WO2023213113A1 - 硅碳复合负极材料的制备方法及其应用 - Google Patents

硅碳复合负极材料的制备方法及其应用 Download PDF

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WO2023213113A1
WO2023213113A1 PCT/CN2023/077215 CN2023077215W WO2023213113A1 WO 2023213113 A1 WO2023213113 A1 WO 2023213113A1 CN 2023077215 W CN2023077215 W CN 2023077215W WO 2023213113 A1 WO2023213113 A1 WO 2023213113A1
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Prior art keywords
silicon
porous carbide
preparation
heating
negative electrode
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PCT/CN2023/077215
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English (en)
French (fr)
Inventor
冯茂华
李长东
吴星宇
阮丁山
刘宝烨
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Hunan Brunp Recycling Technology Co Ltd
Guangdong Brunp Recycling Technology Co Ltd
Hunan Bangpu Automobile Circulation Co Ltd
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Application filed by Hunan Brunp Recycling Technology Co Ltd, Guangdong Brunp Recycling Technology Co Ltd, Hunan Bangpu Automobile Circulation Co Ltd filed Critical Hunan Brunp Recycling Technology Co Ltd
Priority to GB2318194.4A priority Critical patent/GB2621289A/en
Priority to US18/686,455 priority patent/US12401026B2/en
Priority to ES202490006A priority patent/ES3010499A2/es
Priority to HU2400052A priority patent/HUP2400052A1/hu
Priority to DE112023000115.4T priority patent/DE112023000115B4/de
Publication of WO2023213113A1 publication Critical patent/WO2023213113A1/zh
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Definitions

  • the invention belongs to the technical field of lithium-ion batteries, and specifically relates to a preparation method and application of a silicon-carbon composite negative electrode material.
  • Silicon-based anode materials are an anode material with great commercial application prospects due to their abundant sources, low cost, high theoretical lithium storage capacity, and suitable delithiation voltage.
  • silicon will repeatedly shrink and expand during the process of removing/inserting lithium, which can easily cause the negative electrode sheet to lose electrical contact and cause the negative electrode sheet material to become deactivated, which may greatly reduce the application prospects of silicon-based negative electrode materials.
  • practical applications due to its larger specific surface area and the large number of defects and serious side reactions, practical applications also face problems such as low Coulombic efficiency in the first week, insufficient long-term cycle stability, and poor rate performance.
  • the effect of obtaining a silicon-carbon negative electrode material is to improve the diffusion of lithium ions and increase the transmission speed of electrons.
  • it is an effective means to solve the defects of silicon anode materials.
  • porous carbon materials not only have the properties of ordinary carbon materials, but also introduce a rich pore structure to provide space for silicon to expand. They have the advantages of high specific surface area, high contact area, controllable porous structure and easy modification. Therefore, how to optimize the structure of porous carbon materials and combine them with silicon-based anode materials to improve the performance of silicon-carbon anode materials is still a current problem.
  • 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 a silicon-carbon composite negative electrode material.
  • a preparation method of silicon-carbon composite negative electrode material including the following steps:
  • the hypercross-linked polymer is prepared as follows: under an inert atmosphere, mix benzene glycol compounds, solvents and cross-linking agents, cool, and then add a catalyst to mix, The resulting mixture is subjected to a heating reaction to obtain the hypercrosslinked polymer.
  • the benzenediol compound is at least one of terephthalenedimethanol, isophthalenedimethanol, o-phthaledimethanol, terephthalenediol, resorcinol or o-phenylatedethanol.
  • the solvent is at least one of tetrachloromethane, chloroform, ethyl chloride, dichloroethane, trichloroethane, chloropropane, dichloropropane, trichloropropane or tetrachloropropane.
  • the cross-linking agent is dimethyl formal.
  • the catalyst is ferric chloride.
  • step S1 the dosage ratio of the benzene glycol compound, solvent, catalyst and cross-linking agent is (5-10)g: (15-80)mL: (1.2- 6)g: (1-5)mL.
  • step S1 the cooling temperature is 0-12°C.
  • step S1 the benzene glycol compound, solvent and cross-linking agent are mixed for 2-4 hours, and the catalyst is added for 6-12 hours.
  • step S1 the mixture is heated to a reaction temperature of 60-120°C and a time of 1h-3h.
  • the heating and carbonization process is: first heating at 100-320°C for 0.1h-3h, and then heating at 600-1000°C for 8h-24h.
  • Inert gas is introduced and hole expansion is performed under the action of air flow. Further, the gas flow rate of the inert gas is 0.005-0.08m 3 /min.
  • the particle size D50 of the porous carbide is 2-26 ⁇ m, and the specific surface area is 200-350 m 2 /g.
  • the silicon-containing solution is a nano-silicon oxide suspension or a nano-silicon suspension, and the mass percentage of silicon in the silicon-containing solution is 0.001-0.75.
  • the chemical formula of the nano-silica is SiO x , 0 ⁇ x ⁇ 2.
  • the complexing agent is at least one of potassium sodium tartrate, ethylenediaminetetraacetic acid, and tartaric acid.
  • the metal salt is at least one of soluble sulfate, chloride salt, nitrate, bromide salt or phosphate of copper or silver; the reducing agent is At least one of hypophosphorous acid and sodium hypophosphite.
  • step S3 the heating temperature is 550-1100°C, and the heating time is 1-5 hours.
  • the particle size D50 of the silicon-carbon composite negative electrode material is 0.5-23 ⁇ m.
  • step S3 the mass percentage of silicon in the silicon-carbon composite negative electrode material is 0.001-0.35.
  • step S3 the mass percentage of metal in the silicon-carbon composite negative electrode material is 0.001-0.02.
  • step S3 the mass ratio of complexing agent, metal salt and reducing agent added to the silicon-containing porous carbide suspension is (1-10): (0.2-5): (10-50), in which the mass ratio of the metal salt to the silicon in the silicon-containing porous carbide suspension is (0.1-2):3.
  • the inert atmosphere is at least one of neon, helium, argon, krypton, xenon or nitrogen.
  • the invention also provides the application of the preparation method in preparing lithium ion batteries.
  • the present invention at least has the following beneficial effects:
  • the hypercross-linked polymer undergoes high-temperature carbonization treatment to obtain a porous carbide structure.
  • the carbon layer can provide more channels for the transmission of electrons and Li + , provide more internal excess space, and provide greater space for the volume expansion of silicon.
  • the large buffer space can, to a certain extent, buffer the volume effect of the silicon-based anode material during the process of deintercalating lithium and improve the cycle performance of the anode material.
  • silicon is a semiconductor material, its conductivity is poor, and the expansion effect of silicon during cyclic charge and discharge also further deteriorates the structure of the negative electrode material. Therefore, through silicon-embedded metal treatment, the metal salt is reduced with a reducing agent under the action of a complexing agent, so that the silicon layer adsorbed on the porous carbide obtains a metal layer with good ductility and good conductivity. The metal layer is then alloyed with silicon at high temperatures, and the alloyed silicon is more tightly bonded. The stretching, bending, and compression properties of the prepared silicon-carbon composite anode material will be improved. The metal layer can effectively bear the stress of volume change caused by the expansion of silicon, and the electrical conductivity of the material will be improved.
  • Figure 1 is an SEM image of the surface of the silicon-carbon composite negative electrode material prepared in Example 1 of the present invention.
  • a silicon-carbon composite negative electrode material is prepared.
  • the specific process is:
  • the obtained solid was kept at 845°C for 3 hours in an argon atmosphere to obtain porous carbide with silicon-copper alloy, which was then ball-milled (D50 was controlled at about 6.5 ⁇ m) and demagnetized to obtain a silicon-carbon composite anode material, in which silicon , and copper account for 0.07 and 0.004 of the mass percentage of the silicon-carbon composite anode material respectively.
  • a silicon-carbon composite negative electrode material is prepared.
  • the specific process is:
  • the obtained solid is Hold the temperature at 870°C for 3 hours in an argon atmosphere to obtain porous carbide with silicon-copper alloy, which is then ball-milled (D50 is controlled at about 5.9 ⁇ m) and demagnetized to obtain a silicon-carbon composite anode material, in which silicon and copper respectively account for silicon-carbon.
  • the mass percentage of composite negative electrode material is 0.11 and 0.007.
  • a silicon-carbon composite negative electrode material is prepared.
  • the specific process is:
  • a silicon-carbon composite negative electrode material is prepared.
  • the specific process is:
  • Expansion rate of negative electrode piece (thickness of negative electrode piece after filling - thickness of negative electrode piece after drying)/negative electrode piece The thickness after drying * 100%, the calculation results of the expansion rate of the negative electrode piece are shown in Table 1.
  • the porous carbide obtained in step 2 has a higher specific surface area, and the conductivity of the silicon-carbon composite negative electrode material sample is significantly improved compared to the uncomposite sample. At the same time, the expansion rate of silicon-carbon composite negative electrode materials during the charge and discharge process will be better than that of uncomposited ones.
  • Electrochemical performance test The negative electrode sheet of the battery is made by scraping coating.
  • the silicon-containing porous carbide and silicon-carbon composite negative electrode materials prepared in Examples 1-4 are mixed with the conductive agent SuperP and PVDF at a mass ratio of 8 respectively. :1:1, weigh it, add N-methylpyrrolidone (NMP) as the solvent, and mix it evenly; then apply it on the copper foil with a scraper, press it into sheets, and place it in a vacuum oven for drying (80°C , 3h); the coated pole piece is punched into discs with a diameter of 12mm.
  • NMP N-methylpyrrolidone
  • a dry electrode sheet is used on the negative side
  • a lithium sheet is used as the counter electrode on the positive side
  • the separator is Celgard2400
  • the electrolyte is: 1M Li PF6 EC, DMC, DEC (volume ratio is 1:1:1).
  • the prepared half-cell was tested for charge and discharge performance using the CT2001A battery testing system at a voltage of 0.01-2.0V and a current density of 100mA/g. The results are shown in Table 2.
  • the silicon-carbon composite anode material is superior in first charge specific capacity, Coulombic efficiency and 200th cycle capacity retention rate, indicating that the composite
  • the metal layer can effectively bear the stress of volume changes caused by the expansion of silicon, further buffering the volume effect of the silicon-based anode material during the process of deintercalating lithium.

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Abstract

本发明公开了一种硅碳复合负极材料的制备方法及其应用，所述制备方法包括：将超交联聚合物置于惰性气氛下加热碳化，得到多孔碳化物；将多孔碳化物与含硅溶液混合，得到含硅多孔碳化物悬浊液；向含硅多孔碳化物悬浊液中加入络合剂、金属盐和还原剂进行反应，反应结束后固液分离，所得固体在惰性气氛下加热，即得硅碳复合负极材料。本发明通过硅嵌金属处理，在络合剂作用下用还原剂对金属盐进行还原，使得吸附在多孔碳化物上的硅层得到一层金属层，在高温下再将金属层与硅合金化，使材料的伸展、弯曲、压缩性能得到提升，金属层能有效承载硅的膨胀带来的体积变化的应力，材料的电导率也得到提升。

Description

硅碳复合负极材料的制备方法及其应用 技术领域
本发明属于锂离子电池技术领域，具体涉及一种硅碳复合负极材料的制备方法及其应用。
背景技术
硅基负极材料由于具有丰富的来源、低成本、高储锂理论容量、合适的脱锂电压，是一种极具商业化应用前景的负极材料。但与石墨不同的是，硅在脱/嵌锂过程中会反复收缩膨胀，容易导致负极片失去电接触，造成负极片材料失活，这可能极大地降低硅基负极材料的应用前景。此外，因为其比表面积更大以及产生的大量的缺陷严重的副反应，实际应用中也面临着首周库伦效率低、长循环稳定性不足以及倍率性能较差等问题。
目前，通过硅基负极材料与碳材料结合，调控两者间的形态设计，合成稳定性良好的结构，其得到硅-碳负极材料的效果就是能提高锂离子的扩散并增加电子的传输速度，来提升循环稳定性，是解决硅负极材料缺陷的有效手段。
例如，多孔碳材料除了具有普通碳材料的性质，同时，丰富孔结构的引入提供硅可膨胀的空间，具有高比表面积、高接触面积、多孔结构可控和易修饰等优点。因此，如何优化多孔碳材料的结构以及与硅基负极材料结合来提升硅-碳负极材料的性能仍然是当前面临的问题。
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，本发明提出一种硅碳复合负极材料的制备方法及其应用。
根据本发明的一个方面，提出了一种硅碳复合负极材料的制备方法，包括以下步骤：
S1：将超交联聚合物置于惰性气氛下加热碳化，得到多孔碳化物；
S2：将所述多孔碳化物与含硅溶液混合，得到含硅多孔碳化物悬浊液；
S3：向所述含硅多孔碳化物悬浊液中加入络合剂、金属盐和还原剂进行反应，反应结束后固液分离，所得固体在惰性气氛下加热，即得所述硅碳复合负极材料。
在本发明的一些实施方式中，步骤S1中，所述超交联聚合物的制备如下：在惰性气氛下，将苯二醇类化合物、溶剂和交联剂混合，冷却，再加入催化剂混合，所得混合物进行加热反应，得到所述超交联聚合物。优选的，所述苯二醇类化合物为对苯二甲醇、间苯二甲醇、邻苯二甲醇、对苯二乙醇、间苯二乙醇或邻苯二乙醇中的至少一种。所述溶剂为四氯甲烷、三氯甲烷、氯乙烷、二氯乙烷、三氯乙烷、氯丙烷、二氯丙烷、三氯丙烷或四氯丙烷中的至少一种。所述交联剂为二甲醇缩甲醛。所述催化剂为氯化铁。
在本发明的一些实施方式中，步骤S1中，所述苯二醇类化合物、溶剂、催化剂和交联剂的用量配比为(5-10)g：(15-80)mL：(1.2-6)g：(1-5)mL。
在本发明的一些实施方式中，步骤S1中，所述冷却的温度为0-12℃。
在本发明的一些实施方式中，步骤S1中，所述苯二醇类化合物、溶剂和交联剂混合的时间为2-4h，加入所述催化剂混合的时间为6-12h。
在本发明的一些实施方式中，步骤S1中，所述混合物加热反应的温度为60-120℃，时间为1h-3h。
在本发明的一些实施方式中，步骤S1中，所述的加热碳化的过程为：先在100-320℃下加热0.1h-3h，再在600-1000℃下加热8h-24h，加热碳化期间通入惰性气体，在气流作用下进行扩孔处理。进一步地，惰性气体的气流流速为0.005-0.08m3/min。
在本发明的一些实施方式中，步骤S1中，所述多孔碳化物的粒径D50为2-26μm，比表面积为200-350m2/g。
在本发明的一些实施方式中，步骤S2中，所述含硅溶液为纳米氧化硅悬浮液或纳米硅悬浮液，所述含硅溶液中硅的质量百分数为0.001-0.75。所述纳米氧化硅的化学式为SiOx，0<x≤2。
在本发明的一些实施方式中，步骤S3中，所述络合剂为酒石酸钾钠、乙二胺四乙酸、酒石酸中的至少一种。
在本发明的一些实施方式中，步骤S3中，所述金属盐为铜或银的可溶性硫酸盐、氯化盐、硝酸盐、溴化盐或磷酸盐中的至少一种；所述还原剂为次磷酸、次磷酸钠中的至少一种。
在本发明的一些实施方式中，步骤S3中，所述加热的温度为550-1100℃，加热的时间为1-5h。
在本发明的一些实施方式中，步骤S3中，所述硅碳复合负极材料的粒径D50为0.5-23μm。
在本发明的一些实施方式中，步骤S3中，所述硅碳复合负极材料中硅的质量百分数为0.001-0.35。
在本发明的一些实施方式中，步骤S3中，所述硅碳复合负极材料中金属的质量百分数为0.001-0.02。
在本发明的一些实施方式中，步骤S3中，所述含硅多孔碳化物悬浊液中加入络合剂、金属盐和还原剂的质量比为(1-10)：(0.2-5)：(10-50)，其中金属盐与含硅多孔碳化物悬浊液中硅的质量比为(0.1-2):3。
在本发明的一些实施方式中，所述惰性气氛为氖气、氦气、氩气、氪气、氙气或氮气中的至少一种。
本发明还提供所述的制备方法在制备锂离子电池中的应用。
根据本发明的一种优选的实施方式，本发明至少具有以下有益效果：
1、超交联聚合物经过高温碳化处理，得到多孔碳化物结构，其碳层能够为电子和Li+的传输提供更多的通道，提供较多的内部多余空间，为硅的体积膨胀提供较大的缓冲空间，一定程度上缓冲硅基负极材料在脱嵌锂过程中的体积效应，改善负极材料的循环性能。
2、由于硅为半导体材料，其导电性欠佳，并且循环充放电中硅的膨胀效应也使得负极材料的结构进一步恶化。因此通过硅嵌金属处理，在络合剂作用下用还原剂对金属盐进行还原，使得吸附在多孔碳化物上的硅层得到一层延展性、导电性良好的金属层， 在高温下再将金属层与硅合金化，合金化硅结合更紧密。制备得到的硅碳复合负极材料的伸展、弯曲、压缩性能将得到提升，金属层能有效承载的硅的膨胀带来的体积变化的应力，材料的电导率提升。
附图说明
下面结合附图和实施例对本发明做进一步的说明，其中：
图1为本发明实施例1制备的硅碳复合负极材料表面SEM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
本实施例制备了一种的硅碳复合负极材料，具体过程为：
1、将对苯二甲醇(100g)、四氯甲烷、氯化铁和二甲醇缩甲醛按照5g:15mL:2g:1.2mL的比例进行称量，先将对苯二甲醇、四氯甲烷和二甲醇缩甲醛在含有氮气气氛的容器中搅拌2h，然后在2℃的冰水浴中冷却0.5h，最后加入称量好的氯化铁继续搅拌6h，以得到混合均匀的混合物；
2、将混合物在75℃下加热反应3h得的超交联聚合物，用乙醇和水的混合液洗涤多次以洗去多余的四氯甲烷和氯化铁，将含有超交联聚合物的容器送至加热设备中，进行一段加热：110℃，加热3h，后再进行二段加热：865℃，加热15h，其中加热的过程中通入氮气，在气流(0.01m3/min)作用下进行扩孔处理，最后得到多孔碳化物，将得到的多孔碳化物放入球磨机中进行球磨，得到的物料粒度D50为6.3μm左右；
3、将步骤2中得到的球磨后的多孔碳化物80g与100mL纳米氧化硅悬浮液混合5h(纳米氧化硅的粒度在40nm左右，纳米氧化硅悬浮液中硅的百分数质量为0.13)，得到含硅多孔碳化物悬浊液，取一半含硅多孔碳化物悬浊液不进行嵌金属处理，静置3h、固 液分离，所得固体在氩气气氛中以845℃保温3h，得到含硅多孔碳化物，其中硅占含硅多孔碳化物质量百分数的0.07；
4、将另一半含硅多孔碳化物悬浊液、乙二胺四乙酸、硫酸铜和次磷酸混合(含硅多孔碳化物悬浊液中加入乙二胺四乙酸、硫酸铜、次磷酸的质量比为1.2：1.7：12，其中硫酸铜与含硅多孔碳化物悬浊液中硅的质量比为0.2:3)，在75℃下搅拌反应，反应结束后静置3h、固液分离、洗涤除杂，所得固体在氩气气氛中以845℃保温3h，得到具有硅铜合金的多孔碳化物，然后进行球磨(D50控制在6.5μm左右)、除磁，得到硅碳复合负极材料，其中硅、铜分别占硅碳复合负极材料质量百分数的0.07、0.004。
实施例2
本实施例制备了一种的硅碳复合负极材料，具体过程为：
1、将对苯二甲醇(100g)、四氯甲烷、氯化铁和二甲醇缩甲醛按照6g:20mL:2.7g:1.5mL的比例进行称量，先将对苯二甲醇、四氯甲烷和二甲醇缩甲醛在含有氮气气氛的容器中搅拌2h，然后在2℃的冰水浴中冷却0.5h，最后加入称量好的氯化铁继续搅拌6h，以得到混合均匀的混合物；
2、将混合物在75℃下加热反应3h得的超交联聚合物，用乙醇/水混合液洗涤多次以洗去多余的四氯甲烷和氯化铁；将含有超交联聚合物的容器送至加热设备中，进行一段加热：110℃，加热2h；后再进行二段加热：865℃，加热15h。其中加热的过程中通入氮气，以在气流(0.01m3/min)作用下进行扩孔处理，最后得到多孔碳化物，将得到的多孔碳化物放入球磨机中进行球磨，得到的物料粒度D50为5.3μm左右；
3、将步骤2中得到的球磨后的多孔碳化物80g与100mL纳米氧化硅悬浮液混合5h(纳米氧化硅的粒度在40nm左右，纳米氧化硅悬浮液中硅的百分数质量为0.13)，得到含硅多孔碳化物悬浊液，取一半悬浊液不进行嵌金属处理，静置3h、固液分离，所得固体在氩气气氛中以870℃保温3h，得到含硅多孔碳化物，其中硅占含硅多孔碳化物质量百分数的0.11；
4、将另一半将含硅多孔碳化物悬浊液、乙二胺四乙酸、硫酸铜和次磷酸进行混合(含硅多孔碳化物悬浊液中加入乙二胺四乙酸、硫酸铜、次磷酸的质量比为1.6：2.3： 22，其中硫酸铜与含硅多孔碳化物悬浊液中硅的质量比为0.27:3)，在75℃下搅拌反应，反应结束后静置3h、固液分离、洗涤除杂，所得固体在氩气气氛中以870℃保温3h，得到具有硅铜合金的多孔碳化物，然后进行球磨(D50控制在5.9μm左右)、除磁，得到硅碳复合负极材料，其中硅、铜分别占硅碳复合负极材料质量百分数的0.11、0.007。
实施例3
本实施例制备了一种的硅碳复合负极材料，具体过程为：
1、对苯二甲醇(100g)、四氯甲烷、氯化铁和二甲醇缩甲醛按照6g:20mL:2.7g:1.5mL的比例进行称量，先将对苯二甲醇、四氯甲烷和二甲醇缩甲醛在含有氮气气氛的容器中搅拌2h，然后在2℃的冰水浴中冷却0.5h，最后加入称量好的氯化铁继续搅拌6h，以得到混合均匀的混合物；
2、将混合物在75℃下加热反应3h得的超交联聚合物，用乙醇/水混合液洗涤多次以洗去多余的四氯甲烷和氯化铁；将含有超交联聚合物的容器送至加热设备中，进行一段加热：110℃，加热2h；后再进行二段加热：865℃，加热15h，其中加热的过程中通入氖气，以在气流(0.015m3/min)作用下进行扩孔处理，最后得到多孔碳化物，将得到的多孔碳化物放入球磨机中进行球磨，得到的物料粒度D50为5.6μm左右；
3、将步骤2中得到的球磨后的多孔碳化物80g与100mL纳米氧化硅悬浮液混合5h(纳米氧化硅的粒度在40nm左右，纳米氧化硅悬浮液中硅的百分数质量为0.23)，得到含硅多孔碳化物悬浊液，取一半悬浊液不进行嵌金属处理，静置3h、固液分离，所得固体在氩气气氛中以960℃保温2.5h，得到含硅多孔碳化物，其中硅占含硅多孔碳化物质量百分数的0.14；
4、将另一半将含硅多孔碳化物悬浊液、乙二胺四乙酸、硫酸铜和次磷酸进行混合(含硅多孔碳化物悬浊液中加入乙二胺四乙酸、硫酸铜、次磷酸的质量比为3：3.5：28，其中硫酸铜与含硅多孔碳化物悬浊液中硅的质量比为0.3:3)，在75℃下搅拌反应，反应结束后静置3h、固液分离、洗涤除杂，所得固体在氩气气氛中以960℃保温2.5h，得到具有硅铜合金的多孔碳化物，然后进行球磨(D50控制在5.1μm左右)、除磁，得到硅碳复合负极材料，其中硅、铜分别占硅碳复合负极材料质量百分数的0.14、0.006。
实施例4
本实施例制备了一种的硅碳复合负极材料，具体过程为：
1、邻苯二甲醇(100g)、四氯甲烷、氯化铁和二甲醇缩甲醛按照6g:40mL:4.2g:2.0mL的比例进行称量，先将邻苯二甲醇、四氯甲烷和二甲醇缩甲醛在含有氮气气氛的容器中搅拌2h，然后在6℃的冰水浴中冷却0.5h，最后加入称量好的氯化铁继续搅拌6h，以得到混合均匀的混合物；
2、将混合物在75℃下加热反应3h得的超交联聚合物，用乙醇/水混合液洗涤多次以洗去多余的四氯甲烷和氯化铁；将含有超交联聚合物的容器送至加热设备中，进行一段加热：110℃，加热2h；后再进行二段加热：735℃，加热15h，其中加热的过程中通入氖气，以在气流(0.015m3/min)作用下进行扩孔处理，最后得到多孔碳化物，将得到的多孔碳化物放入球磨机中进行球磨，得到的物料粒度D50为3.4μm左右；
3、将步骤2中得到的球磨后的多孔碳化物80g与100mL纳米氧化硅悬浮液混合5h(纳米氧化硅的粒度在40nm左右，纳米氧化硅悬浮液中硅的百分数质量为0.24)，得到含硅多孔碳化物悬浊液，取一半悬浊液不进行嵌金属处理，静置3h、固液分离，所得固体在氩气气氛中以960℃保温2.5h，得到含硅多孔碳化物，其中硅占含硅多孔碳化物质量百分数的0.15；
4、将另一半将含硅多孔碳化物悬浊液、酒石酸钾钠、氯化银和次磷酸进行混合(含硅多孔碳化物悬浊液中加入酒石酸钾钠、氯化银、次磷酸的质量比为8：3.2：36，其中氯化银与含硅多孔碳化物悬浊液中硅的质量比为0.3:3)，在60℃下搅拌反应，反应结束后静置3h、固液分离、洗涤除杂，所得固体在氩气气氛中以960℃保温2.5h，得到具有硅银合金的多孔碳化物，然后进行球磨(D50控制在3.5μm左右)、除磁，得到硅碳复合负极材料，其中硅、银分别占硅碳复合负极材料质量百分数的0.15、0.003。
试验例
1、用四探针法测试实施例1-4得到含硅多孔碳化物以及硅碳复合负极材料的电导率，其结果如表1所示。
2、负极极片膨胀率＝(负极极片充满后的厚度-负极极片干燥后的厚度)/负极极片 干燥后的厚度*100％，负极极片膨胀率计算结果如表1所示。
表1负极材料的比表面积、电导率、负极极片膨胀率
从表1的测试结果可以看出：步骤2得到的多孔碳化物比表面积较高，硅碳复合负极材料的样品较未复合的样品的电导率有显著提升。同时，硅碳复合负极材料在充放电过程中的膨胀率也会比未复合的较优。
3、电化学性能测试：通过刮涂的方式制作电池的负极极片，实施例1-4制备得到的含硅多孔碳化物和硅碳复合负极材料，分别与导电剂SuperP、PVDF按照质量比8:1:1进行称取，加N-甲基吡咯烷酮(NMP)作溶剂，将其混合均匀；后将其用刮刀涂覆在铜箔上、压片并放置在真空烘箱内进行干燥(80℃，3h)；涂覆好的极片并冲切成直径为12mm的圆片。在半电池中，负极侧使用干燥的电极片，正极侧使用锂片为对电极，隔膜为Celgard2400，电解液：1M Li PF6的EC、DMC、DEC(体积比为1:1:1)。利用CT2001A型电池检测系统对制备的半电池，在电压为0.01-2.0V，电流密度为100mA/g下进行了充放电性能测试，其结果如表2所示。
表2负极材料的电化学性能

从表2的测试结果可以看出，与未复合的含硅多孔碳化物相比，硅碳复合负极材料在首次充电比容量、库伦效率和第200圈容量保持率上都较优，表明复合的金属层能有效承载硅的膨胀带来的体积变化的应力，进一步缓冲硅基负极材料在脱嵌锂过程中的体积效应。
上面结合附图对本发明实施例作了详细说明，但是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. 一种硅碳复合负极材料的制备方法，其特征在于，包括以下步骤：
    S1：将超交联聚合物置于惰性气氛下加热碳化，得到多孔碳化物；
    S2：将所述多孔碳化物与含硅溶液混合，得到含硅多孔碳化物悬浊液；
    S3：向所述含硅多孔碳化物悬浊液中加入络合剂、金属盐和还原剂进行反应，反应结束后固液分离，所得固体在惰性气氛下加热，即得所述硅碳复合负极材料。
  2. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述超交联聚合物的制备如下：在惰性气氛下，将苯二醇类化合物、溶剂和交联剂混合，冷却，再加入催化剂混合，所得混合物进行加热反应，得到所述超交联聚合物。
  3. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述的加热碳化的过程为：先在100-320℃下加热0.1h-3h，再在600-1000℃下加热8h-24h，加热碳化期间通入惰性气体，在气流作用下进行扩孔处理。
  4. 根据权利要求1所述的制备方法，其特征在于，步骤S1中，所述多孔碳化物的粒径D50为2-26μm，比表面积为200-350m2/g。
  5. 根据权利要求1所述的制备方法，其特征在于，步骤S2中，所述含硅溶液为纳米氧化硅悬浮液或纳米硅悬浮液，所述含硅溶液中硅的质量百分数为0.001-0.75。
  6. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述络合剂为酒石酸钾钠、乙二胺四乙酸、酒石酸中的至少一种。
  7. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述金属盐为铜或银的可溶性硫酸盐、氯化盐、硝酸盐、溴化盐或磷酸盐中的至少一种；所述还原剂为次磷酸、次磷酸钠中的至少一种。
  8. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述加热的温度为550-1100℃，加热的时间为1-5h。
  9. 根据权利要求1所述的制备方法，其特征在于，步骤S3中，所述硅碳复合负极材料的粒径D50为0.5-23μm。
  10. 如权利要求1-9中任一项所述的制备方法在制备锂离子电池中的应用。
PCT/CN2023/077215 2022-05-05 2023-02-20 硅碳复合负极材料的制备方法及其应用 Ceased WO2023213113A1 (zh)

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