WO2024000885A1 - Preparation method for sodium ion battery porous hard carbon material, and product and use thereof - Google Patents

Preparation method for sodium ion battery porous hard carbon material, and product and use thereof Download PDF

Info

Publication number
WO2024000885A1
WO2024000885A1 PCT/CN2022/122270 CN2022122270W WO2024000885A1 WO 2024000885 A1 WO2024000885 A1 WO 2024000885A1 CN 2022122270 W CN2022122270 W CN 2022122270W WO 2024000885 A1 WO2024000885 A1 WO 2024000885A1
Authority
WO
WIPO (PCT)
Prior art keywords
hard carbon
sodium ion
porous hard
gluconate
ion batteries
Prior art date
Application number
PCT/CN2022/122270
Other languages
French (fr)
Chinese (zh)
Inventor
张苗
阮丁山
李长东
毛林林
郑爽
Original Assignee
广东邦普循环科技有限公司
湖南邦普循环科技有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东邦普循环科技有限公司, 湖南邦普循环科技有限公司 filed Critical 广东邦普循环科技有限公司
Publication of WO2024000885A1 publication Critical patent/WO2024000885A1/en

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/133—Electrodes based on 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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 field of battery materials, and in particular to a preparation method of porous hard carbon materials for sodium ion batteries and their products and applications.
  • negative electrode materials play an important role in improving the energy density and cycle life of the battery.
  • the ionic radius of sodium ions is larger than that of lithium ions
  • hard carbon materials are considered to be the most promising anode materials for sodium-ion batteries due to their high specific capacity and long cycle life.
  • the microporous area is the main active site for sodium storage reaction. Therefore, designing an appropriate pore structure is the key to obtaining high-performance hard carbon anode materials.
  • the purpose of the present invention is to provide a method for preparing porous hard carbon materials for sodium ion batteries.
  • This method uses gluconate and glucose as carbon sources, and at the same time controls carbon pyrolysis by regulating gluconate.
  • the pore-forming efficiency in the process, the pore structure of the finally prepared porous hard carbon material is evenly distributed, and the size is suitable for the deintercalation behavior of sodium ions during the charge and discharge process.
  • the resulting product can be used in sodium-ion batteries to demonstrate high capacity and high cycle stability.
  • a method for preparing porous hard carbon materials for sodium ion batteries including the following steps:
  • the precursor C is kept at 1200-1600°C for 1-3 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • a metal salt pore-forming agent is generally introduced at the same time.
  • the pore-forming agent can fully adjust the carbon framework. structure, making the final product rich in holes.
  • glucose used as the carbon source
  • not any pore-forming agent can achieve the ideal pore-forming effect. If pore-forming agents such as oxalate metal salts and citric acid metal salts are used to create pores, the final result will be
  • the prepared porous hard carbon material has a relatively large true density and a relatively large specific surface area.
  • gluconate combined with glucose is selected as the raw material.
  • the gluconate acts both as a carbon source and as a pore-forming agent.
  • the technical solution of the present invention also introduces preheating. In this step, the number, size and distribution of metal oxides in the raw materials can be effectively controlled through preheating at appropriate temperatures, thereby controlling the number, size and distribution of pores in the hard carbon material.
  • the preparation method has simple operation steps, does not involve high technical requirements and high equipment requirements, and can realize industrial large-scale production.
  • the gluconate is at least one of calcium gluconate, magnesium gluconate, zinc gluconate, iron gluconate, and copper gluconate.
  • the gluconate is magnesium gluconate.
  • the above types of gluconates can achieve ideal pore-forming effects, making the carbon framework structure of the final porous hard carbon material suitable for the deintercalation of sodium ions during the transmission process.
  • the temperature during the freeze-drying process in step (2) is -50 ⁇ -80°C
  • the vacuum degree is 10 ⁇ 20Pa
  • the time is 12 ⁇ 36h.
  • the inventor's experiments show that the freeze-drying step has a great impact on the pore-forming performance of the product.
  • Preheating and high-temperature treatment after the carbon source freeze-drying process can make the closed-pore volume density of the product greater, which is more beneficial.
  • the inert atmosphere in step (3) is any one of nitrogen, argon, and helium, and the temperature rise rate during heat preservation is 3 to 5°C/min.
  • glucose When preheating the carbon source, glucose can be effectively carbonized and cracked to form a preliminary carbon skeleton.
  • metal salts penetrate into the carbon skeleton during this process and form metal oxides to regulate the pore structure. Controlling the appropriate heating rate can Effectively make the distribution of this pore-forming agent more even.
  • the acid solution used for pickling in step (3) is at least one of hydrochloric acid solution and sulfuric acid solution, and the molar concentration of the acid solution is 0.5-1 mol/L.
  • the metal oxides in the precursor material can be effectively removed by the acid solution with the above concentration. It should be noted that the pickling treatment is not limited to the above conditions. As long as the same treatment effect can be achieved, other reagents can also be used.
  • the inert atmosphere in step (4) is any one of nitrogen, argon, and helium, and the temperature rise rate during heat preservation is 5-10°C/min.
  • the precursor material can be effectively transformed into a hard carbon material with appropriate pore distribution.
  • Another object of the present invention is to provide a porous hard carbon negative electrode material for a sodium ion battery prepared by the method for preparing a porous hard carbon material for a sodium ion battery, and a sodium ion battery prepared by using the porous hard carbon negative electrode material for a sodium ion battery.
  • the porous hard carbon material of the sodium ion battery prepared by the method of the present invention has a small true density, which can reach less than 1.4g/cm 3 , and at the same time, the maximum closed-pore volume density can be close to 0.3cm 3 /g, and has excellent application in sodium ion batteries. electrochemical properties.
  • the present invention provides a method for preparing porous hard carbon materials for sodium ion batteries.
  • the method uses gluconate and glucose as carbon sources, and at the same time controls the carbon pyrolysis process by regulating gluconate.
  • Pore-forming efficiency, the pore structure of the finally prepared porous hard carbon material is uniformly distributed, and the size is suitable for the deintercalation behavior of sodium ions during the charge and discharge process.
  • the resulting product can be applied to sodium-ion batteries to demonstrate high capacity and high cycle stability.
  • the invention also provides a porous hard carbon negative electrode material for a sodium ion battery prepared by the method for preparing a porous hard carbon material for a sodium ion battery and a sodium ion battery prepared by using the porous hard carbon negative electrode material for a sodium ion battery.
  • Figure 1 is a scanning electron microscope image of the porous hard carbon material of the sodium ion battery of the present invention.
  • An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention includes the following steps:
  • the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • the obtained product was observed under a scanning electron microscope. As shown in Figure 1, the material had a uniform morphology and no obvious agglomeration.
  • Example 1 The only difference between this embodiment and Example 1 is that the added amount of magnesium gluconate is 208g.
  • Example 1 The only difference between this embodiment and Example 1 is that the added amount of magnesium gluconate is 249g.
  • An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention includes the following steps:
  • the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention includes the following steps:
  • the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention includes the following steps:
  • the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention includes the following steps:
  • the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention includes the following steps:
  • the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention includes the following steps:
  • the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • the insulation temperature in step (3) is 400°C and the time is 3 hours.
  • the insulation temperature in step (3) is 800°C and the time is 1 hour.
  • a porous hard carbon material and a preparation method thereof which method includes the following steps:
  • the precursor In a nitrogen atmosphere, the precursor is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material.
  • the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  • Example 1 The only difference between this comparative example and Example 1 is that the insulation temperature in step (3) is 900°C and the time is 0.5 h.
  • the only difference between this comparative example and Example 1 is that the insulation temperature in step (3) is 300°C and the time is 4 hours.
  • Comparative Example 2 adopts the conventional pre-drying treatment method, and the closed-pore volume density of the obtained product is significantly smaller, indicating that the pre-freeze drying treatment of the carbon source has a greater impact on the pore structure of the final product.
  • Comparative Examples 3 and 4 used existing conventional metal salts of other types instead of gluconate, and the characterization results of the obtained products were not much different from Comparative Example 1, indicating that not any metal salt pore-forming agent is suitable for preparing sodium ions according to the present invention. Porous carbon materials for batteries.
  • the closed cell volume density of Comparative Examples 10 and 11 is quite different from that of Example 1, indicating that both the preliminary sintering temperature and time will affect the pore structure of the final product. Whether the degree of sintering is too high or too low, it is difficult to achieve the desired effect. .
  • each prepared porous hard carbon material was used as a porous hard carbon negative electrode material for a sodium ion battery.
  • the electrochemical performance test was carried out at a current density of 0 to 2V and the results are shown in Table 3.
  • the first discharge specific capacity of the products of each example is higher, reaching more than 400mAh/g, with Example 3 having the highest discharge specific capacity; and in terms of Coulombic efficiency, Compared with the product of Comparative Example 1, the Coulombic efficiency of Example 1 is the highest.
  • the product of Comparative Example 2 has higher Coulombic efficiency, its initial discharge specific capacity is lower, indicating that more sodium ions are not effectively deintercalated during the first charge and discharge process.
  • the products of Comparative Examples 3 and 4 were both low in discharge specific capacity and Coulombic efficiency, indicating that porous hard carbon materials prepared using non-preferred metal salt pore-forming agents are difficult to be used as negative electrode materials for sodium ion batteries.
  • the products of Comparative Examples 5 and 6 had unsatisfactory pre-burning effects during the preparation process, and it was also difficult to achieve ideal performance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Secondary Cells (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

A preparation method for a sodium ion battery porous hard carbon material, and a product and the use thereof, belonging to the field of battery materials. The preparation method for the sodium ion battery porous hard carbon material uses both gluconate and glucose as a carbon source. In addition, the pore forming efficiency during a carbon pyrolysis process is controlled by regulating the type of the gluconate, so that a finally prepared porous hard carbon material has a uniformly distributed pore structure, the pore size being suitable for the deintercalation behavior of sodium ions during charging and discharging processes. Therefore, high capacity and high cycling stability can be achieved when the obtained product is used to a sodium ion battery. Also provided is a sodium ion battery porous hard carbon negative electrode material prepared by the preparation method for the sodium ion battery porous hard carbon material.

Description

一种钠离子电池多孔硬碳材料的制备方法及其制品、应用Preparation method of porous hard carbon material for sodium ion battery and its products and applications 技术领域Technical field
本发明涉及电池材料领域，具体涉及一种钠离子电池多孔硬碳材料的制备方法及其制品、应用。The invention relates to the field of battery materials, and in particular to a preparation method of porous hard carbon materials for sodium ion batteries and their products and applications.
背景技术Background technique
负极材料作为钠离子电池的四大组成材料之一，在提高电池的能量密度和循环寿命方面起到了重要的作用。然而，由于钠离子的离子半径大于锂离子，在锂离子电池中广泛应用的石墨负极材料无法直接用于钠离子电池，因此需要开发新的负极材料以供离子半径较大的钠离子(r＝0.113nm)嵌入和脱出。As one of the four major components of sodium-ion batteries, negative electrode materials play an important role in improving the energy density and cycle life of the battery. However, since the ionic radius of sodium ions is larger than that of lithium ions, the graphite anode material widely used in lithium-ion batteries cannot be directly used in sodium-ion batteries. Therefore, new anode materials need to be developed to accommodate sodium ions with larger ionic radius (r= 0.113nm) insertion and extraction.
在众多储钠负极材料中，硬碳材料因具有高的比容量和长循环寿命等优势被认为最有应用前景的钠离子电池负极材料。硬碳含有两种类型的纳米区域：一种是短程有序宽晶面间距(d＝0.37～0.4nm)的石墨化碳区域，另一种是石墨区域间的微孔。这两个区域均可以进行储钠反应，其中微孔区域是储钠反应的主要活性位，因此设计合适的孔道结构是取得高性能硬碳负极材料的关键。Among many sodium storage anode materials, hard carbon materials are considered to be the most promising anode materials for sodium-ion batteries due to their high specific capacity and long cycle life. Hard carbon contains two types of nanoregions: one is a graphitized carbon region with short-range order and wide interplanar spacing (d=0.37~0.4nm), and the other is micropores between graphite regions. Both areas can carry out sodium storage reactions. The microporous area is the main active site for sodium storage reaction. Therefore, designing an appropriate pore structure is the key to obtaining high-performance hard carbon anode materials.
发明内容Contents of the invention
基于现有技术的不足，本发明的目的在于提供了一种钠离子电池多孔硬碳材料的制备方法，该方法以葡萄糖酸盐和葡萄糖共同作为碳源，同时通过调控葡萄糖酸盐控制碳热解过程中的造孔效率，最终制备的多孔硬碳材料孔结构分布均匀，尺寸适合于钠离子在充放电过程中的脱嵌行为，将所得产品应用于钠离子电池可展现出高容量和高循环稳定性。Based on the shortcomings of the existing technology, the purpose of the present invention is to provide a method for preparing porous hard carbon materials for sodium ion batteries. This method uses gluconate and glucose as carbon sources, and at the same time controls carbon pyrolysis by regulating gluconate. The pore-forming efficiency in the process, the pore structure of the finally prepared porous hard carbon material is evenly distributed, and the size is suitable for the deintercalation behavior of sodium ions during the charge and discharge process. The resulting product can be used in sodium-ion batteries to demonstrate high capacity and high cycle stability.
为了达到上述目的，本发明采取的技术方案为：In order to achieve the above objects, the technical solutions adopted by the present invention are:
一种钠离子电池多孔硬碳材料的制备方法，包括以下步骤：A method for preparing porous hard carbon materials for sodium ion batteries, including the following steps:
(1)将葡萄糖酸盐和葡萄糖溶于水配制成有机溶液A；所述葡萄糖酸盐和葡萄糖的摩尔比为0.8～1.2；(1) Dissolve gluconate and glucose in water to prepare organic solution A; the molar ratio of gluconate and glucose is 0.8 to 1.2;
(2)将有机溶液A经冷冻干燥处理得到冻干物B；(2) freeze-dry organic solution A to obtain lyophilizate B;
(3)将冻干物B在惰性气氛下400～800℃保温1～3h，所得产物经酸洗和抽滤洗涤处理后，得前驱体C；(3) The lyophilizate B is incubated at 400-800°C for 1-3 hours under an inert atmosphere, and the resulting product is washed with acid and suction filtration to obtain precursor C;
(4)在惰性气氛下，将前驱体C在1200～1600℃下保温1～3h，冷却，即得所述钠离子 电池多孔硬碳材料。(4) In an inert atmosphere, the precursor C is kept at 1200-1600°C for 1-3 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
现有技术领域中，多孔硬碳材料在制备过程中除了选用适合的无定型碳源外，一般还会同时引入金属盐造孔剂，在碳热解过程中，造孔剂可充分调节碳架结构，使得最终产品富含孔洞。然而经过发明人实验发现，当选用葡萄糖作为碳源时，并非任意的造孔剂可以实现理想的造孔效果，若采用诸如草酸金属盐、柠檬酸金属盐等造孔剂进行造孔，其最终制备的多孔硬碳材料的真密度偏大，比表面积偏大，应用于钠离子电池负极材料时不仅放电比容量不高，同时库伦效率低，循环稳定性差。因此，本发明技术方案所述方法中选用葡萄糖酸盐配合葡萄糖作为原料，葡萄糖酸盐既作为碳源，也作为造孔剂发生作用，而在高温煅烧前，本发明技术方案还引入了预热步骤，通过适当温度的预热处理可以有效调控原料中金属氧化物的数量、尺寸和分布，从而起到调控硬碳材料孔洞的数量、尺寸和分布的作用。所述制备方法操作步骤简单，未涉及高技术要求和高设备要求，可实现工业化大规模生产。In the current technical field, in addition to selecting a suitable amorphous carbon source during the preparation process of porous hard carbon materials, a metal salt pore-forming agent is generally introduced at the same time. During the carbon pyrolysis process, the pore-forming agent can fully adjust the carbon framework. structure, making the final product rich in holes. However, the inventor found through experiments that when glucose is used as the carbon source, not any pore-forming agent can achieve the ideal pore-forming effect. If pore-forming agents such as oxalate metal salts and citric acid metal salts are used to create pores, the final result will be The prepared porous hard carbon material has a relatively large true density and a relatively large specific surface area. When used as anode material for sodium-ion batteries, it not only has a low specific discharge capacity, but also has low Coulombic efficiency and poor cycle stability. Therefore, in the method described in the technical solution of the present invention, gluconate combined with glucose is selected as the raw material. The gluconate acts both as a carbon source and as a pore-forming agent. Before high-temperature calcination, the technical solution of the present invention also introduces preheating. In this step, the number, size and distribution of metal oxides in the raw materials can be effectively controlled through preheating at appropriate temperatures, thereby controlling the number, size and distribution of pores in the hard carbon material. The preparation method has simple operation steps, does not involve high technical requirements and high equipment requirements, and can realize industrial large-scale production.
优选地，所述葡萄糖酸盐为葡萄糖酸钙、葡萄糖酸镁、葡萄糖酸锌、葡萄糖酸铁、葡萄糖酸铜中的至少一种。Preferably, the gluconate is at least one of calcium gluconate, magnesium gluconate, zinc gluconate, iron gluconate, and copper gluconate.
更优选地，所述葡萄糖酸盐为葡萄糖酸镁。More preferably, the gluconate is magnesium gluconate.
经发明人实验筛选，上述种类的葡萄糖酸盐均可以达到理想的造孔效果，使得最终制备多孔硬碳材料的碳架结构适用于钠离子传输过程中的脱嵌。After experimental screening by the inventor, the above types of gluconates can achieve ideal pore-forming effects, making the carbon framework structure of the final porous hard carbon material suitable for the deintercalation of sodium ions during the transmission process.
优选地，所述步骤(2)中冷冻干燥处理时的温度为-50～-80℃，真空度为10～20Pa，时间为12～36h。Preferably, the temperature during the freeze-drying process in step (2) is -50~-80°C, the vacuum degree is 10~20Pa, and the time is 12~36h.
经发明人实验可知，冷冻干燥这一步骤对产品的造孔性能有较大影响，在碳源冷冻干燥处理后再进行预热及高温处理可以使得产品的闭孔体积密度更大，更有利于钠离子的脱嵌效应。The inventor's experiments show that the freeze-drying step has a great impact on the pore-forming performance of the product. Preheating and high-temperature treatment after the carbon source freeze-drying process can make the closed-pore volume density of the product greater, which is more beneficial. Deintercalation effect of sodium ions.
优选地，所述步骤(3)中的惰性气氛为氮气、氩气、氦气中的任意一种，保温时的升温速率为3～5℃/min。Preferably, the inert atmosphere in step (3) is any one of nitrogen, argon, and helium, and the temperature rise rate during heat preservation is 3 to 5°C/min.
对碳源进行预热处理时，可以有效使葡萄糖炭化裂解形成初步的碳骨架，同时金属盐在此过程中渗透入碳骨架中并形成金属氧化物进行孔洞结构调控，而控制适当的升温速率可以有效使这种造孔剂的分布更加均匀。When preheating the carbon source, glucose can be effectively carbonized and cracked to form a preliminary carbon skeleton. At the same time, metal salts penetrate into the carbon skeleton during this process and form metal oxides to regulate the pore structure. Controlling the appropriate heating rate can Effectively make the distribution of this pore-forming agent more even.
优选地，所述步骤(3)中酸洗所用酸溶液为盐酸溶液、硫酸溶液中的至少一种，所述酸溶液的摩尔浓度为0.5～1mol/L。Preferably, the acid solution used for pickling in step (3) is at least one of hydrochloric acid solution and sulfuric acid solution, and the molar concentration of the acid solution is 0.5-1 mol/L.
通过上述浓度的酸溶液可以有效去除前驱体材料中的金属氧化物。需要说明的是，所述酸洗处理并不局限于上述条件，只要能达到相同的处理效果，其他试剂也均可以使用。The metal oxides in the precursor material can be effectively removed by the acid solution with the above concentration. It should be noted that the pickling treatment is not limited to the above conditions. As long as the same treatment effect can be achieved, other reagents can also be used.
优选地，所述步骤(4)中的惰性气氛为氮气、氩气、氦气中的任意一种，保温时的升温速率为5～10℃/min。Preferably, the inert atmosphere in step (4) is any one of nitrogen, argon, and helium, and the temperature rise rate during heat preservation is 5-10°C/min.
在所述温度及升温速率下，前驱体材料可以有效转化为合适孔洞分布的硬碳材料。At the above-mentioned temperature and heating rate, the precursor material can be effectively transformed into a hard carbon material with appropriate pore distribution.
本发明的另一目的在于提供所述钠离子电池多孔硬碳材料的制备方法制备得到的钠离子电池多孔硬碳负极材料，以及采用该钠离子电池多孔硬碳负极材料制备得到的钠离子电池。Another object of the present invention is to provide a porous hard carbon negative electrode material for a sodium ion battery prepared by the method for preparing a porous hard carbon material for a sodium ion battery, and a sodium ion battery prepared by using the porous hard carbon negative electrode material for a sodium ion battery.
本发明所述方法制备的钠离子电池多孔硬碳材料真密度较小，可达到1.4g/cm 3以下，同时闭孔体积密度最大可接近0.3cm 3/g，应用在钠离子电池中具有优异的电化学性能。 The porous hard carbon material of the sodium ion battery prepared by the method of the present invention has a small true density, which can reach less than 1.4g/cm 3 , and at the same time, the maximum closed-pore volume density can be close to 0.3cm 3 /g, and has excellent application in sodium ion batteries. electrochemical properties.
本发明的有益效果在于：本发明提供了一种钠离子电池多孔硬碳材料的制备方法，该方法以葡萄糖酸盐和葡萄糖共同作为碳源，同时通过调控葡萄糖酸盐控制碳热解过程中的造孔效率，最终制备的多孔硬碳材料孔结构分布均匀，尺寸适合于钠离子在充放电过程中的脱嵌行为，将所得产品应用于钠离子电池可展现出高容量和高循环稳定性。本发明还提供了所述钠离子电池多孔硬碳材料的制备方法制备得到的钠离子电池多孔硬碳负极材料以及采用该钠离子电池多孔硬碳负极材料制备得到的钠离子电池。The beneficial effects of the present invention are: the present invention provides a method for preparing porous hard carbon materials for sodium ion batteries. The method uses gluconate and glucose as carbon sources, and at the same time controls the carbon pyrolysis process by regulating gluconate. Pore-forming efficiency, the pore structure of the finally prepared porous hard carbon material is uniformly distributed, and the size is suitable for the deintercalation behavior of sodium ions during the charge and discharge process. The resulting product can be applied to sodium-ion batteries to demonstrate high capacity and high cycle stability. The invention also provides a porous hard carbon negative electrode material for a sodium ion battery prepared by the method for preparing a porous hard carbon material for a sodium ion battery and a sodium ion battery prepared by using the porous hard carbon negative electrode material for a sodium ion battery.
说明书附图Instructions with pictures
图1为本发明所述钠离子电池多孔硬碳材料的扫描电镜图。Figure 1 is a scanning electron microscope image of the porous hard carbon material of the sodium ion battery of the present invention.
具体实施方式Detailed ways
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、对比例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。In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific examples and comparative examples. The purpose is to understand the content of the present invention in detail, but not to limit the present invention. All other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the protection scope of the present invention. The experimental reagents and instruments designed for the implementation and comparative examples of the present invention are all commonly used ordinary reagents and instruments unless otherwise specified.
实施例1Example 1
本发明所述一种钠离子电池多孔硬碳材料的制备方法及其制品、应用的一种实施例，所述方法包括以下步骤：An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention. The method includes the following steps:
(1)将166g葡萄糖酸镁和90g葡萄糖(两者摩尔比0.8)溶于1500mL去离子水配制成有机溶液A；(1) Dissolve 166g magnesium gluconate and 90g glucose (molar ratio of the two 0.8) in 1500mL deionized water to prepare organic solution A;
(2)将有机溶液A置入冷冻干燥机中经-70℃，15Pa冷冻干燥处理24h得到冻干物B；(2) Place organic solution A into a freeze dryer and freeze-dry at -70°C, 15 Pa for 24 hours to obtain lyophilizate B;
(3)将冻干物B在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体C；(3) The lyophilizate B was heated to 600°C at a rate of 3°C/min in a nitrogen atmosphere and kept for 2 hours, then cooled to room temperature. The resulting product was pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the pH of the filtered water was normal. After sex, precursor C is obtained;
(4)在氮气气氛下，将前驱体C以10℃/min的升温速率升温至1500℃下保温2h，冷却， 即得所述钠离子电池多孔硬碳材料。将所得产品进行扫描电镜观察，如图1所示，该材料形貌均匀，无明显团聚。(4) In a nitrogen atmosphere, the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery. The obtained product was observed under a scanning electron microscope. As shown in Figure 1, the material had a uniform morphology and no obvious agglomeration.
实施例2Example 2
本实施例与实施例1的差别仅在于，所述葡萄糖酸镁的添加量为208g。The only difference between this embodiment and Example 1 is that the added amount of magnesium gluconate is 208g.
实施例3Example 3
本实施例与实施例1的差别仅在于，所述葡萄糖酸镁的添加量为249g。The only difference between this embodiment and Example 1 is that the added amount of magnesium gluconate is 249g.
实施例4Example 4
本发明所述一种钠离子电池多孔硬碳材料的制备方法及其制品、应用的一种实施例，所述方法包括以下步骤：An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention. The method includes the following steps:
(1)将215g葡萄糖酸钙和90g葡萄糖(两者摩尔比为1)溶于1500mL去离子水配制成有机溶液A；(1) Dissolve 215g calcium gluconate and 90g glucose (the molar ratio of the two is 1) in 1500mL deionized water to prepare organic solution A;
(2)将有机溶液A置入冷冻干燥机中经-70℃，15Pa冷冻干燥处理24h得到冻干物B；(2) Place organic solution A into a freeze dryer and freeze-dry at -70°C, 15 Pa for 24 hours to obtain lyophilizate B;
(3)将冻干物B在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体C；(3) The lyophilizate B was heated to 600°C at a rate of 3°C/min in a nitrogen atmosphere and kept for 2 hours, then cooled to room temperature. The resulting product was pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the pH of the filtered water was normal. After sex, precursor C is obtained;
(4)在氮气气氛下，将前驱体C以10℃/min的升温速率升温至1500℃下保温2h，冷却，即得所述钠离子电池多孔硬碳材料。(4) In a nitrogen atmosphere, the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
实施例5Example 5
本发明所述一种钠离子电池多孔硬碳材料的制备方法及其制品、应用的一种实施例，所述方法包括以下步骤：An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention. The method includes the following steps:
(1)将228g葡萄糖酸锌和90g葡萄糖(两者摩尔比为1)溶于1500mL去离子水配制成有机溶液A；(1) Dissolve 228g zinc gluconate and 90g glucose (the molar ratio of the two is 1) in 1500mL deionized water to prepare organic solution A;
(2)将有机溶液A置入冷冻干燥机中经-70℃，15Pa冷冻干燥处理24h得到冻干物B；(2) Place organic solution A into a freeze dryer and freeze-dry at -70°C, 15 Pa for 24 hours to obtain lyophilizate B;
(3)将冻干物B在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体C；(3) The lyophilizate B was heated to 600°C at a rate of 3°C/min in a nitrogen atmosphere and kept for 2 hours, then cooled to room temperature. The resulting product was pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the pH of the filtered water was normal. After sex, precursor C is obtained;
(4)在氮气气氛下，将前驱体C以10℃/min的升温速率升温至1500℃下保温2h，冷却，即得所述钠离子电池多孔硬碳材料。(4) In a nitrogen atmosphere, the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
实施例6Example 6
本发明所述一种钠离子电池多孔硬碳材料的制备方法及其制品、应用的一种实施例，所述方法包括以下步骤：An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention. The method includes the following steps:
(1)将223g葡萄糖酸铁和90g葡萄糖(两者摩尔比为1)溶于1500mL去离子水配制成 有机溶液A；(1) Dissolve 223g iron gluconate and 90g glucose (the molar ratio of the two is 1) in 1500mL deionized water to prepare organic solution A;
(2)将有机溶液A置入冷冻干燥机中经-70℃，15Pa冷冻干燥处理24h得到冻干物B；(2) Place organic solution A into a freeze dryer and freeze-dry at -70°C, 15 Pa for 24 hours to obtain lyophilizate B;
(3)将冻干物B在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体C；(3) The lyophilizate B was heated to 600°C at a rate of 3°C/min in a nitrogen atmosphere and kept for 2 hours, then cooled to room temperature. The resulting product was pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the pH of the filtered water was normal. After sex, precursor C is obtained;
(4)在氮气气氛下，将前驱体C以10℃/min的升温速率升温至1500℃下保温2h，冷却，即得所述钠离子电池多孔硬碳材料。(4) In a nitrogen atmosphere, the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
实施例7Example 7
本发明所述一种钠离子电池多孔硬碳材料的制备方法及其制品、应用的一种实施例，所述方法包括以下步骤：An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention. The method includes the following steps:
(1)将227g葡萄糖酸铜和90g葡萄糖(两者摩尔比为1)溶于1500mL去离子水配制成有机溶液A；(1) Dissolve 227g copper gluconate and 90g glucose (the molar ratio of the two is 1) in 1500mL deionized water to prepare organic solution A;
(2)将有机溶液A置入冷冻干燥机中经-70℃，15Pa冷冻干燥处理24h得到冻干物B；(2) Place organic solution A into a freeze dryer and freeze-dry at -70°C, 15 Pa for 24 hours to obtain lyophilizate B;
(3)将冻干物B在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体C；(3) The lyophilizate B was heated to 600°C at a rate of 3°C/min in a nitrogen atmosphere and kept for 2 hours, then cooled to room temperature. The resulting product was pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the pH of the filtered water was normal. After sex, precursor C is obtained;
(4)在氮气气氛下，将前驱体C以10℃/min的升温速率升温至1500℃下保温2h，冷却，即得所述钠离子电池多孔硬碳材料。(4) In a nitrogen atmosphere, the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
实施例8Example 8
本发明所述一种钠离子电池多孔硬碳材料的制备方法及其制品、应用的一种实施例，所述方法包括以下步骤：An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention. The method includes the following steps:
(1)将109g葡萄糖酸钠和90g葡萄糖(两者摩尔比为1)溶于1500mL去离子水配制成有机溶液A；(1) Dissolve 109g sodium gluconate and 90g glucose (the molar ratio of the two is 1) in 1500mL deionized water to prepare organic solution A;
(2)将有机溶液A置入冷冻干燥机中经-70℃，15Pa冷冻干燥处理24h得到冻干物B；(2) Place organic solution A into a freeze dryer and freeze-dry at -70°C, 15 Pa for 24 hours to obtain lyophilizate B;
(3)将冻干物B在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体C；(3) The lyophilizate B was heated to 600°C at a rate of 3°C/min in a nitrogen atmosphere and kept for 2 hours, then cooled to room temperature. The resulting product was pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the pH of the filtered water was normal. After sex, precursor C is obtained;
(4)在氮气气氛下，将前驱体C以10℃/min的升温速率升温至1500℃下保温2h，冷却，即得所述钠离子电池多孔硬碳材料。(4) In a nitrogen atmosphere, the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
实施例9Example 9
本发明所述一种钠离子电池多孔硬碳材料的制备方法及其制品、应用的一种实施例，所述方法包括以下步骤：An embodiment of the preparation method of porous hard carbon material for sodium ion batteries and its products and applications according to the present invention. The method includes the following steps:
(1)将117g葡萄糖酸钾和90g葡萄糖(两者摩尔比为1)溶于1500mL去离子水配制成 有机溶液A；(1) Dissolve 117g potassium gluconate and 90g glucose (the molar ratio of the two is 1) in 1500mL deionized water to prepare organic solution A;
(2)将有机溶液A置入冷冻干燥机中经-70℃，15Pa冷冻干燥处理24h得到冻干物B；(2) Place organic solution A into a freeze dryer and freeze-dry at -70°C, 15 Pa for 24 hours to obtain lyophilizate B;
(3)将冻干物B在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体C；(3) The lyophilizate B was heated to 600°C at a rate of 3°C/min in a nitrogen atmosphere and kept for 2 hours, then cooled to room temperature. The resulting product was pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the pH of the filtered water was normal. After sex, precursor C is obtained;
(4)在氮气气氛下，将前驱体C以10℃/min的升温速率升温至1500℃下保温2h，冷却，即得所述钠离子电池多孔硬碳材料。(4) In a nitrogen atmosphere, the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
实施例10Example 10
本实施例与实施例1的差别仅在于，所述步骤(3)的保温温度为400℃，时间为3h。The only difference between this embodiment and Embodiment 1 is that the insulation temperature in step (3) is 400°C and the time is 3 hours.
实施例11Example 11
本实施例与实施例1的差别仅在于，所述步骤(3)的保温温度为800℃，时间为1h。The only difference between this embodiment and Embodiment 1 is that the insulation temperature in step (3) is 800°C and the time is 1 hour.
对比例1Comparative example 1
一种多孔硬碳材料及其制备方法，所述方法包括以下步骤：A porous hard carbon material and a preparation method thereof, which method includes the following steps:
(1)将100g葡萄糖在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体；(1) Heat 100g of glucose to 600°C at a rate of 3°C/min under a nitrogen atmosphere and keep it for 2 hours, then cool to room temperature. The resulting product is pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the pH of the filtered water is neutral. , get the precursor;
(2)在氮气气氛下，将前驱体以10℃/min的升温速率升温至1500℃下保温2h，冷却，即得所述多孔硬碳材料。(2) In a nitrogen atmosphere, the precursor is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material.
对比例2Comparative example 2
一种钠离子电池多孔硬碳材料及其制备方法，所述方法包括以下步骤：A porous hard carbon material for sodium ion batteries and a preparation method thereof, which method includes the following steps:
(1)将208g葡萄糖酸镁和90g葡萄糖(两者摩尔比为1)溶于1500mL去离子水配制成有机溶液A；(1) Dissolve 208g magnesium gluconate and 90g glucose (the molar ratio of the two is 1) in 1500mL deionized water to prepare organic solution A;
(2)将有机溶液A置于蒸发皿中60℃干燥24h，得到干燥物B；(2) Place organic solution A in an evaporating dish and dry at 60°C for 24 hours to obtain dried product B;
(3)将干燥物B在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体C；(3) The dried product B was heated to 600°C at a rate of 3°C/min in a nitrogen atmosphere and kept for 2 hours, then cooled to room temperature. The resulting product was pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the filtered water was pH neutral. Finally, precursor C is obtained;
(4)在氮气气氛下，将前驱体C以10℃/min的升温速率升温至1500℃下保温2h，冷却，即得所述钠离子电池多孔硬碳材料。(4) In a nitrogen atmosphere, the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
对比例3Comparative example 3
一种钠离子电池多孔硬碳材料及其制备方法，所述方法包括以下步骤：A porous hard carbon material for sodium ion batteries and a preparation method thereof, which method includes the following steps:
(1)将107g柠檬酸镁和90g葡萄糖(两者摩尔比为1)溶于1500mL去离子水配制成有机溶液A；(1) Dissolve 107g magnesium citrate and 90g glucose (the molar ratio of the two is 1) in 1500mL deionized water to prepare organic solution A;
(2)将有机溶液A置入冷冻干燥机中经-70℃，15Pa冷冻干燥处理24h得到冻干物B；(2) Place organic solution A into a freeze dryer and freeze-dry at -70°C, 15 Pa for 24 hours to obtain lyophilizate B;
(3)将冻干物B在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体C；(3) The lyophilizate B was heated to 600°C at a rate of 3°C/min in a nitrogen atmosphere and kept for 2 hours, then cooled to room temperature. The resulting product was pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the pH of the filtered water was normal. After sex, precursor C is obtained;
(4)在氮气气氛下，将前驱体C以10℃/min的升温速率升温至1500℃下保温2h，冷却，即得所述钠离子电池多孔硬碳材料。(4) In a nitrogen atmosphere, the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
对比例4Comparative example 4
一种钠离子电池多孔硬碳材料及其制备方法，所述方法包括以下步骤：A porous hard carbon material for sodium ion batteries and a preparation method thereof, which method includes the following steps:
(1)将74g草酸镁和90g葡萄糖(两者摩尔比为1)溶于1500mL去离子水配制成有机溶液A；(1) Dissolve 74g magnesium oxalate and 90g glucose (the molar ratio of the two is 1) in 1500mL deionized water to prepare organic solution A;
(2)将有机溶液A置入冷冻干燥机中经-70℃，15Pa冷冻干燥处理24h得到冻干物B；(2) Place organic solution A into a freeze dryer and freeze-dry at -70°C, 15 Pa for 24 hours to obtain lyophilizate B;
(3)将冻干物B在氮气气氛下以3℃/min速率升温至600℃保温2h，冷却至室温，所得产物经1mol/L的盐酸溶液酸洗和抽滤洗涤至滤水呈pH中性后，得前驱体C；(3) The lyophilizate B was heated to 600°C at a rate of 3°C/min in a nitrogen atmosphere and kept for 2 hours, then cooled to room temperature. The resulting product was pickled with 1 mol/L hydrochloric acid solution and washed with suction filtration until the pH of the filtered water was normal. After sex, precursor C is obtained;
(4)在氮气气氛下，将前驱体C以10℃/min的升温速率升温至1500℃下保温2h，冷却，即得所述钠离子电池多孔硬碳材料。(4) In a nitrogen atmosphere, the precursor C is heated to 1500°C at a heating rate of 10°C/min, kept at 1500°C for 2 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
对比例5Comparative example 5
本对比例与实施例1的差别仅在于，所述步骤(3)的保温温度为900℃，时间为0.5h。The only difference between this comparative example and Example 1 is that the insulation temperature in step (3) is 900°C and the time is 0.5 h.
对比例6Comparative example 6
本对比例与实施例1的差别仅在于，所述步骤(3)的保温温度为300℃，时间为4h。The only difference between this comparative example and Example 1 is that the insulation temperature in step (3) is 300°C and the time is 4 hours.
效果例1Effect example 1
为了验证本发明所述制备方法制备产品的质量，将各实施例和对比例产品进行真密度和闭孔体积密度测试，其中真密度采用真密度仪直接测试，而闭孔体积密度则根据计算公式：闭孔体积密度＝1/真密度-1/2.26计算得到。测试结果如表1所示。In order to verify the quality of the products prepared by the preparation method of the present invention, the true density and closed cell volume density of the products of each example and comparative example were tested. The true density was directly tested using a true density meter, while the closed cell volume density was measured according to the calculation formula. : Calculated by closed cell volume density=1/true density-1/2.26. The test results are shown in Table 1.
表1Table 1
Figure PCTCN2022122270-appb-000001
Figure PCTCN2022122270-appb-000001
从表1可以看出，各实施例产品制备的钠离子电池多孔硬碳材料均具有较低的真密度和较大的闭孔体积密度，相比直接采用葡萄糖常规制备的对比例1产品具有显著改性提升，其中以实施例3效果最佳；相比于实施例1～7，实施例8和9采用了非优选的葡萄糖酸盐，所 得产品中孔洞结构的改善程度非常有限。实施例10和11与实施例1的闭孔体积密度相接近。对比例2产品采用了常规了前置干燥处理方法，所得到的产品闭孔体积密度明显较小，说明碳源的前置冷冻干燥处理对最终产品的孔洞结构有较大影响。对比例3和4采用了现有常规的其他种类金属盐代替葡萄糖酸盐，所得产品的表征结果与对比例1差距不大，说明并非任意金属盐造孔剂适用于制备本发明所述钠离子电池多孔碳材料。此外，对比例10和11与实施例1的闭孔体积密度相差较大，表明初步烧结温度和时间均会影响最终产品的孔洞结构，无论是烧结程度过高或过低均难以达到理想的效果。It can be seen from Table 1 that the porous hard carbon materials for sodium ion batteries prepared by the products of each example have lower true density and larger closed cell volume density. Compared with the product of Comparative Example 1, which is conventionally prepared directly from glucose, it has significantly higher Modification improvement, among which Example 3 has the best effect; compared with Examples 1 to 7, Examples 8 and 9 use non-preferred gluconate, and the degree of improvement of the hole structure in the obtained product is very limited. The closed cell volume densities of Examples 10 and 11 are close to those of Example 1. The product of Comparative Example 2 adopts the conventional pre-drying treatment method, and the closed-pore volume density of the obtained product is significantly smaller, indicating that the pre-freeze drying treatment of the carbon source has a greater impact on the pore structure of the final product. Comparative Examples 3 and 4 used existing conventional metal salts of other types instead of gluconate, and the characterization results of the obtained products were not much different from Comparative Example 1, indicating that not any metal salt pore-forming agent is suitable for preparing sodium ions according to the present invention. Porous carbon materials for batteries. In addition, the closed cell volume density of Comparative Examples 10 and 11 is quite different from that of Example 1, indicating that both the preliminary sintering temperature and time will affect the pore structure of the final product. Whether the degree of sintering is too high or too low, it is difficult to achieve the desired effect. .
进一步地，将各实施例和对比例产品进行比表面积测试(采用比表面积测定仪直接测试)，结果如表2所示。Further, the products of each example and comparative example were tested for specific surface area (direct testing using a specific surface area measuring instrument), and the results are shown in Table 2.
表2Table 2
Figure PCTCN2022122270-appb-000002
Figure PCTCN2022122270-appb-000002
从表2可以看出，各实施例产品相比于对比例1产品其比表面积均有所降低，孔洞结构的改善效果明显；相比之下，对比例3和4产品的比表面积反而更大。It can be seen from Table 2 that the specific surface area of the products of each example is reduced compared with the product of Comparative Example 1, and the improvement effect of the hole structure is obvious; in contrast, the specific surface areas of the products of Comparative Examples 3 and 4 are larger. .
效果例2Effect example 2
为了验证本发明所述产品的电化学性能，将各制备多孔硬碳材料作为钠离子电池多孔硬碳负极材料使用，将各材料制备成钠离子电池(钠片为对电极)并在20mA/g的电流密度，0～2V的工作电压下进行电化学性能测试，结果如表3所示。In order to verify the electrochemical performance of the product of the present invention, each prepared porous hard carbon material was used as a porous hard carbon negative electrode material for a sodium ion battery. The electrochemical performance test was carried out at a current density of 0 to 2V and the results are shown in Table 3.
表3table 3
Figure PCTCN2022122270-appb-000003
Figure PCTCN2022122270-appb-000003
从表3可以看出，除实施例8和9外，各实施例产品的首次放电比容量均较高，达到了400mAh/g以上，以实施例3放电比容量最高；而在库伦效率方面，各实施例相比于对比例1产品均显著提升，以实施例1的库伦效率最高。相比之下，对比例2产品虽然库伦效率较高， 但初始放电比容量较低，说明有较多的钠离子在首次充放电过程中未被进行有效脱嵌。对比例3和4产品无论是放电比容量亦或是库伦效率均较低，说明采用非优选的金属盐造孔剂制备的多孔硬碳材料难以应用在钠离子电池负极材料当中。对比例5和6的产品在制备过程中预烧过程效果不理想，同样难以达到理想的性能。As can be seen from Table 3, except for Examples 8 and 9, the first discharge specific capacity of the products of each example is higher, reaching more than 400mAh/g, with Example 3 having the highest discharge specific capacity; and in terms of Coulombic efficiency, Compared with the product of Comparative Example 1, the Coulombic efficiency of Example 1 is the highest. In contrast, although the product of Comparative Example 2 has higher Coulombic efficiency, its initial discharge specific capacity is lower, indicating that more sodium ions are not effectively deintercalated during the first charge and discharge process. The products of Comparative Examples 3 and 4 were both low in discharge specific capacity and Coulombic efficiency, indicating that porous hard carbon materials prepared using non-preferred metal salt pore-forming agents are difficult to be used as negative electrode materials for sodium ion batteries. The products of Comparative Examples 5 and 6 had unsatisfactory pre-burning effects during the preparation process, and it was also difficult to achieve ideal performance.
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。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and do not limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that The technical solution of the present invention may be modified or equivalently substituted without departing from the essence and scope of the technical solution of the present invention.

Claims (10)

  1. 一种钠离子电池多孔硬碳材料的制备方法，其特征在于，包括以下步骤：A method for preparing porous hard carbon materials for sodium ion batteries, which is characterized by including the following steps:
    (1)将葡萄糖酸盐和葡萄糖溶于水配制成有机溶液A；所述葡萄糖酸盐和葡萄糖的摩尔比为0.8～1.2；(1) Dissolve gluconate and glucose in water to prepare organic solution A; the molar ratio of gluconate and glucose is 0.8 to 1.2;
    (2)将有机溶液A经冷冻干燥处理得到冻干物B；(2) freeze-dry organic solution A to obtain lyophilizate B;
    (3)将冻干物B在惰性气氛下400～800℃保温1～3h，所得产物经酸洗和抽滤洗涤处理后，得前驱体C；(3) The lyophilizate B is incubated at 400-800°C for 1-3 hours under an inert atmosphere, and the resulting product is washed with acid and suction filtration to obtain precursor C;
    (4)在惰性气氛下，将前驱体C在1200～1600℃下保温1～3h，冷却，即得所述钠离子电池多孔硬碳材料。(4) In an inert atmosphere, the precursor C is kept at 1200-1600°C for 1-3 hours, and then cooled to obtain the porous hard carbon material for the sodium ion battery.
  2. 如权利要求1所述的钠离子电池多孔硬碳材料的制备方法，其特征在于，所述葡萄糖酸盐为葡萄糖酸钙、葡萄糖酸镁、葡萄糖酸锌、葡萄糖酸铁、葡萄糖酸铜中的至少一种。The method for preparing porous hard carbon materials for sodium ion batteries according to claim 1, wherein the gluconate is at least one of calcium gluconate, magnesium gluconate, zinc gluconate, iron gluconate and copper gluconate. A sort of.
  3. 如权利要求2所述的钠离子电池多孔硬碳材料的制备方法，其特征在于，所述葡萄糖酸盐为葡萄糖酸镁。The method for preparing porous hard carbon materials for sodium ion batteries according to claim 2, wherein the gluconate is magnesium gluconate.
  4. 如权利要求1所述的钠离子电池多孔硬碳材料的制备方法，其特征在于，所述步骤(2)中冷冻干燥处理时的温度为-50～-80℃，真空度为10～20Pa，时间为12～36h。The method for preparing porous hard carbon materials for sodium ion batteries according to claim 1, wherein the temperature during the freeze-drying process in step (2) is -50~-80°C, and the vacuum degree is 10~20Pa. The time is 12~36h.
  5. 如权利要求1所述的钠离子电池多孔硬碳材料的制备方法，其特征在于，所述步骤(3)中的惰性气氛为氮气、氩气、氦气中的任意一种，保温时的升温速率为3～5℃/min。The method for preparing porous hard carbon materials for sodium ion batteries according to claim 1, wherein the inert atmosphere in step (3) is any one of nitrogen, argon, and helium, and the temperature rise during heat preservation The rate is 3~5℃/min.
  6. 如权利要求1所述的钠离子电池多孔硬碳材料的制备方法，其特征在于，所述步骤(3)中酸洗所用的酸溶液为盐酸溶液、硫酸溶液中的至少一种，所述酸溶液的摩尔浓度为0.5～1mol/L。The method for preparing porous hard carbon materials for sodium ion batteries according to claim 1, wherein the acid solution used for pickling in step (3) is at least one of hydrochloric acid solution and sulfuric acid solution, and the acid The molar concentration of the solution is 0.5~1mol/L.
  7. 如权利要求1所述的钠离子电池多孔硬碳材料的制备方法，其特征在于，所述步骤(4)中的惰性气氛为氮气、氩气、氦气中的任意一种，保温时的升温速率为5～10℃/min。The method for preparing porous hard carbon materials for sodium ion batteries according to claim 1, wherein the inert atmosphere in step (4) is any one of nitrogen, argon, and helium, and the temperature rise during heat preservation The rate is 5~10℃/min.
  8. 一种钠离子电池多孔硬碳负极材料，其由权利要求1～7中任一项所述的钠离子电池多孔硬碳材料的制备方法制备得到。A porous hard carbon negative electrode material for a sodium ion battery, which is prepared by the method for preparing a porous hard carbon material for a sodium ion battery according to any one of claims 1 to 7.
  9. 一种钠离子电池用负极片，其特征在于，包括权利要求8所述的钠离子电池多孔硬碳负极材料。A negative electrode sheet for sodium ion batteries, characterized by comprising the porous hard carbon negative electrode material for sodium ion batteries described in claim 8.
  10. 一种钠离子电池，其特征在于，包括权利要求9所述的钠离子电池用负极片。A sodium-ion battery, characterized by comprising the negative electrode sheet for sodium-ion batteries according to claim 9.
PCT/CN2022/122270 2022-06-28 2022-09-28 Preparation method for sodium ion battery porous hard carbon material, and product and use thereof WO2024000885A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202210745653.7 2022-06-28
CN202210745653.7A CN114988390A (en) 2022-06-28 2022-06-28 Preparation method of porous hard carbon material of sodium ion battery, product and application thereof

Publications (1)

Publication Number Publication Date
WO2024000885A1 true WO2024000885A1 (en) 2024-01-04

Family

ID=83036898

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/122270 WO2024000885A1 (en) 2022-06-28 2022-09-28 Preparation method for sodium ion battery porous hard carbon material, and product and use thereof

Country Status (3)

Country Link
CN (1) CN114988390A (en)
FR (1) FR3137215A1 (en)
WO (1) WO2024000885A1 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114988390A (en) * 2022-06-28 2022-09-02 广东邦普循环科技有限公司 Preparation method of porous hard carbon material of sodium ion battery, product and application thereof

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106654268A (en) * 2016-12-09 2017-05-10 太原理工大学 Method for preparing porous carbon material for lithium/sodium-ion battery
CN107093712A (en) * 2017-04-07 2017-08-25 西南大学 Anode material of lithium-ion battery and preparation method thereof
US20180301714A1 (en) * 2015-12-25 2018-10-18 Graduate School At Shenzhen, Tsinghua University Battery electrode material of ionised sodium and preparation method thereof
CN109678130A (en) * 2018-12-20 2019-04-26 电子科技大学 A kind of hard carbon material for sodium-ion battery cathode and preparation method thereof and related sodium-ion battery
CN113735095A (en) * 2021-08-06 2021-12-03 深圳市德方纳米科技股份有限公司 Porous hard carbon material and preparation method and application thereof
CN114524425A (en) * 2022-01-26 2022-05-24 广东海洋大学 Hard carbon material, preparation method thereof and application thereof in sodium-ion battery
CN114988390A (en) * 2022-06-28 2022-09-02 广东邦普循环科技有限公司 Preparation method of porous hard carbon material of sodium ion battery, product and application thereof

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2021077635A (en) * 2019-11-01 2021-05-20 学校法人東京理科大学 Negative electrode active material, manufacturing method thereof, negative electrode, and sodium ion battery

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20180301714A1 (en) * 2015-12-25 2018-10-18 Graduate School At Shenzhen, Tsinghua University Battery electrode material of ionised sodium and preparation method thereof
CN106654268A (en) * 2016-12-09 2017-05-10 太原理工大学 Method for preparing porous carbon material for lithium/sodium-ion battery
CN107093712A (en) * 2017-04-07 2017-08-25 西南大学 Anode material of lithium-ion battery and preparation method thereof
CN109678130A (en) * 2018-12-20 2019-04-26 电子科技大学 A kind of hard carbon material for sodium-ion battery cathode and preparation method thereof and related sodium-ion battery
CN113735095A (en) * 2021-08-06 2021-12-03 深圳市德方纳米科技股份有限公司 Porous hard carbon material and preparation method and application thereof
CN114524425A (en) * 2022-01-26 2022-05-24 广东海洋大学 Hard carbon material, preparation method thereof and application thereof in sodium-ion battery
CN114988390A (en) * 2022-06-28 2022-09-02 广东邦普循环科技有限公司 Preparation method of porous hard carbon material of sodium ion battery, product and application thereof

Also Published As

Publication number Publication date
FR3137215A1 (en) 2023-12-29
CN114988390A (en) 2022-09-02

Similar Documents

Publication Publication Date Title
CN110416503B (en) Soft carbon coated sodium titanium phosphate mesoporous composite material and preparation method and application thereof
CN110085813B (en) Hard carbon composite material and preparation method thereof
CN110571436A (en) Preparation method of three-dimensional porous carbon loaded flaky molybdenum disulfide current collector for lithium metal cathode
CN107910506B (en) Preparation method of NaCl modified graphene net coated β -FeOOH lithium ion battery negative electrode material
CN113054183A (en) Preparation method of CoNi bimetal organic framework derived carbon-sulfur composite material
WO2024000885A1 (en) Preparation method for sodium ion battery porous hard carbon material, and product and use thereof
CN111554891A (en) Method for preparing lithium-sulfur battery cathode material from three-dimensional mesoporous biochar
CN114141986A (en) Negative electrode material, preparation method and sodium ion battery
CN110808361A (en) Method for preparing lithium-sulfur battery cathode material based on bacterial cellulose
CN109244393A (en) A kind of lithium sulfur battery anode material and preparation method thereof of long circulating high rate capability
CN114229825A (en) Metal monoatomic-doped three-dimensional porous carbon material and preparation method and application thereof
CN113517427B (en) Preparation method and application of carbon-coated antimony/antimony trisulfide composite material
Shao et al. Amorphous hollow carbon film as a flexible host for liquid Na-K alloy anode
CN112174119B (en) Method for preparing graphene foam from antibiotic fungi residues
CN110165179B (en) Lithium battery negative electrode material, preparation method thereof and lithium battery containing negative electrode material
CN109461864A (en) A kind of preparation method of polyetherimide amine blends diaphragm and the application in lithium-sulfur cell
CN111943259A (en) Carbon-coated mesoporous dual-phase titanium dioxide and preparation method and energy storage application thereof
CN108987732B (en) SiO composite cathode material of lithium ion battery and preparation method thereof
CN113896193B (en) Surface modified exfoliated graphite as well as preparation method and application thereof
CN111952569B (en) Silicon oxide-based negative electrode material for lithium ion battery and preparation method thereof
CN109830666A (en) A kind of vanadic anhydride positive electrode and preparation method and application
CN115863569A (en) Plant carbon-supported metal compound nano composite material and preparation method and application thereof
CN112002890B (en) Lithium-sulfur battery positive electrode material and preparation method thereof
CN114744148A (en) Preparation method of hard carbon cathode of high-rate-performance sodium ion battery
CN114914416A (en) CoSe 2 Preparation method of decorative porous carbon cloth

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22948973

Country of ref document: EP

Kind code of ref document: A1