WO2023173772A1 - 硬碳负极材料的制备方法和应用 - Google Patents

硬碳负极材料的制备方法和应用 Download PDF

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WO2023173772A1
WO2023173772A1 PCT/CN2022/131441 CN2022131441W WO2023173772A1 WO 2023173772 A1 WO2023173772 A1 WO 2023173772A1 CN 2022131441 W CN2022131441 W CN 2022131441W WO 2023173772 A1 WO2023173772 A1 WO 2023173772A1
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sintering
hard carbon
negative electrode
electrode material
carbon negative
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PCT/CN2022/131441
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English (en)
French (fr)
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郑爽
李长东
毛林林
阮丁山
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广东邦普循环科技有限公司
湖南邦普循环科技有限公司
湖南邦普汽车循环有限公司
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Priority to MA62914A priority Critical patent/MA62914A1/fr
Priority to DE112022000884.9T priority patent/DE112022000884T5/de
Priority to GB2313102.2A priority patent/GB2618729B/en
Priority to HU2400038A priority patent/HUP2400038A1/hu
Priority to US18/284,763 priority patent/US20240088388A1/en
Publication of WO2023173772A1 publication Critical patent/WO2023173772A1/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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • C—CHEMISTRY; METALLURGY
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    • C01B32/00—Carbon; Compounds thereof
    • C01B32/30—Active carbon
    • C01B32/312—Preparation
    • C01B32/318—Preparation characterised by the starting materials
    • C01B32/324—Preparation characterised by the starting materials from waste materials, e.g. tyres or spent sulfite pulp liquor
    • 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
    • H01M4/04—Processes of manufacture in general
    • H01M4/0471—Processes of manufacture in general involving thermal treatment, e.g. firing, sintering, backing particulate active material, thermal decomposition, pyrolysis
    • H—ELECTRICITY
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    • 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
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    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • 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
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    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
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    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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    • C01P2006/00—Physical properties of inorganic compounds
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    • C01P2006/13—Surface area thermal stability thereof at high temperatures
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    • C01P2006/40—Electric properties
    • H—ELECTRICITY
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    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
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    • 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
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    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the invention belongs to the technical field of sodium ion battery materials, and specifically relates to the preparation method and application of hard carbon negative electrode materials.
  • lithium-ion batteries With the popularity of new energy vehicles, the consumption of lithium-ion batteries has increased sharply. As an important resource in lithium batteries, nickel, cobalt and manganese have gradually become scarce, and their prices have gradually increased. In order to alleviate the pressure of mining resources, sodium-ion batteries, which have a charge and discharge mechanism similar to lithium batteries, have once again attracted people's attention. Sodium salt is found all over the world and can effectively alleviate the pressure caused by insufficient nickel, cobalt and manganese resources.
  • graphite a commonly used negative electrode in lithium-ion batteries, is not suitable for sodium-ion batteries because the diameter of sodium ions is larger than the diameter of lithium ions and cannot be deintercalated between graphite layers.
  • sodium ions cannot form a stable phase structure with graphite.
  • Other anode materials for sodium-ion batteries were also studied at the same time, including graphitized hard carbon, alloys, oxides and organic composites. However, most current anode materials will produce large volume expansion during the sodium ion intercalation process, resulting in irreversible capacity fading.
  • the present invention aims to solve at least one of the technical problems existing in the above-mentioned prior art. To this end, the present invention proposes a preparation method and application of hard carbon anode materials.
  • the hard carbon anode materials produced by the preparation method have a reversible capacity of no less than 350 mAh/g and excellent cycle stability and first Coulombic efficiency.
  • a preparation method of hard carbon negative electrode material including the following steps:
  • the starch is sintered for the first time, crushed, air and nitrogen are introduced for the second sintering, and porous hard block particles are obtained;
  • Air and nitrogen are introduced for the second sintering: the oxygen concentration in the air is about 20.7%. After compression by the air compressor, the oxygen concentration is about 16%.
  • the nitrogen and air introduced at the same time here are to dilute the air.
  • the oxygen concentration is controlled, so that the oxygen concentration is controllable.
  • the oxygen concentration is controlled within a suitable range, on the one hand, it is to improve the safety issues during the sintering process, and on the other hand, it is to introduce oxygen molecules so that the oxygen molecules can fully react. Part of the molecule reacts with carbon to form oxygen-containing functional groups as active sites. At the same time, another part of the oxygen reacts with part of the carbon to generate CO and CO 2 , forming pores on the surface and inside the material. This pore helps to store sodium ions and improves the electrochemistry of the material. performance.
  • the starch is at least one of corn starch, mung bean starch, potato starch, wheat starch, tapioca starch or lotus root starch.
  • the first sintering atmosphere is a nitrogen atmosphere.
  • the temperature of the first sintering is 180-240°C, and the time of the first sintering is 8-48 hours.
  • the first sintering is in a nitrogen atmosphere, which breaks the hydrogen bonds between the glucose chains in the starch, generates ether bonds, and undergoes a cross-linking reaction to stabilize its chemical structure, so that the hard solid solid will not undergo pyrolysis and expansion at higher temperatures. .
  • the oxygen volume content of the second sintering is 4 to 10%.
  • the temperature of the second sintering is 200-250°C, and the time of the second sintering is 3-12 hours.
  • the second sintering is under aerobic conditions:
  • oxygen molecules fully react with the material to form oxygen-containing functional groups as active sites.
  • oxygen reacts with part of the carbon to generate CO and CO 2 , forming pores on the surface and inside the material, which help to store sodium ions. Thereby improving the electrochemical performance of the material.
  • the porous hard block particles are broken into particles with a particle size Dv50 of 5 to 6 ⁇ m.
  • the temperature of the third sintering is 400-500°C, and the time of the third sintering is 2-4 hours.
  • the atmosphere for the third sintering is nitrogen atmosphere.
  • the porous hard block solid is aromaticized.
  • the temperature of the fourth sintering is 1200-1400°C, and the time of the fourth sintering is 2-4 hours.
  • the fourth sintering atmosphere is a nitrogen atmosphere.
  • the oxygen-containing functional groups and bound water of the hard carbon material can be removed to further rearrange the structure and reduce the diameter and specific surface area of the pores caused by low-oxygen sintering, because excessive pores and specific surface area will cause The formation of excessive SEI film reduces the first Coulombic efficiency.
  • the particle size Dv50 of the hard carbon negative electrode material is 4 to 6 ⁇ m, and the Dv90 is 9 to 12 ⁇ m.
  • a hard carbon negative electrode material is prepared by the above method, and the hard carbon negative electrode material has a reversible capacity of not less than 330mAh/g.
  • the main component of the hard carbon negative electrode material is C, which is a kind of amorphous carbon and is difficult to graphitize at high temperatures above 2500°C.
  • its shape is block-shaped particles with rounded edges.
  • the hard carbon negative electrode material has a specific surface area of 0.8 to 1.2 m 2 /g, a Dv50 of 4 to 6 ⁇ m, and a Dv90 of 9 to 12 ⁇ m.
  • a sodium ion battery includes the hard carbon negative electrode material prepared by the above preparation method.
  • the sodium ion battery further includes sodium carboxymethyl cellulose, a conductive agent, and an adhesive.
  • the conductive agent is acetylene black.
  • the binder is polyvinylidene fluoride.
  • the present invention uses starch as the raw material of the hard carbon negative electrode material. After four sinterings, the hydrogen bonds between the glucose chains in the starch are first broken to generate ether bonds and a cross-linking reaction occurs; and then the third step is carried out in an oxygen-containing atmosphere. During secondary sintering, oxygen molecules fully react with the material to form oxygen-containing functional groups as active sites. At the same time, oxygen reacts with part of the carbon to generate CO and CO 2 , and pores are formed on the surface and inside of the material. This pore helps to store sodium ions, thus Improve the electrochemical performance of the material; continue with the third sintering to aromatize the porous hard solid solid.
  • the hard carbon negative electrode material prepared by the present invention has a reversible capacity of no less than 330 mAh/g and a first Coulombic efficiency of no less than 88%.
  • the multi-stage sintering method of the present invention prepares high-performance hard carbon materials.
  • the synthesis method is simple and easy to operate.
  • the raw material is starch, which comes from a wide range of sources. The price is cheaper than commonly used sugar and cellulose raw materials.
  • Figure 1 is an SEM image of the hard carbon negative electrode material prepared in Example 1 of the present invention.
  • Figure 2 is a pore size distribution diagram of the hard carbon negative electrode material prepared in Example 1 of the present invention.
  • Figure 3 is an XRD pattern of the hard carbon negative electrode material prepared in Example 1 of the present invention.
  • Figure 4 is a charge-discharge curve of the hard carbon negative electrode material in Example 2 of the present invention.
  • the hard carbon negative electrode material of Example 1, sodium carboxymethyl cellulose, acetylene black conductive agent, and PVDF (polyvinylidene fluoride) adhesive were dissolved in deionized water in a mass ratio of 95:2:1:2. Prepare a slurry in water, and then apply it on the copper foil to obtain the pole piece. The pole piece is then dried in a drying oven at 80°C for 8 hours. Finally, the button battery is assembled in a glove box filled with argon atmosphere. The electrolytic The liquid is NaClO 4 dissolved in ethylene carbonate and propylene carbonate with a volume ratio of 1:1, and sodium metal foil is used as the counter electrode and reference electrode.
  • Figure 1 is a scanning electron microscope image of the hard carbon negative electrode material of Example 1. It can be seen from the figure that the morphology of the material is block-shaped particles with relatively rounded edges.
  • Figure 2 is a pore size distribution diagram of the hard carbon negative electrode material of Example 1. It can be seen from the figure that the pore width in the material is concentrated below 3nm.
  • Figure 3 is an XRD pattern of the hard carbon negative electrode material of Example 1. It can be seen from the figure that the half-peak width of the diffraction peak (002) is larger and the angle is smaller, indicating that the material has higher disorder and larger interlayer spacing.
  • the hard carbon negative electrode material of Example 2 sodium carboxymethyl cellulose, acetylene black conductive agent, and PVDF (polyvinylidene fluoride) adhesive were dissolved in deionized water in a mass ratio of 95:2:1:2. Prepare a slurry in water, and then apply it on the copper foil to obtain the pole piece. The pole piece is then dried in a drying oven at 80°C for 8 hours. Finally, the button battery is assembled in a glove box filled with argon atmosphere. The electrolytic The liquid is NaClO 4 dissolved in ethylene carbonate and propylene carbonate with a volume ratio of 1:1, and sodium metal foil is used as the counter electrode and reference electrode.
  • Figure 4 is a charge-discharge curve of the hard carbon negative electrode material in Example 2 of the present invention. It can be seen from the figure that the charge specific capacity of the material is as high as 336.7mAh/g, and the first efficiency is as high as 88.19%, indicating that the hard carbon anode material prepared in Example 2 has high reversible capacity and first efficiency.
  • the hard carbon negative electrode material of Example 3 sodium carboxymethylcellulose, acetylene black conductive agent, and PVDF (polyvinylidene fluoride) adhesive were dissolved in deionized water in a mass ratio of 95:2:1:2. Prepare a slurry in water, and then apply it on the copper foil to obtain the pole piece. The pole piece is then dried in a drying oven at 80°C for 8 hours. Finally, the button battery is assembled in a glove box filled with argon atmosphere. The electrolytic The liquid is NaClO 4 dissolved in ethylene carbonate and propylene carbonate with a volume ratio of 1:1, and sodium metal foil is used as the counter electrode and reference electrode.
  • the preparation method of the hard carbon negative electrode material in this comparative example includes the following steps:
  • Example 1 Dissolve the hard carbon material, sodium carboxymethyl cellulose, acetylene black conductive agent, and PVDF (polyvinylidene fluoride) adhesive in Example 1 in deionized water in a ratio of 95:2:1:2 to form a slurry. The material is then coated on the copper foil, and the pole piece is placed in a drying oven and dried at 80°C for 8 hours. Finally, the button cell was assembled in a glove box filled with argon atmosphere. The electrolyte used was NaClO 4 dissolved in ethylene carbonate and propylene carbonate with a volume ratio of 1:1. Sodium metal foil served as counter and reference electrodes.
  • Example 2 Dissolve the hard carbon material, sodium carboxymethyl cellulose, acetylene black conductive agent, and PVDF (polyvinylidene fluoride) adhesive in Example 2 in deionized water in a ratio of 95:2:1:2 to form a slurry. The material is then coated on the copper foil, and the pole piece is placed in a drying oven and dried at 80°C for 8 hours. Finally, the button cell was assembled in a glove box filled with argon atmosphere. The electrolyte used was NaClO 4 dissolved in ethylene carbonate and propylene carbonate with a volume ratio of 1:1. Sodium metal foil served as counter and reference electrodes.
  • Table 1 is a comparison of the specific surface area of the samples prepared in Examples 1, 2, 3 and Comparative Examples 1 and 2. It is found that as the oxygen content increases during the sintering process, the specific surface area of the material increases slightly, while the carbonization process changes the material. The structure is rearranged, the pores are filled, and the specific surface area is reduced. In Comparative Example 1, the specific surface area was too large because the carbon material was not aromatized and carbonized. Comparative Example 2 did not perform aerobic sintering, resulting in a very low specific surface area of the hard carbon material.
  • Table 2 is a comparison of the electrochemical properties of the samples prepared in Examples 1, 2, 3 and Comparative Examples 1 and 2. It is found that as the oxygen content increases during the sintering process, the specific capacity and first effect of the prepared materials increase. Increase, but excessive specific surface area leads to a large increase in SEI film, which will lead to a reduction in specific capacity and first effect.
  • Example 1 331.2 85.75
  • Example 2 336.7 88.19
  • Example 3 337.1 86.29 Comparative example 1 269.2 66.12 Comparative example 2 285.3 74.69

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Abstract

一种硬碳负极材料的制备方法和应用，该制备方法包括以下步骤：将淀粉进行第一次烧结，破碎，通入空气和氮气进行第二次烧结，得到多孔硬块颗粒；将多孔硬块颗粒，进行第三次烧结，继续升温，进行第四次烧结，得到硬碳负极材料。制备的硬碳负极材料具有不低于330mAh/g的可逆容量以及优异的循环稳定性和首次库伦效率。

Description

硬碳负极材料的制备方法和应用 技术领域
本发明属于钠离子电池材料技术领域，具体涉及硬碳负极材料的制备方法和应用。
背景技术
随着新能源车的普及，锂离子电池的消耗量急剧增加，随之作为锂电池中重要资源的镍钴锰等也逐渐短缺，价格逐步提升。为了能够缓解矿产资源发掘的压力，拥有和锂电池相类似的充放电机理的钠离子电池再度引起人们的关注。钠盐遍布全球各地，可以有效缓解镍钴锰资源不足带来的压力。而作为锂离子电池中常用的负极石墨却并不适用于钠离子电池，因为钠离子直径大于锂离子直径，无法在石墨层间进行脱嵌。另外，钠离子无法和石墨形成稳定的相结构。作为钠离子电池的其他负极材料也同期被研究，包括石墨化硬碳、合金、氧化物和有机复合物等。然而目前大部分负极材料都会在钠离子嵌入过程中产生很大的体积膨胀，导致不可逆的容量衰减。
发明内容
本发明旨在至少解决上述现有技术中存在的技术问题之一。为此，本发明提出硬碳负极材料的制备方法和应用，该制备方法制得的硬碳负极材料具有不低于350mAh/g的可逆容量以及优异的循环稳定性和首次库伦效率。
为实现上述目的，本发明采用以下技术方案：
一种硬碳负极材料的制备方法，包括以下步骤：
(1)将淀粉进行第一次烧结，破碎，通入空气和氮气进行第二次烧结，得到多孔硬块颗粒；
(2)将所述多孔硬块颗粒，进行第三次烧结，继续升温，进行第四次烧结，得到硬碳负极材料。
通入空气和氮气进行第二次烧结：空气中的氧浓度在20.7％左右，经过空压机压缩后，氧浓度含量在16％左右，此处同时通入的氮气与空气是为了稀释空气中的氧浓度，从而使氧浓度可控，当氧浓度控制在一个合适的范围内，一方面是为了提高烧结过程中的安全性问题，另一方面是引入氧分子，使氧分子充分反应，氧分子一部分与碳反应形成含氧官能团作为活性位点，同时另一部分氧与部分碳反应生成CO和CO 2使得材料表面及内部形成孔隙，该孔隙有助于钠离子的储存从而提升材料的电化学性能。
优选地，步骤(1)中，所述淀粉为玉米淀粉、绿豆淀粉、马铃薯淀粉、小麦淀粉、木薯淀粉或莲藕淀粉中的至少一种。
优选地，步骤(1)中，所述第一次烧结的气氛为氮气气氛。
优选地，步骤(1)中，所述第一次烧结的温度为180～240℃，第一次烧结的时间为8～48h。
第一次烧结是在氮气的气氛下，使淀粉中的葡萄糖链间氢键断裂，生成醚键，发生交联反应，稳定其化学结构，使硬块固体在更高温时不会发生热解膨胀现象。
优选地，步骤(1)中，所述第二次烧结的氧体积含量为4～10％。
优选地，步骤(1)中，所述第二次烧结的温度为200～250℃，第二次烧结的时间为3～12h。
第二次烧结是在有氧的条件下：
2C+O 2＝2CO；
C+O 2＝CO 2。
第二次烧结过程中氧分子与物料充分反应，形成含氧官能团作为活性位点，同时氧与部分碳反应生成CO和CO 2，材料表面及内部形成孔隙，该孔隙有助于钠离子的储存从而提升材料的电化学性能。
优选地，步骤(2)中，所述第三次烧结前还包括将多孔硬块颗粒破碎至粒径Dv50为5～6μm的颗粒。
优选地，步骤(2)中，所述第三次烧结的温度为400～500℃，第三次烧结的时间为2～4h。
优选地，步骤(2)中，所述第三次烧结的气氛为氮气气氛。
第三次烧结过程中，使得多孔硬块固体芳环化。
优选地，步骤(2)中，所述第四次烧结的温度为1200～1400℃，第四次烧结的时间为2～4h。
优选地，步骤(2)中，所述第四次烧结的气氛为氮气气氛。
第四次烧结过程中，可以除去硬碳材料的含氧官能团及结合水，让结构进一步重排，缩小低氧烧结时造成的孔隙的直径和比表面积，因为过大的孔隙和比表面积会致使过多SEI膜的形成从而降低首次库伦效率。
优选地，步骤(2)中，所述硬碳负极材料的粒径Dv50为4～6μm，Dv90为9～12μm。
一种硬碳负极材料，由上述方法制得，且所述硬碳负极材料具有不低于330mAh/g 的可逆容量。
优选地，所述硬炭负极材料的主要成分是C，是无定形碳中的一种，是在2500℃以上的高温下都难以石墨化，同时它的形貌呈边缘圆滑的块状颗粒。
优选地，所述硬碳负极材料的比表面积为0.8～1.2m 2/g，Dv50为4～6μm，Dv90为9～12μm。
一种钠离子电池，包括上述的制备方法制得的硬碳负极材料。
优选地，所述钠离子电池还包括羧甲基纤维素钠、导电剂、粘接剂。
进一步优选地，所述导电剂为乙炔黑。
进一步优选地，所述粘结剂为聚偏氟乙烯。
相对于现有技术，本发明的有益效果如下：
(1)本发明以淀粉作为硬碳负极材料的原料，经过四次烧结，先将淀粉中的葡萄糖链间氢键断裂，生成醚键，发生交联反应；再在含氧的气氛中进行第二次烧结，氧分子与物料充分反应，形成含氧官能团作为活性位点，同时氧与部分碳反应生成CO和CO 2，材料表面及内部形成孔隙，该孔隙有助于钠离子的储存，从而提升材料的电化学性能；再继续进行第三次烧结，使得多孔硬块固体芳环化，最后，第四次烧结过程中除去硬碳材料的含氧官能团及结合水，让结构进一步重排，缩小低氧烧结时造成的孔隙的直径和比表面积，提高首次库伦效率。本发明制备的硬碳负极材料具有不低于330mAh/g的可逆容量以及不低于88％的首次库伦效率。
(2)本发明多级烧结的方法制备出高性能的硬碳材料，其合成方法简单易操作，原料为淀粉，来源广，价格比现在常用的糖类及纤维素类原料便宜。
附图说明
图1为本发明实施例1制得的硬碳负极材料的SEM图；
图2为本发明实施例1制得的硬碳负极材料的孔径分布图；
图3为本发明实施例1制得的硬碳负极材料的XRD图；
图4为本发明实施例2的硬炭负极材料的充放电曲线图。
具体实施方式
以下将结合实施例对本发明的构思及产生的技术效果进行清楚、完整地描述，以充分地理解本发明的目的、特征和效果。显然，所描述的实施例只是本发明的一部分实施例，而不是全部实施例，基于本发明的实施例，本领域的技术人员在不付出创造性劳动的前提下所获得的其他实施例，均属于本发明保护的范围。
实施例1
本实施例的硬碳负极材料的制备方法，包括以下步骤：
(1)称取500g玉米淀粉置于氮气气氛下的220℃低温炉内进行第一次烧结8h，发生交联反应，获得硬块固体；
(2)将硬块固体破碎，置于通入氮气和压缩空气的205℃的低温炉内进行第二次烧结12h，维持炉内的氧含量在5％，得到多孔黑色颗粒；
(3)将多孔黑色颗粒破碎至Dv50为5～6μm的粉末，置于氮气气氛下，先在400℃下进行第三次烧结2h，再升高温度至1400℃进行第四次烧结2h，得到硬碳负极材料。
将实施例1的硬碳负极材料、羧甲基纤维素钠、乙炔黑导电剂、PVDF(聚偏氟乙烯)粘接剂以质量比为95:2:1:2的配比溶于去离子水中配成浆料，然后涂布在铜箔上，得到极片，再将极片放于80℃的干燥箱中干燥8h，最后在充满氩气气氛的手套箱中组装扣式电池，所用电解液为NaClO 4溶于体积比为1:1的碳酸乙烯酯和碳酸丙烯酯制成，钠金属箔作为对电极和参比电极。
图1为实施例1的硬碳负极材料的扫描电镜图。从图中可以看出材料形貌呈边缘较为圆滑的块状颗粒。
图2为实施例1的硬碳负极材料的孔径分布图。从图中可以看出材料中孔隙宽度集中在3nm以下。
图3为实施例1的硬碳负极材料的XRD图。从图中可以看出衍射峰(002)半峰宽较大，角度偏小，说明材料无序度较高，层间距较大。
实施例2
本实施例的硬碳负极材料的制备方法，包括以下步骤：
(1)称取500g玉米淀粉置于氮气气氛下的220℃低温炉内进行第一次烧结8h，发生交联反应，获得硬块固体；
(2)将硬块固体破碎，置于通入氮气和压缩空气的205℃的低温炉内进行第二次烧结12h，维持炉内的氧含量在7％，得到多孔黑色颗粒；
(3)将多孔黑色颗粒破碎至Dv50为5～6μm的粉末，置于氮气气氛下，先在400℃下进行第三次烧结2h，再升高温度至1400℃进行第四次烧结2h，得到硬碳负极材料。
将实施例2的硬碳负极材料、羧甲基纤维素钠、乙炔黑导电剂、PVDF(聚偏氟乙烯)粘接剂以质量比为95:2:1:2的配比溶于去离子水中配成浆料，然后涂布在铜箔上，得到极片，再将极片放于80℃的干燥箱中干燥8h，最后在充满氩气气氛的手套箱中组 装扣式电池，所用电解液为NaClO 4溶于体积比为1:1的碳酸乙烯酯和碳酸丙烯酯制成，钠金属箔作为对电极和参比电极。
图4为本发明实施例2的硬炭负极材料的充放电曲线图。从图中可以得出材料的充电比容量高达336.7mAh/g，首效高达88.19％，说明实施例2制备的硬碳负极材料具备较高的可逆容量和首效。
实施例3
本实施例的硬碳负极材料的制备方法，包括以下步骤：
(1)称取500g玉米淀粉置于氮气气氛下的220℃低温炉内进行第一次烧结8h，发生交联反应，获得硬块固体；
(2)将硬块固体破碎，置于通入氮气和压缩空气的205℃的低温炉内进行第二次烧结12h，维持炉内的氧含量在9％，得到多孔黑色颗粒；
(3)将多孔黑色颗粒破碎至Dv50为5～6μm的粉末，置于氮气气氛下，先在400℃下进行第三次烧结2h，再升高温度至1400℃进行第四次烧结2h，得到硬碳负极材料。
将实施例3的硬碳负极材料、羧甲基纤维素钠、乙炔黑导电剂、PVDF(聚偏氟乙烯)粘接剂以质量比为95:2:1:2的配比溶于去离子水中配成浆料，然后涂布在铜箔上，得到极片，再将极片放于80℃的干燥箱中干燥8h，最后在充满氩气气氛的手套箱中组装扣式电池，所用电解液为NaClO 4溶于体积比为1:1的碳酸乙烯酯和碳酸丙烯酯制成，钠金属箔作为对电极和参比电极。
对比例1(不进行第三和第四次烧结)
本对比例的硬碳负极材料的制备方法，包括以下步骤：
(1)称取500g玉米淀粉置于氮气气氛下的220℃低温炉内进行第一次烧结8h，发生交联反应，获得硬块固体；
(2)将硬块固体破碎，置于通入氮气和压缩空气的205℃的低温炉内进行第二次烧结12h，维持炉内的氧含量在5％，得到硬碳负极材料。
将对比例1的硬碳材料、羧甲基纤维素钠、乙炔黑导电剂、PVDF(聚偏氟乙烯)粘接剂以95:2:1:2的配比溶于去离子水中配成浆料，然后涂布在铜箔上，极片放于干燥箱中在80℃下干燥8h。最后在充满氩气气氛的手套箱中组装扣式电池，所用电解液为NaClO 4溶于体积比为1:1的碳酸乙烯酯和碳酸丙烯酯制成。钠金属箔作为对电极和参比电极。
对比例2(不进行有氧烧结)
本实施例的硬碳负极材料的制备方法，包括以下步骤：
(1)称取500g玉米淀粉置于氮气气氛下的220℃低温炉内烧结8h，发生交联反应，获得硬块固体；
(2)将硬块固体破碎至Dv50为5～6μm的粉末，置于氮气气氛下，先在400℃下进行第二次烧结2h，再升高温度至1400℃进行第三次烧结2h，得到硬碳负极材料。
将对比例2的硬碳材料、羧甲基纤维素钠、乙炔黑导电剂、PVDF(聚偏氟乙烯)粘接剂以95:2:1:2的配比溶于去离子水中配成浆料，然后涂布在铜箔上，极片放于干燥箱中在80℃下干燥8h。最后在充满氩气气氛的手套箱中组装扣式电池，所用电解液为NaClO 4溶于体积比为1:1的碳酸乙烯酯和碳酸丙烯酯制成。钠金属箔作为对电极和参比电极。
理化性能：
表1为实施例1、2、3与对比例1、2制备的样品的比表面积对比，发现随着烧结过程中氧含量的增加，材料的比表面积有稍许的提高，而碳化过程对材料进行结构重排，填补了孔隙，缩小了比表面积。对比例1由于没有使碳材料芳环化和碳化，使得比表面积过大。对比例2由于没有进行有氧烧结，导致硬碳材料的比表面积很低。
表1实施例1-3和对比例1-2制备的硬碳材料的比表面积测试数据
样品 比表面积(m 2/g)
实施例1 0.83
实施例2 1.02
实施例3 1.17
对比例1 18.16
对比例2 0.15
电化学性能：
表2为实施例1、2、3与对比例1、2制备的样品的电化学性能对比，发现，随着烧结过程中氧含量的增加，所制备的材料的比容量及首效均有所升高，但比表面积过大导致SEI膜的大量增加，会导致比容量及首效的降低。
表2实施例1-3和对比例1-2制备的硬碳材料的电化学性能测试数据
样品 充电比容量(mAh g -1) 库伦效率(％)
实施例1 331.2 85.75
实施例2 336.7 88.19
实施例3 337.1 86.29
对比例1 269.2 66.12
对比例2 285.3 74.69
本发明不限于上述实施例，在所属技术领域普通技术人员所具备的知识范围内，还可以在不脱离本发明宗旨的前提下作出各种变化。此外，在不冲突的情况下，本发明的实施例及实施例中的特征可以相互组合。

Claims (10)

  1. 一种硬碳负极材料的制备方法，其特征在于，包括以下步骤：
    (1)将淀粉进行第一次烧结，破碎，通入空气和氮气进行第二次烧结，得到多孔硬块颗粒；
    (2)将所述多孔硬块颗粒，进行第三次烧结，继续升温，进行第四次烧结，得到硬碳负极材料。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述淀粉为玉米淀粉、绿豆淀粉、马铃薯淀粉、小麦淀粉、木薯淀粉或莲藕淀粉中的至少一种。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述第一次烧结的温度为180～240℃，第一次烧结的时间为8～48h。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述第二次烧结的气氛中的氧体积含量为4～10％。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤(1)中，所述第二次烧结的温度为200～250℃，第二次烧结的时间为3～12h。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤(2)中，所述第三次烧结的温度为400～500℃，第三次烧结的时间为2～4h；所述第三次烧结的气氛为氮气气氛。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤(2)中，所述第四次烧结的温度为1200～1400℃，第四次烧结的时间为2～4h。
  8. 一种硬碳负极材料，其特征在于，是由权利要求1-7任一项所述的制备方法制备得到，且所述硬碳负极材料具有不低于330mAh/g的可逆容量。
  9. 根据权利要求8所述的硬碳负极材料，其特征在于，所述硬碳负极材料的比表面积为0.8～1.2m 2/g，Dv50为4～6μm，Dv90为9～12μm。
  10. 一种钠离子电池，其特征在于，包括权利要求8-9任一项所述的硬碳负极材料。
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