosphoric acid solution, and a hydrofluoric acid solution, and the pickling treatment time is 2 to 8h, the temperature is 50 ⁇ 80°C.
  • the pre-carbonized carbon powder B of the present invention is not limited to the above-mentioned treatment when removing nano-frame template materials. It can also be used for some treatments that can also remove nano-frame template materials without affecting the carbon materials inside the material. The same can be used interchangeably. For example, when nano-silica with higher purity is selected as the nano-skeleton template material, an alkaline solution can be used for collaborative removal according to the actual situation.
  • the protective atmosphere in step (3) is any one of nitrogen, argon, and helium.
  • the beneficial effect of the present invention is that the present invention provides a hard carbon material and a preparation method thereof.
  • the method first uses a nano-skeleton template material and starch to compositely smelt to form a preliminary three-dimensional composite structure precursor.
  • the precursor undergoes preheating at a specific temperature.
  • its microstructure After carbonization treatment, its microstructure further forms a new carbon segment structure and macroscopically transforms into a stable three-dimensional aromatic ring cubic network structure.
  • the nano-skeleton template material is removed in situ by pickling treatment, the carbon cubic network structure A certain amount of pore structure is left in the material.
  • the material undergoes structural rearrangement.
  • the pore structure on the surface repairs itself and eventually forms closed pores.
  • the rich internal pore structure is retained while reducing the product size. specific surface area.
  • the invention also provides a sodium ion battery prepared by further applying the hard carbon material.
  • Figure 1 is a scanning electron microscope image of the pre-carbonized powder B described in Embodiment 1 of the present invention after being pickled to remove the nano-framework template material;
  • Figure 2 is a scanning electron microscope image of the hard carbon material according to Embodiment 1 of the present invention.
  • Figure 3 is a pore size distribution diagram of the pre-carbonized powder B described in Embodiment 1 of the present invention after being pickled to remove the nano-skeleton template material;
  • Figure 4 is a pore size distribution diagram of the hard carbon material according to Embodiment 1 of the present invention.
  • Figure 5 is an XRD pattern of the hard carbon material according to Embodiment 1 of the present invention.
  • Figure 6 is a scanning electron microscope image of the hard carbon material described in Comparative Example 2 of the present invention.
  • Figure 7 is a schematic diagram of the hard carbon material described in Comparative Example 2 of the present invention.
  • Figure 8 is a pore size distribution diagram of the hard carbon material described in Comparative Example 3 of the present invention.
  • Figure 9 is a graph of the first charge and discharge curve when the hard carbon material described in Embodiment 1 of the present invention is applied to the negative electrode material of a sodium ion battery.
  • Pre-carbonized carbon powder B is pickled with 2 mol/L hydrochloric acid solution at 60°C for 4 hours to remove the nano-skeleton template material, then washed with deionized water and dried at 80°C for 10 hours, then transferred to a nitrogen atmosphere with a temperature increase of 5°C The temperature is increased to 1400°C for high-temperature carbonization treatment for 3 hours to obtain the hard carbon material.
  • Pre-carbonized carbon powder B is pickled with 2 mol/L hydrochloric acid solution at 70°C for 3 hours to remove the nano-framework template material, then washed with deionized water and dried at 80°C for 10 hours, then transferred to a nitrogen atmosphere with a temperature increase of 2°C The temperature is increased to 1200°C for high-temperature carbonization treatment for 4 hours to obtain the hard carbon material.
  • Pre-carbonized carbon powder B is pickled with 2 mol/L hydrochloric acid solution at 80°C for 2 hours to remove the nano-framework template material, then washed with deionized water and dried at 80°C for 10 hours, then transferred to a nitrogen atmosphere with a temperature increase of 5°C The temperature is increased to 1400°C for high-temperature carbonization treatment for 3 hours to obtain the hard carbon material.
  • Embodiment 1 The only difference between this embodiment and Embodiment 1 is that the added amount of nano zinc chloride is 10 g.
  • a method for preparing hard carbon materials including the following steps:
  • the pre-carbonized carbon powder B is transferred to a nitrogen atmosphere and heated to 1200°C for high-temperature carbonization at a heating rate of 5°C for 3 hours to obtain the hard carbon material.
  • a method for preparing hard carbon materials including the following steps:
  • Precursor A is pickled with 2 mol/L hydrochloric acid solution at 60°C for 4 hours to remove the nanoframework template material, then washed with deionized water and dried at 80°C for 10 hours, then transferred to a nitrogen atmosphere and heated at a heating rate of 5°C. After carbonization treatment at 1400°C for 3 hours, the hard carbon material is obtained.
  • a method for preparing hard carbon materials including the following steps:
  • Pre-carbonized carbon powder B is pickled with 2 mol/L hydrochloric acid solution at 60°C for 4 hours to remove the nano-framework template material, then washed with deionized water and dried at 80°C for 10 hours, then transferred to a nitrogen atmosphere with a temperature increase of 10°C The temperature is increased to 1400°C for high-temperature carbonization treatment for 3 hours to obtain the hard carbon material.
  • Example 1 The only difference between this comparative example and Example 1 is that the temperature during the high-temperature carbonization treatment in step (3) is 800°C.
  • Example 1 The only difference between this comparative example and Example 1 is that the particle size of the nano zinc chloride is 100 to 150 nm.
  • a method for preparing hard carbon materials including the following steps:
  • Pre-carbonized carbon powder B is pickled with 2 mol/L hydrochloric acid solution at 60°C for 4 hours to remove the nano-skeleton template material, then washed with deionized water and dried at 80°C for 10 hours, then transferred to a nitrogen atmosphere with a temperature increase of 5°C The temperature is increased to 1400°C for high-temperature carbonization treatment for 3 hours to obtain the hard carbon material.
  • a method for preparing hard carbon materials including the following steps:
  • Pre-carbonized carbon powder B is pickled with 2 mol/L hydrochloric acid solution at 60°C for 4 hours to remove the nano-framework template material, then washed with deionized water and dried at 80°C for 10 hours, then transferred to a nitrogen atmosphere with a temperature increase of 5°C The temperature is increased to 1400°C for high-temperature carbonization treatment for 3 hours to obtain the hard carbon material.
  • the pore structure undergoes a self-healing phenomenon of tension retraction, and the pore size distribution becomes concentrated. Micropores below 5nm. It can be seen from the XRD pattern of the final product that there is no residual nano-framework template material or other generated impurities in the product, and the XRD pattern only shows the characteristic peaks of carbon.
  • the specific surface area of the pre-carbonized carbon powder B obtained by the preparation method of each embodiment is larger after pickling treatment.
  • the pore structure undergoes self-rearrangement due to the structural rearrangement of the material itself. Repair makes the specific surface area of the final product significantly smaller, and since the surface pores form closed pores after self-repair, the true density of the product also becomes relatively smaller (within a certain range, the closed pore volume is inversely proportional to the true density).
  • the product of Comparative Example 1 does not introduce any structural modification components, and the specific surface area before high-temperature carbonization is small.
  • the product of Comparative Example 2 is not pre-carbonized during the preparation process. Although new segment structures can still be formed, these structures are not stable. Instead, the microstructure of the product will collapse and form a flake structure, as shown in Figure 6. Macroscopically, the product also shows an expansion state after high-temperature carbonization, as shown in Figure 7.
  • the high-temperature carbonization conditions set in Comparative Examples 3 and 4 are not optimal. Although the specific surface area of the products finally prepared before relatively high-temperature carbonization has decreased, the degree of self-healing of the pore structure is insufficient.
  • the pore diameter of the product described in Figure 8 It can be seen from the distribution diagram that the pore diameter of this product is mainly distributed in the range of 1000 to 1500 nm, which is quite different from the pore diameter distribution of the hard carbon material described in the embodiment of the present invention.
  • the specific surface area of the pre-carbonized sample was too large and the pore structure was too much.
  • the specific surface area of the subsequent high-temperature carbonization did not decrease much. This is due to the material
  • the self-healing function of the material is to utilize the tension retraction of the material during the process of pyrolysis and carbonization, but this "repair" ability is limited.
  • the purpose of reducing the specific surface area cannot be achieved. Because the pre-carbonization temperature of the product in Comparative Example 7 is too high, the structure tends to be stabilized, resulting in an insignificant "self-healing" effect of subsequent materials and little change in specific surface area.
  • the pre-carbonization temperature of the product in Comparative Example 8 is too low, resulting in an insignificant change in the specific surface area before and after pre-carbonization, and the unstable structure inside the structure is not completely removed, resulting in a significant increase in the specific surface area during subsequent high-temperature carbonization. This is due to the high-temperature carbonization process.
  • the unstable functional groups in the material undergo a series of extremely complex reactions such as chain scission, dehydration, decarboxylation, and condensation to form a pore structure.
  • the structure is further stabilized and finally forms a hard carbon material containing a pore structure.
  • the specific capacity of the products of each embodiment can reach 330mAh/g during the first charge after the SEI film is generated by the first discharge, and the first charge and discharge efficiency also reaches more than 85%, indicating that the hardness of the present invention is
  • carbon materials are used as negative electrode materials for sodium-ion batteries, due to the preferential structure, they can provide sufficient deintercalation sites for sodium ions to ensure a high specific capacity. At the same time, they can significantly reduce the energy consumed by the SEI film formed during the first full charge process. The number of irreversible sodium ions ensures high Coulombic efficiency.

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Abstract

本发明公开了一种硬碳材料及其制备方法与应用，属于电池材料领域。本发明所述硬碳材料的孔径为0.5～20nm，真密度为1.3～2.26g/cm3，比表面积≤5m2/g。所述硬碳材料的制备方法先以纳米骨架模板材料和淀粉复合熔炼形成初步立体的复合结构前驱体，经过特定温度的预碳化处理后转化为稳定的三维芳环化立方网状结构，酸洗处理原位去除纳米骨架模板材料后，该碳立方网状结构中留下了一定数量的孔隙，进一步经过高温碳化后发生结构重排，表面的孔隙结构发生自我修复并形成闭孔，最终保留内部丰富孔隙结构的同时减少了产品的比表面积，在应用于钠离子电池负极材料时，可有效改善初始脱嵌效率低的问题。

Description

一种硬碳材料及其制备方法与应用 技术领域
本发明电池材料领域，具体涉及一种硬碳材料及其制备方法与应用。
背景技术
在构建新能源社会中，大规模储电是众多应用中的关键技术。但现有的电化学体系主要为二次锂电池体系，由于地球上锂资源少，加上其广泛采集使用带来的短缺，使得目前的二次锂电池体系无法实现大规模储能应用，急需开发下一代综合性能优异的储能电池体系。
钠与锂属于同族元素，和锂具有相似的物化性质，并且具有资源丰富、对环境友好和价格低廉(比锂的原材料碳酸锂便宜30～40倍)的特点。此外，钠离子的电极电位(Na +/Na)较锂离子的(Li +/Li)高0.3V，具有更加稳定的电化学性能和安全性能。然而钠离子的离子半径(r＝0.113nm)较锂离子(r＝0.076nm)更大，使得钠离子在刚性晶格中相对稳定，在规整的石墨结构、高温石墨化的碳中间相微球几乎没有嵌钠容量。部分热解硬碳可得到近280mAh/g的可逆嵌钠容量，但初始不可逆容量较高，动力学性能差。一般而言，硬碳材料嵌钠的不可逆容量问题可以通过结构优化，降低比表面积来改善，但目前现有技术的改善程度依然不够可观。
发明内容
基于现有技术存在的缺陷，本发明的目的在于提供了一种硬碳材料及其制备方法，所述制备方法以淀粉和纳米骨架模板材料为原料熔炼得到前驱体，随后依次经预碳化、去模板化以及高温碳化等系列步骤，无需引入额外的加工设备或二次加工碳源即可最终获得高性能的硬碳材料，该产品带有丰富且稳定的孔隙结构，比表面积小，可有效改善目前硬碳材料用于钠离子电池负极材料时初始不可逆容量高的瓶颈问题，同时为钠离子脱嵌过程提供足够的可逆位点。
为了达到上述目的，本发明采取的技术方案为：
一种硬碳材料，所述硬碳材料的孔径为0.5～20nm，真密度为1.3～2.26g/cm 3，比表面积≤5m 2/g。
本发明所述硬碳材料的制备方法制备得到的产品孔隙结构丰富，碳架结构稳定，比表面积小，应用在钠离子电池负极材料时初始钠脱嵌过程生成SEI膜消耗的不可逆钠离子量变少，有效改善初始可逆比容量和初始库伦效率。
本发明的另一目的在于提供一种钠离子电池，所述钠离子电池中的负极材料由本发明所述硬碳材料制备得到。
本发明的再一目的在于提供所述硬碳材料的制备方法，包括以下步骤：
(1)在保护气氛下将纳米骨架模板材料和淀粉混合熔炼至均匀，冷却，得前驱体A；所述纳米骨架模板材料和淀粉的质量比为1：(5～20)；所述纳米骨架模板材料的粒径为1～80nm；
(2)将前驱体A在保护气氛下升温至400～700℃预碳化处理4～8h，得预碳化碳粉B；
(3)预碳化碳粉B经酸洗处理去除纳米骨架模板材料后，转移至保护气氛下以1～5℃的升温速率升温至1000～1500℃碳化处理0.5～6h，即得所述硬碳材料。
本发明所述硬碳材料的制备方法中，先以纳米骨架模板材料和淀粉复合熔炼，此时糊化的淀粉包裹在纳米骨架模板材料外并被纳米骨架模板材料支撑成为立体的复合结构，该前驱体经过特定温度的预碳化处理后其微观结构进一步形成新的碳链段结构并宏观转化为稳定的三维芳环化立方网状结构，当分布均匀的纳米骨架模板材料经酸洗处理原位去除后，该碳立方网状结构中留下了一定数量的孔隙结构，后续经过高温碳化并设置特殊的温区及升温速率，可使得材料发生结构重排，表面的孔隙结构开始自我修复，产生一定程度的张力回缩现象并最终形成闭孔，最终在保留内部丰富的孔隙结构的同时，减少了产品的比表面积，在应用于钠离子电池负极材料时，可有效改善现有产品钠离子初始脱嵌过程中初始脱嵌效率低(因负极材料比表面积过大而生成大面积SEI膜导致)的问题。另一方面，本发明所述方法中，纳米骨架模板材料的粒径大小也会影响最终制备硬碳材料的形貌，若粒径过大，则会直接造成初始生成的孔隙结构过大，后续高温下的自我修复程度有限。
同时，发明人经过多次试验发现，若前驱体在高温碳化前不进行预碳化，则材料中生成的链段结构将在高温热解过程直接断裂，导致结构崩塌，呈现不 理想的片状结构，难以应用于钠离子脱嵌当中；即使进行了预碳化处理，在后续的高温碳化过程中，孔隙结构的自我修复程度与碳化温度、升温速率均有联系，若选择碳化条件不当，同样难以实现理想的孔隙结构张力回缩。
优选地，所述纳米骨架模板材料为纳米金属氧化物、纳米非金属氧化物、纳米卤化物、纳米金属单质、纳米非金属单质中的至少一种。
更优选地，所述纳米骨架模板材料为纳米氧化镁、纳米氧化锌、纳米氧化铝、纳米二氧化钼、纳米二氧化钛、纳米氧化铁、纳米二氧化硅、纳米二氧化硒、纳米氯化镁、纳米氯化锌、纳米氯化铁、纳米铁单质、纳米铜单质、纳米银单质、纳米金单质、纳米硅单质、纳米硒单质、纳米锑单质、纳米硫单质中的至少一种。
更优选地，所述纳米骨架模板材料和淀粉的质量比为1：(10～20)。
上述优选的纳米骨架模板材料与淀粉混合时稳定性较高，不会发生明显的反应，可充分作为骨架模板与淀粉复合成为前驱体。
优选地，所述纳米骨架模板材料的粒径为10～40nm。
优选地，所述淀粉为土豆淀粉、玉米淀粉、小麦淀粉、红薯淀粉、木薯淀粉、大米淀粉、紫薯淀粉中的至少一种。
优选地，所述步骤(1)中的保护气氛为氮气、氩气、氦气中的任意一种，混合熔炼时的温度为200～235℃，时间为4～20h，混合速率为100～500rpm。
在所述熔炼环境下，纳米骨架模板材料可充分被包裹进糊化的淀粉当中并均匀分散。
优选地，所述步骤(2)中升温时的速率为5～10℃/min。
在所述升温速率下，淀粉中的碳分子链经脱水、脱氧等系列反应后发生重排形成新链段结构，进而转化为稳定的立方网状结构。
优选地，所述步骤(3)中酸洗处理所用的酸洗溶液为盐酸溶液、硫酸溶液、硝酸溶液、磷酸溶液、氢氟酸溶液中的至少一种，酸洗处理时的时间为2～8h，温度为50～80℃。
需要说明的是，本发明所述预炭化碳粉B进行去除纳米骨架模板材料时并不局限于上述处理，对于一些同样可去除纳米骨架模板材料且不会影响到材料内部碳材料的处理均可同等替换使用，例如当纳米骨架模板材料选用纯度较高纳米二氧化硅时，可根据实际情况复合选用碱性溶液协同去除。
优选地，所述步骤(3)中的保护气氛为氮气、氩气、氦气中的任意一种。
本发明的有益效果在于，本发明提供了一种硬碳材料及其制备方法，该方法先以纳米骨架模板材料和淀粉复合熔炼形成初步立体的复合结构前驱体，该前驱体经过特定温度的预碳化处理后其微观结构进一步形成新的碳链段结构并宏观转化为稳定的三维芳环化立方网状结构，当其中纳米骨架模板材料经酸洗处理原位去除后，该碳立方网状结构中留下了一定数量的孔隙结构，进一步经过特定条件的高温碳化后材料发生结构重排，表面的孔隙结构发生自我修复并最终形成闭孔，最终在保留内部丰富的孔隙结构的同时减少了产品的比表面积。当应用于钠离子电池负极材料时，可有效改善现有产品因SEI膜不可逆消耗钠离子数量过多而导致的初始脱嵌效率低的问题。本发明还提供了所述硬碳材料进一步应用制备的钠离子电池。
附图说明
图1为本发明实施例1所述预炭化粉B经过酸洗处理去除纳米骨架模板材料后的扫描电镜图；
图2为本发明实施例1所述硬碳材料的扫描电镜图；
图3为本发明实施例1所述预炭化粉B经过酸洗处理去除纳米骨架模板材料后的孔径分布图；
图4为本发明实施例1所述硬碳材料的孔径分布图；
图5为本发明实施例1所述硬碳材料的XRD图；
图6为本发明对比例2所述硬碳材料的扫描电镜图；
图7为本发明对比例2所述硬碳材料的示意图；
图8为本发明对比例3所述硬碳材料的孔径分布图；
图9为本发明实施例1所述硬碳材料应用于钠离子电池负极材料时的首次充放电曲线图。
具体实施方式
为了更好地说明本发明的目的、技术方案和优点，下面将结合具体实施例及对比例对本发明作进一步说明，其目的在于详细地理解本发明的内容，而不是对本发明的限制。本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明的保护范围。本发明实施所设计的实验试剂 及仪器，除非特别说明，均为常用的普通试剂及仪器。
实施例1
本实施例所述硬碳材料及其制备方法的一种实施例，包括以下步骤：
(1)在氮气气氛下将20g纳米骨架模板材料纳米氯化锌(粒径10～40nm)和100g玉米淀粉的混合物在230℃的熔炼炉中以200rpm的转速混合熔炼8h至均匀，冷却至50℃，得前驱体A；
(2)将前驱体A置入烧结炉中，在氮气气氛下以3℃/min升温至500℃预碳化处理6h，冷却至50℃，得预碳化碳粉B；
(3)预碳化碳粉B经2mol/L盐酸溶液60℃酸洗处理4h去除纳米骨架模板材料后，用去离子水洗涤干净并在80℃干燥10h，转移至氮气气氛下以5℃的升温速率升温至1400℃高温碳化处理3h，即得所述硬碳材料。
实施例2
本实施例所述硬碳材料及其制备方法的一种实施例，包括以下步骤：
(1)在氮气气氛下将10g纳米骨架模板材料纳米二氧化钛(粒径15～30nm)和100g玉米淀粉的混合物在220℃的熔炼炉中以200rpm的转速混合熔炼10h至均匀，冷却至50℃，得前驱体A；
(2)将前驱体A置入烧结炉中，在氮气气氛下以5℃/min升温至700℃预碳化处理4h，冷却至50℃，得预碳化碳粉B；
(3)预碳化碳粉B经2mol/L盐酸溶液70℃酸洗处理3h去除纳米骨架模板材料后，用去离子水洗涤干净并在80℃干燥10h，转移至氮气气氛下以2℃的升温速率升温至1200℃高温碳化处理4h，即得所述硬碳材料。
实施例3
本实施例所述硬碳材料及其制备方法的一种实施例，包括以下步骤：
(1)在氮气气氛下将5g纳米骨架模板材料纳米硒粉(粒径10～40nm)和100g玉米淀粉的混合物在210℃的熔炼炉中以200rpm的转速混合熔炼18h至均匀，冷却至50℃，得前驱体A；
(2)将前驱体A置入烧结炉中，在氮气气氛下以3℃/min升温至600℃预碳化处理5h，冷却至50℃，得预碳化碳粉B；
(3)预碳化碳粉B经2mol/L盐酸溶液80℃酸洗处理2h去除纳米骨架模板材料后，用去离子水洗涤干净并在80℃干燥10h，转移至氮气气氛下以5℃的升温速率升温至1400℃高温碳化处理3h，即得所述硬碳材料。
实施例4
本实施例与实施例1的差别仅在于，纳米氯化锌的添加量为10g。
对比例1
一种硬碳材料的制备方法，包括以下步骤：
(1)在氮气气氛下将100g玉米淀粉的混合物在230℃的熔炼炉中以200rpm的转速熔炼8h，冷却至50℃，得前驱体A；
(2)将前驱体A置入烧结炉中，在氮气气氛下以3℃/min升温至400℃预碳化处理2h，冷却至50℃，得预碳化碳粉B；
(3)预碳化碳粉B转移至氮气气氛下以5℃的升温速率升温至1200℃高温碳化处理3h，即得所述硬碳材料。
对比例2
一种硬碳材料的制备方法，包括以下步骤：
(1)在氮气气氛下将20g纳米骨架模板材料纳米氯化锌(粒径10～40nm)和100g玉米淀粉的混合物在230℃的熔炼炉中以200rpm的转速混合熔炼8h至均匀，冷却至50℃，得前驱体A；
(2)前驱体A经2mol/L盐酸溶液60℃酸洗处理4h去除纳米骨架模板材料后，用去离子水洗涤干净并在80℃干燥10h，转移至氮气气氛下以5℃的升温速率升温至1400℃高温碳化处理3h，即得所述硬碳材料。
对比例3
一种硬碳材料的制备方法，包括以下步骤：
(1)在氮气气氛下将20g纳米骨架模板材料纳米氯化锌(粒径10～40nm)和100g玉米淀粉的混合物在230℃的熔炼炉中以200rpm的转速混合熔炼8h至均匀，冷却至50℃，得前驱体A；
(2)将前驱体A置入烧结炉中，在氮气气氛下以3℃/min升温至500℃预碳化处理6h，冷却至50℃，得预碳化碳粉B；
(3)预碳化碳粉B经2mol/L盐酸溶液60℃酸洗处理4h去除纳米骨架模板材料后，用去离子水洗涤干净并在80℃干燥10h，转移至氮气气氛下以10℃的升温速率升温至1400℃高温碳化处理3h，即得所述硬碳材料。
对比例4
本对比例与实施例1的差别仅在于，所述步骤(3)中高温碳化处理时的温度为800℃。
对比例5
本对比例与实施例1的差别仅在于，所述纳米氯化锌的添加量为25g。
对比例6
本对比例与实施例1的差别仅在于，所述纳米氯化锌的粒径为100～150nm。
对比例7
一种硬碳材料的制备方法，包括以下步骤：
(1)在氮气气氛下将20g纳米骨架模板材料纳米氯化锌(粒径10～40nm)和100g玉米淀粉的混合物在230℃的熔炼炉中以200rpm的转速混合熔炼8h至均匀，冷却至50℃，得前驱体A；
(2)将前驱体A置入烧结炉中，在氮气气氛下以3℃/min升温至800℃预碳化处理3h，冷却至50℃，得预碳化碳粉B；
(3)预碳化碳粉B经2mol/L盐酸溶液60℃酸洗处理4h去除纳米骨架模板材料后，用去离子水洗涤干净并在80℃干燥10h，转移至氮气气氛下以5℃的升温速率升温至1400℃高温碳化处理3h，即得所述硬碳材料。
对比例8
一种硬碳材料的制备方法，包括以下步骤：
(1)在氮气气氛下将20g纳米骨架模板材料纳米氯化锌(粒径10～40nm)和100g玉米淀粉的混合物在230℃的熔炼炉中以200rpm的转速混合熔炼8h至均匀，冷却至50℃，得前驱体A；
(2)将前驱体A置入烧结炉中，在氮气气氛下以3℃/min升温至300℃预碳化处理10h，冷却至50℃，得预碳化碳粉B；
(3)预碳化碳粉B经2mol/L盐酸溶液60℃酸洗处理4h去除纳米骨架模板材料后，用去离子水洗涤干净并在80℃干燥10h，转移至氮气气氛下以5℃的升温速率升温至1400℃高温碳化处理3h，即得所述硬碳材料。
效果例1
为了验证本发明所述硬碳材料的制备方法所得产品的优选形貌和结构，将实施例1方法各阶段产物进行扫描电镜观察、比表面及孔径分布测试及XRD测试，结果如图1～5所示。从图1和2可以看出，本发明所得预炭化粉B经过酸洗处理去除纳米骨架模板材料后原位生成了丰富的孔隙结构，该结构分布在材料表面及内部，而经过高温碳化处理后的硬碳材料颗粒均匀且未见团聚现象；在高温碳化前样品的孔径分布主要集中在100～150nm，当进一步高温碳化处理后，孔隙结构发生张力回缩的自我修复现象，孔径分布变为集中5nm以下的微孔。从最终产品的XRD图可以看出，该产品未残留纳米骨架模板材料或生成的其他杂质，XRD图中只显示碳的特征峰。
效果例2
基于效果例1的测试结果，将各实施例和对比例最终产品及阶段性产品(高温碳化处理前的粉体)均进行比表面积测试并统计，结果如表1所示。
表1
Figure PCTCN2022122920-appb-000001
从表1可以看出，各实施例制备方法得到的预碳化碳粉B经过酸洗处理后 的比表面积均较大，而经过高温碳化处理后，由于材料本身的结构重排致使孔隙结构发生自我修复，使得最终产品的比表面积显著变小，而由于该自我修复后表面孔隙形成闭孔，因此产品的真密度也相对变小(在一定范围内，闭孔体积与真密度呈反比关系)。相比之下，对比例1产品未引入任何的结构改性组分，在高温碳化前的比表面积较小，经过高温碳化后，该产品的比表面积显著提升，会消耗大量的钠离子去形成SEI膜导致不可逆容量高、首效低。对比例2产品在制备过程中不进行预碳化，虽然依然可形成新的链段结构，但这些结构并不稳定，反而会导致产品的微观结构崩塌并形成片状结构，如图6所示，而宏观上该产品在高温碳化后也呈现膨胀状态，如图7所示。对比例3和4中设置的高温碳化条件并非优选，虽然相较高温碳化前最终制备的产品的比表面积均有所下降，但孔隙结构的自我修复程度不足，其中从图8所述产品的孔径分布图可以看出，该产品的孔径主要分布在1000～1500nm内，与本发明实施例所述硬碳材料的孔径分布差异较大。对比例5和6产品，由于模板剂的用量过多以及粒径过大，使得预炭化后的样品比表面积过大，孔隙结构过多，随后高温炭化比表面积并没有下降很多，这是由于材料的自我修复作用是利用材料在热解和炭化的过程中的张力回缩，但是这种“修复”能力是有限，当孔隙结构过多时，达不到减小比表面积的目的。对比例7的产品由于预炭化温度过高，结构趋于稳定化，导致后续材料的“自我修复”效果不明显，比表面积变化不大。对比例8的产品的预炭化温度过低，导致预炭化前后比表面积变化不明显，结构内部的不稳定结构没有完全去除，导致后续高温炭化时，比表面积增大明显，这是由于在高温碳化过程中，材料中的不稳定官能团发生断链、脱水、脱羧、缩合等一系列极为复杂的反应后，形成孔隙结构，与此同时结构进一步稳定最终形成含有孔隙结构的硬炭材料。
进一步地，将各实施例和对比例产品应用于钠离子半电池中进行性能测试，具体步骤为：
将实施例/对比例所得硬碳材料、羧甲基纤维素钠、Super P导电炭黑以及聚合物粘结剂按质量比95:2:1:2混合并用去离子水调配成浆料，涂布在铜箔上并干燥，裁切，得到碳负极片，以钠金属为对电极和参比电极、NaClO 4溶于体积比为1:1的碳酸乙烯酯和碳酸丙烯酯的混合液为电解液在保护气氛下组装成扣式半电池，随后在0～2V工作电压，0.1C电流密度下进行电化学性能测试，结果 如表2所示。
表2
Figure PCTCN2022122920-appb-000002
从表2可以看出，各实施例产品在首次放电生成SEI膜后的首次充电时的比容量均可达到330mAh/g，而首次充放电效率也达到了85％以上，说明本发明所述硬碳材料作为钠离子电池负极材料时由于结构的优选性，可提供充分的脱嵌位点给钠离子以保障比容量较高，同时可显著减少在首次充分电过程中形成的SEI膜时消耗的不可逆钠离子数量，保障较高的库伦效率。从图9实施例1所得产品制备的钠离子电池的首次充放电曲线可以看出，曲线在首次放电时出现了SEI膜生成对应的平台，同时依然保持了较高的充电比容量，说明极片上既生成了足够的SEI膜，同时也可保障较高的可逆比容量，电化学性能优异。相比之下，各对比例产品由于结构难以达到理想效果，依然无法避免因SEI膜生成而产生的大量不可逆钠离子消耗损失。
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。

Claims (10)

  1. 一种硬碳材料，其特征在于，所述硬碳材料的孔径为0.5～20nm，真密度为1.3～2.26g/cm 3，比表面积≤5m 2/g。
  2. 一种钠离子电池，其特征在于，所述钠离子电池中的负极材料由权利要求1所述硬碳材料制备得到。
  3. 如权利要求1所述硬碳材料的制备方法，其特征在于，包括以下步骤：
    (1)在保护气氛下将纳米骨架模板材料和淀粉混合熔炼至均匀，冷却，得前驱体A；所述纳米骨架模板材料和淀粉的质量比为1：(5～20)；所述纳米骨架模板材料的粒径为1～80nm；
    (2)将前驱体A在保护气氛下升温至400～700℃预碳化处理4～8h，得预碳化碳粉B；
    (3)预碳化碳粉B经酸洗处理去除纳米骨架模板材料后，转移至保护气氛下以1～5℃的升温速率升温至1000～1500℃碳化处理0.5～6h，即得所述硬碳材料。
  4. 如权利要求3所述硬碳材料的制备方法，其特在于，所述纳米骨架模板材料为纳米金属氧化物、纳米非金属氧化物、纳米卤化物、纳米金属单质、纳米非金属单质中的至少一种。
  5. 如权利要求4所述硬碳材料的制备方法，其特在于，所述纳米骨架模板材料为纳米氧化镁、纳米氧化锌、纳米氧化铝、纳米二氧化钼、纳米二氧化钛、纳米氧化铁、纳米二氧化硅、纳米二氧化硒、纳米氯化镁、纳米氯化锌、纳米氯化铁、纳米铁单质、纳米铜单质、纳米银单质、纳米金单质、纳米硅单质、纳米硒单质、纳米锑单质、纳米硫单质中的至少一种。
  6. 如权利要求3所述硬碳材料的制备方法，其特在于，所述纳米骨架模板材料和淀粉的质量比为1：(10～20)。
  7. 如权利要求3所述硬碳材料的制备方法，其特在于，所述纳米骨架模板材料的粒径为10～40nm。
  8. 如权利要求3所述硬碳材料的制备方法，其特在于，所述淀粉为土豆淀 粉、玉米淀粉、小麦淀粉、红薯淀粉、木薯淀粉、大米淀粉、紫薯淀粉中的至少一种。
  9. 如权利要求3所述硬碳材料的制备方法，其特在于，所述步骤(1)中的保护气氛为氮气、氩气、氦气中的任意一种，混合熔炼时的温度为200～235℃，时间为4～20h，混合速率为100～500rpm。
  10. 如权利要求3所述硬碳材料的制备方法，其特在于，所述步骤(2)中升温时的速率为5～10℃/min。
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