WO2023050466A1 - 一种生物质炭制备锂/钠离子电池硬碳负极的方法 - Google Patents

一种生物质炭制备锂/钠离子电池硬碳负极的方法 Download PDF

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WO2023050466A1
WO2023050466A1 PCT/CN2021/123168 CN2021123168W WO2023050466A1 WO 2023050466 A1 WO2023050466 A1 WO 2023050466A1 CN 2021123168 W CN2021123168 W CN 2021123168W WO 2023050466 A1 WO2023050466 A1 WO 2023050466A1
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biomass charcoal
negative electrode
hard carbon
lithium
preparing
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PCT/CN2021/123168
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French (fr)
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陈永
郑恒
莫言
曹博凯
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海南大学
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Priority to US17/595,274 priority Critical patent/US20240043276A1/en
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • 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
    • 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
    • H01M4/36—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
    • C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
    • 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
    • C01P2006/40—Electric properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
    • 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

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  • the present application relates to the field of biological materials, in particular to a method for preparing a hard carbon negative electrode of a lithium/sodium ion battery from biomass charcoal.
  • the present application proposes a method for preparing a hard carbon negative electrode of a lithium/sodium ion battery by using biomass charcoal to solve the above problems.
  • Biochar pretreatment Add hydrochloric acid to pickle the modified biomass charcoal for 3-12 hours, and then wash it with deionized water until neutral; there are residual biomass and impurities in the biomass charcoal, which need to be pickled Step removal, the biomass after pickling retains hydrochloric acid, and needs to be washed with a large amount of deionized water to achieve the purpose of adjusting pH and removing impurities;
  • the modified biochar is obtained by immersing the biochar in the modifying solution for 0.2 to 2.5 hours at 20 to 40°C, and then drying at 150 to 200°C to obtain the modified biochar , the biochar is soaked in the modified solution to make the cellulose swell and form fine pores.
  • the intramolecular crosslinking reaction of the biochar occurs, and the internal molecules undergo an aromatization reaction, continuously forming new carbon molecules, and at the same time improving
  • the liquid has a certain dehydration effect, and under high temperature drying, it is easy to make the hydrogen and oxygen elements in the biochar come out in the form of water, and activate the biochar.
  • the modifying solution is a solution of N-N dimethylformamide and metasemicarbazide hydrochloride in a volume ratio of 1-5:3.
  • the concentration of hydrochloric acid in the S1 is 0.5-1.5M.
  • the mass volume ratio g/mL of biochar and hydrochloric acid in the S1 is 1:0.077-0.13.
  • the mass volume ratio g/mL of biochar and absolute ethanol in the S2 is 0.6-1.3:3-5.
  • the rotation speed of the ball mill in S2 is 200-500 rpm, and the ball milling time is 3-12 hours.
  • the heating program of the tubular furnace in S3 is 30-1000°C: the heating rate is 4-6°C/min, 1000-1300°C: the heating rate is 3-5°C/min, the heating rate should not be too high, otherwise It is easy to cause damage to the internal structure.
  • the cooling rate of the tube furnace in S3 is 3-5°C/min, and the temperature of the product is kept to drop slowly, otherwise, cracks will appear inside the product and performance will be reduced.
  • This application utilizes biomass charcoal to prepare the method of lithium/sodium ion battery hard carbon negative electrode, optimizes the process treatment, modifies the biomass charcoal, conducts pyrolytic carbonization after activation of the biomass charcoal, adds argon gas for treatment, and sets the carbonization temperature and carbonization Time, control the cooling rate, so that the obtained biomass carbon forms amorphous carbon after carbonization, with low degree of graphitization, less surface defects, larger charge-discharge specific capacity, and stable performance during cycle charge-discharge; at the same time, this
  • the application process is relatively simple, reducing special complex processes, and does not require special control of the shape, which is suitable for large-scale industrial production; the product performance is relatively good, and it has certain competitive advantages.
  • Fig. 1 is the Raman figure in embodiment 3;
  • Fig. 2 is the long cycle charge and discharge capacity in embodiment 3;
  • Fig. 3 is the XRD pattern among the embodiment 3;
  • FIG. 4 is the voltage-capacity diagram of the first three turns in Example 3.
  • a method for preparing lithium/sodium ion battery hard carbon negative electrode by biochar comprising the following steps:
  • Biochar pretreatment add 0.5M hydrochloric acid to the modified biochar and pickle for 3 hours.
  • the mass volume ratio of biochar to hydrochloric acid g/mL is 1:0.077, and then wash with deionized water until neutral ;
  • the modified biochar is to impregnate the biochar in the modified solution, the modified solution is a N-N dimethylformamide and m-semicarbazide hydrochloride solution with a volume ratio of 1:3, at 20 ° C Immersed for 0.2h, and then dried at 150°C to obtain modified biochar;
  • a method for preparing lithium/sodium ion battery hard carbon negative electrode by biochar comprising the following steps:
  • Biochar pretreatment add 1.5M hydrochloric acid to the modified biochar and pickle for 12 hours.
  • the mass volume ratio of biochar to hydrochloric acid g/mL is 1:0.13, and then wash with deionized water until neutral ;
  • the modified biochar is to impregnate the biochar in the modified solution, the modified solution is a N-N dimethylformamide and m-semicarbazide hydrochloride solution with a volume ratio of 5:3, at 40 ° C Immersed for 2.5 hours, and then dried at 200 ° C to obtain modified biochar;
  • Preparation of precursor material pour the above washed biochar into a stainless steel ball mill tank and add absolute ethanol for dry ball milling.
  • the mass-to-volume ratio of biochar to absolute ethanol g/mL is 1.3:5, and the speed of the ball mill is 500rpm, ball milling time is 12h;
  • a method for preparing lithium/sodium ion battery hard carbon negative electrode by biochar comprising the following steps:
  • Biochar pretreatment add 1M hydrochloric acid to the modified biochar and pickle for 8 hours, the mass volume ratio of biochar to hydrochloric acid g/mL is 1:0.12, and then wash with deionized water until neutral;
  • the modified biochar is to impregnate the biochar in the modification solution, the modification solution is N-N dimethylformamide and m-semicarbazide hydrochloride solution with a volume ratio of 4:3, at 30°C Immerse for 1.3h, then dry at 180°C to obtain modified biochar;
  • biomass charcoal is not modified, specifically a method for preparing a hard carbon negative electrode of a lithium/sodium ion battery from biomass charcoal, comprising the following steps:
  • Biochar pretreatment add 1M hydrochloric acid to the biochar and pickle it for 8 hours, the mass volume ratio of biochar to hydrochloric acid g/mL is 1:0.12, and then wash it with deionized water until neutral;
  • Example 3 0.64 196.0
  • Example 4 0.72 170.4
  • the biomass carbon has generated amorphous carbon after carbonization, wherein, as can be seen from Figure 1, the appearance of the two carbon material characteristic peaks of D peak and G peak in Example 3 indicates that the material is transformed from pure biomass to For carbon materials, the I D / I G value of Example 3 is 0.64, which shows that the degree of graphitization of the generated material is very low, which proves the intrinsic amorphous characteristics and non-crystallization properties of hard carbon; as can be seen from Figure 2, after 100 cycles The capacitance is 196.0mAh ⁇ g -1 , indicating that the performance is stable during the cycle charge and discharge process;
  • Example 3 Comparing Example 3 with Examples 1-2, it is shown that carbonization temperature and carbonization time have a greater impact on the biomass carbon. Compared with Example 4, the activation effect of the biomass carbon modified by the present application is obvious, and the degree of graphitization Lower, less surface defects.
  • Example 3 The hard carbon negative electrode material prepared in Example 3 was characterized by XRD, and the type and content of the phase were analyzed from FIG. 3 to produce a pure phase.

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  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
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Abstract

本申请提供一种生物质炭制备锂/钠离子电池硬碳负极的方法，包括以下步骤：S1生物质炭预处理、S2制备前驱体材料、S3热解炭化，经生物质炭的改性，设置炭化温度和炭化时间，控制降温速率，使得到的生物质碳在碳化后生成了无定形碳，石墨化程度低，表面缺陷少，具有更大的充放电比容量，循环充放电过程中性能稳定；同时，本申请工艺相对简单，减少特殊的复杂工艺，无需对形貌做特殊调控，适合大规模工业化生产；产品性能相对较好，具备一定竞争优势。

Description

一种生物质炭制备锂/钠离子电池硬碳负极的方法 技术领域
本申请涉及生物材料领域，特别涉及一种生物质炭制备锂/钠离子电池硬碳负极的方法。
背景技术
近年来，手机、平板电脑、笔记本电脑等便携式电子产品的快速发展，以及新能源电动汽车的不断普及，对能量存储系统的需求在不断提高。石墨作为锂离子电池负极材料，因其具有稳定性好、循环寿命长等优点，被广泛使用。然而，由于石墨的理论比容量仅为372mAh/g，使石墨负极材料已无法满足对高能量密度和功率密度日益增长的需求；并且通过包覆等工艺获得的包覆石墨负极材料在长循环稳定性上表现稍差；生物质炭由多种天然原材料热解而成，微观结构由石墨片层无序堆叠而成，是一款较好的制备负极材料的原材料，但是目前方法制得的炭负极材料形貌不规整，表面缺陷多，电容量小，长循环充放电过程中性能欠佳，存在制备方法时间长、步骤繁琐等缺点，导致成本高。
发明内容
鉴以此，本申请提出一种生物质炭制备锂/钠离子电池硬碳负极的方法，来解决上述问题。
本申请的技术方案是这样实现的：一种生物质炭制备锂/钠离子电池硬碳负极的方法，包括以下步骤：
S1、生物质炭预处理：将改性后的生物质炭添加盐酸酸洗3～12h，后用去离子水洗涤至中性；生物质碳中存在残留的生物质和杂质，需经过酸洗步骤脱除，酸洗后的生物质留存盐酸，需使用大量去离子水冲洗以达到调节pH和去除杂质的目的；
S2、制备前驱体材料：将上述水洗后的生物质炭倒入球磨罐加入无水乙醇球磨粉碎，球磨完成后过滤干燥得到前驱体材料；生物质材料需在不锈钢球磨罐内进行，球磨可分为湿法球磨和干法球磨；
S3、热解炭化：将上述获得的前驱体材料放置在管式炉中，在氩气氛围中进行炭化，炭化温度为1200～1300℃，炭化时间为0.5～3h，通气量为10～30mL/min，炭化结束后继续保温1～3h，降温至800～1100℃，继续通氩气自然冷却至25～30℃，得到硬碳负极材料；保温时间不宜过长，否则产品性能下降，过短则会造成碳化不完全，性能下降。
进一步的，所述改性生物质炭是将生物质炭浸渍于改性液中，在20～40℃下浸渍0.2～2.5h，再于150～200℃下干燥，制得改性生物质炭，生物质炭浸渍于改性液中使得纤维素溶胀，形成细微孔隙，在此过程中，生物质炭分子内交联反应，内部分子发生芳构化反应，不断形成新的碳分子，同时改性液具有一定的脱水作用在高温干燥下容易使得生物质炭中的氢和氧元素以水的形式脱出，将生物质炭活化。
进一步的，所述改性液为体积比为1～5:3的N-N二甲基甲酰胺和间氨基苯脲盐酸盐溶液。
进一步的，所述S1中盐酸浓度为0.5～1.5M。
进一步的，所述S1中生物质炭和盐酸的质量体积比g/mL为1：0.077～0.13。
进一步的，所述S2中生物质炭和无水乙醇的质量体积比g/mL为0.6～1.3:3～5。
进一步的，所述S2中球磨机转速为200～500rpm，球磨时间为3～12h。
进一步的，所述S3中管式炉升温程序为30-1000℃：升温速率为4～6℃/min，1000-1300℃：升温速率为3～5℃/min，升温速率不宜过高，否则容易造成内部结构破坏。
进一步的，所述S3中管式炉降温速率为3～5℃/min，保持产物温度缓慢下降，否则会造成产品内部出现裂纹，降低性能等现象。
与现有技术相比，本申请的有益效果是：
本申请利用生物质炭制备锂/钠离子电池硬碳负极的方法，优化工艺处理，将生物质炭进行改性，生物质炭活化后进行热解炭化，加入氩气处理，设置炭化温度和炭化时间，控制降温速率，使得到的生物质碳在碳化后生成了无定形碳，石墨化程度低，表面缺陷少，具有更大的充放电比容量，循环充放电过程中性能稳定；同时，本申请工艺相对简单，减少特殊的复杂工艺，无需对形貌做特殊调控，适合大规模工业化生产；产品性能相对较好，具备一定竞争优势。
附图说明
图1为实施例3中的Raman图；
图2为实施例3中的长循环充放电容量；
图3为实施例3中的XRD图；
图4为实施例3中的前三圈电压-容量图。
具体实施方式
为了更好理解本申请技术内容，下面提供具体实施例，对本申请做进一步的说明。
本申请实施例所用的实验方法如无特殊说明，均为常规方法。
本申请实施例所用的材料、试剂等，如无特殊说明，均可从商业途径得到。
实施例1
一种生物质炭制备锂/钠离子电池硬碳负极的方法，包括以下步骤：
S1、生物质炭预处理：将改性后的生物质炭添加0.5M盐酸酸洗3h，生物质炭和盐酸的质量体积比g/mL为1：0.077，后用去离子水洗涤至中性；所述改性生物质炭是将生物质炭浸渍于改性液中，改性液为体积比为1:3的N-N二甲基甲酰胺和间氨基苯脲盐酸盐溶液，在20℃下浸渍0.2h，再于150℃下干燥，制得改性生物质炭；
S2、制备前驱体材料：将上述水洗后的生物质炭倒入不锈钢球磨罐加入无水乙醇湿法球磨粉碎，生物质炭和无水乙醇的质量体积比g/mL为0.6:3，球磨机转速为200rpm，球磨时间为3h；
S3、热解炭化：将上述获得的前驱体材料放置在管式炉中，在氩气氛围中进行炭化，炭化温度为1200℃，炭化时间为0.5h，通气量为10mL/min，炭化结束后继续保温1h，其中管式炉升温程序为30-1000℃：升温速率为4℃/min，1000-1200℃：升温速率为3℃/min；降温至800℃，降温速率为3℃/min，继续通氩气自然冷却至25℃，得到硬碳负极材料。
实施例2
一种生物质炭制备锂/钠离子电池硬碳负极的方法，包括以下步骤：
S1、生物质炭预处理：将改性后的生物质炭添加1.5M盐酸酸洗12h，生物质炭和盐酸的质量体积比g/mL为1：0.13，后用去离子水洗涤至中性；所述改性生物质炭是将生物质炭浸渍于改性液中，改性液为体积比为5:3的N-N二甲基甲酰胺和间氨基苯脲盐酸盐溶液，在40℃下浸渍2.5h，再于200℃下干燥，制得改性生物质炭；
S2、制备前驱体材料：将上述水洗后的生物质炭倒入不锈钢球磨罐加入无水乙醇干法球磨粉碎，生物质炭和无水乙醇的质量体积比g/mL为1.3:5，球磨机转速为500rpm，球磨时间为12h；
S3、热解炭化：将上述获得的前驱体材料放置在管式炉中，在氩气氛围中进行炭化，炭化温度为1300℃，炭化时间为3h，通气量为30mL/min，炭化结束后继续保温3h，其中管式炉升温程序为30-1000℃：升温速率为6℃/min，1000-1300℃：升温速率为5℃/min；降温至1100℃，降温速率为5℃/min，继续通氩气自然冷却至30℃，得到硬碳负极材料。
实施例3
一种生物质炭制备锂/钠离子电池硬碳负极的方法，包括以下步骤：
S1、生物质炭预处理：将改性后的生物质炭添加1M盐酸酸洗8h，生物质炭和盐酸的质量体积比g/mL为1：0.12，后用去离子水洗涤至中性；所述改性生物质炭是将生物质炭浸渍于改性液中，改性液为体积比为4:3的N-N二甲基甲酰胺和间氨基苯脲盐酸盐溶液，在30℃下浸渍1.3h，再于180℃下干燥，制得改性生物质炭；
S2、制备前驱体材料：将上述水洗后的生物质炭倒入不锈钢球磨罐加入无水乙醇湿法球磨粉碎，生物质炭和无水乙醇的质量体积比g/mL为0.9:4，球磨机转速为400rpm，球磨时间为7h；
S3、热解炭化：将上述获得的前驱体材料放置在管式炉中，在氩气氛围中进行炭化，炭化温度为1250℃，炭化时间为2h，通气量为20mL/min，炭化结束后继续保温2h，其中管式炉升温程序为30-1000℃：升温速率为5℃/min，1000-1250℃：升温速率为4℃/min；降温至1000℃，降温速率为4℃/min，继续通氩气自然冷却至25～30℃，得到硬碳负极材料。
实施例4
本实施例与实施例3的区别在于，生物质炭未经改性，具体为一种生物质炭制备锂/钠离子电池硬碳负极的方法，包括以下步骤：
S1、生物质炭预处理：将生物质炭添加1M盐酸酸洗8h，生物质炭和盐酸的质量体积比g/mL为1：0.12，后用去离子水洗涤至中性；
S2、制备前驱体材料：将上述水洗后的生物质炭倒入不锈钢球磨罐加入无水乙醇湿法球磨粉碎，生物质炭和无水乙醇的质量体积比g/mL为0.9:4，球磨机转速为400rpm，球磨时间为7h；
S3、热解炭化：将上述获得的前驱体材料放置在管式炉中，在氩气氛围中进行炭化，炭化温度为1250℃，炭化时间为2h，通气量为20mL/min，炭化结束后继续保温2h，其中管式炉升温程序为30-1000℃：升温速率为5℃/min，1000-1250℃：升温速率为4℃/min；降温至1000℃，降温速率为4℃/min，继续通氩气自然冷却至25～30℃，得到硬碳负极材料。
一、性能测试
(1)将上述实施例1～4制得的硬碳负极材料经Raman进行性能测试，再经按1C＝400mA·g -1的电流，先恒流恒压放电至5mV，再恒流充电至1.5V，循环100圈进行恒电流性能测试，充放电100圈，测试得出电容量：
  I D/I G值 电容量(mAh·g -1)
实施例1 0.69 185.6
实施例2 0.70 180.3
实施例3 0.64 196.0
实施例4 0.72 170.4
由上述结果可知，生物质碳在碳化后生成了无定形碳，其中，由图1可知实施例3的D峰和G峰这两个碳材料特征峰的出现表明材料由单纯的生物质转变为碳材料，实施例3的I D/I G值为0.64表明了生成的材料石墨化程度很低，证明了硬碳本征的无定形特性与非晶化属性；从图2可知，循环100圈电容量196.0mAh·g -1，说明循环充放电过程中性能稳定；
实施例3与实施例1～2比较，说明碳化温度、碳化时间对该生物质碳的影响较大，与实施例4比较，经本申请改性后的生物质炭活化效果明显，石墨化程度较低，表面缺陷少。
(2)将实施例3制得的硬碳负极材料进行XRD表征，由图3分析该物相的种类与含量，产生纯相。
(3)将实施例3制得的硬碳负极材料测试电压-容量，由图4可知曲线比较平滑，说明该负极材料比较稳定。
以上所述仅为本申请的较佳实施例而已，并不用以限制本申请，凡在本申请的精神和原则之内，所作的任何修改、等同替换、改进等，均应包含在本申请的保护范围之内。

Claims (9)

  1. 一种生物质炭制备锂/钠离子电池硬碳负极的方法，其特征在于：包括以下步骤：
    S1、生物质炭预处理：将改性后的生物质炭添加盐酸酸洗3～12h，后用去离子水洗涤至中性；
    S2、制备前驱体材料：将上述水洗后的生物质炭倒入球磨罐加入无水乙醇球磨粉碎，球磨完成后过滤干燥得到前驱体材料；
    S3、热解炭化：将上述获得的前驱体材料放置在管式炉中，在氩气氛围中进行炭化，炭化温度为1200～1300℃，炭化时间为0.5～3h，通气量为10～30mL/min，炭化结束后继续保温1～3h，降温至800～1100℃，继续通氩气自然冷却至25～30℃，得到硬碳负极材料。
  2. 如权利要求1所述的一种生物质炭制备锂/钠离子电池硬碳负极的方法，其特征在于：所述改性生物质炭是将生物质炭浸渍于改性液中，在20～40℃下浸渍0.2～2.5h，再于150～200℃下干燥，制得改性生物质炭。
  3. 如权利要求2所述的一种生物质炭制备锂/钠离子电池硬碳负极的方法，其特征在于：所述改性液为体积比为1～5:3的N-N二甲基甲酰胺和间氨基苯脲盐酸盐溶液。
  4. 如权利要求1所述的一种生物质炭制备锂/钠离子电池硬碳负极的方法，其特征在于：所述S1中盐酸浓度为0.5～1.5M。
  5. 如权利要求1所述的一种生物质炭制备锂/钠离子电池硬碳负极的方法，其特征在于：所述S1中生物质炭和盐酸的质量体积比g/mL为1：0.077～0.13。
  6. 如权利要求1所述的一种生物质炭制备锂/钠离子电池硬碳负极的方法，其特征在于：所述S2中生物质炭和无水乙醇的质量体积比g/mL为0.6～1.3:3～5。
  7. 如权利要求1所述的一种生物质炭制备锂/钠离子电池硬碳负极的方法，其特征在于：所述S2中球磨机转速为200～500rpm，球磨时间为3～12h。
  8. 如权利要求1所述的一种生物质炭制备锂/钠离子电池硬碳负极的方法，其特征在于：所述S3中管式炉升温程序为30-1000℃：升温速率为4～6℃/min，1000-1300℃：升温速率为3～5℃/min。
  9. 如权利要求1所述的一种生物质炭制备锂/钠离子电池硬碳负极的方法，其特征在于：所述S3中管式炉降温速率为3～5℃/min。
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