WO2021004150A1 - 一种锂离子电池负极材料SnS/ND-CN的制备方法 - Google Patents

一种锂离子电池负极材料SnS/ND-CN的制备方法 Download PDF

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WO2021004150A1
WO2021004150A1 PCT/CN2020/089806 CN2020089806W WO2021004150A1 WO 2021004150 A1 WO2021004150 A1 WO 2021004150A1 CN 2020089806 W CN2020089806 W CN 2020089806W WO 2021004150 A1 WO2021004150 A1 WO 2021004150A1
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negative electrode
electrode material
sns
lithium
solution
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French (fr)
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殷立雄
宋佳琪
李书航
黄剑锋
杨军
蔺英
韩浪
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陕西科技大学
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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
    • H01M10/052—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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • 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
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • 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
    • 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
    • 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 invention belongs to the technical field of preparation methods of lithium ion battery negative electrode materials, and relates to a preparation method of lithium ion battery negative electrode material SnS/ND-CN.
  • the energy density of lithium-ion power batteries must reach 350Wh kg -1 or more.
  • the energy density of power lithium-ion batteries using graphite as the negative electrode material on the market is generally below 240Wh kg -1 , and the capacity of the graphite electrode is very close to the theoretical capacity, and the improvement space is limited. Therefore, the development of new high-capacity anode materials is very important. SnS-based materials have attracted wide attention from scientists due to their high capacity, low toxicity, and easy preparation.
  • SnS electrode materials have been studied less, with lower lithium insertion potential and higher theoretical capacity (782mAh/g).
  • SnS is an important group IV-VI compound semiconductor material. By controlling the concentration of tin element, it can display the properties of both n-type semiconductor and p-type semiconductor.
  • the crystal has a distorted NaCl structure. In each layer, Sn atoms and S Atoms are bonded by strong covalent bonds, while atoms between layers are bonded by weaker van der Waals forces. SnS has become a potential anode material for lithium-ion batteries due to its unique structure and high theoretical capacity.
  • the main electrochemical reactions of SnS electrode materials during charging and discharging are conversion reactions and alloying reactions.
  • the reversible capacity of SnS electrode materials mainly comes from alloying reactions.
  • SnS electrode materials and lithium metal undergo intercalation and desorption reactions, conversion reactions, etc.
  • the reaction expression of the electrochemical reaction process is the following is the reaction expression of the electrochemical reaction process:
  • the electrode has a large volume expansion during charging and discharging, which will cause the electrode to powder and even fall off the current collector. , Leading to its poor cycle stability and structural stability; but its poor electrical conductivity, which affects the transfer rate of electrons, resulting in its slower kinetic reaction leading to its poor electrochemical performance.
  • the technical problem solved by the present invention is to provide a method for preparing lithium ion battery negative electrode material SnS/ND-CN with low preparation cost, simple operation method and short preparation cycle, which is applied to lithium ion battery negative electrode and has excellent cycle stability.
  • a preparation method of SnS/ND-CN, a negative electrode material for lithium ion batteries includes the following steps:
  • Step 1 Put the melamine in a high-temperature container and calcinate in a calcining furnace at 550-700°C to obtain gC 3 N 4 precursor; combine 1 to 3 g of gC 3 N 4 precursor and 1 to 3 g of magnesium The powder is mixed and kept at 700 ⁇ 800°C in an inert gas atmosphere, the powder is washed and dried to obtain ND-CN;
  • Step 2 Add 1 ⁇ 1.5g of ND-CN to 40 ⁇ 60ml of ethylene glycol, stir and dissolve, then add 0.5 ⁇ 1g of CN 2 H 4 S to dissolve to obtain solution B;
  • Step 4 Put solution C into a hydrothermal kettle for hydrothermal reaction at 160-200°C to obtain a turbid liquid precursor
  • Step 5 Take out the turbid liquid precursor after centrifugal washing and drying to obtain SnS/ND-CN as the negative electrode material of the lithium ion battery.
  • the high temperature resistant container in step 1 is a porcelain boat; the calcining furnace is a muffle furnace and the calcining time is 3 to 5 hours.
  • step 1 the inert gas is argon and the holding time is 2 to 4 hours.
  • step 1 is washing with acetic acid and water.
  • drying in step 1 is vacuum drying at 60-80° C. for 8-12 hours.
  • the stirring in step 2 is magnetic stirring for 20-40 minutes.
  • the stirring in step 3 is magnetic stirring for 20-40 minutes.
  • the filling ratio of the hydrothermal kettle in step 4 is 40-60%; the hydrothermal reaction time is 18-24h.
  • step 5 the centrifugal washing in step 5 is washed with water and absolute ethanol.
  • drying in step 5 is vacuum drying at 60-80° C. for 8-12 hours.
  • the present invention has the following beneficial technical effects:
  • the invention provides a method for preparing SnS/ND-CN as a negative electrode material for lithium ion batteries.
  • the prepared SnS/ND-CN realizes SnS nano-sizing and forms a nano-sheet structure of SnS/ND-CN, which has a larger
  • the specific surface area increases the chance of contact with the electrolyte and reactive sites, which is beneficial to the migration of lithium ions, and alleviates the volume change during charging and discharging, which is beneficial to improve the electrochemical performance of the material and also shorten the lithium ion diffusion path , So as to achieve the purpose of fast charging;
  • the morphology of SnS/ND-CN can be adjusted by controlling the hydrothermal reaction temperature, which can relieve its volume expansion and stabilize its structure; during the preparation process, SnS and carbon materials are loaded or Coating, so as to provide it with a good electron transmission channel, which can alleviate its volume expansion; SnS is compounded with the active component, and the composite active component reacts with the lithium ion to provide
  • Example 1 is an XRD pattern of SnS/ND-CN, a negative electrode material for lithium ion batteries prepared in Example 3;
  • Example 2 is an SEM image of SnS/ND-CN, a negative electrode material for lithium ion batteries prepared in Example 3;
  • Example 3 is a TEM image of SnS/ND-CN, a negative electrode material for lithium ion batteries prepared in Example 3;
  • Figure 4 is a partial view of Figure 3;
  • Example 5 is a graph showing the cycle performance of SnS/ND-CN, a negative electrode material for lithium ion batteries prepared in Example 3.
  • a preparation method of SnS/ND-CN, a negative electrode material for lithium ion batteries includes the following steps:
  • Step 1 Place melamine in a porcelain boat and calcinate in a muffle furnace at 550°C for 5 hours to obtain gC 3 N 4 precursor; mix 1 g of gC 3 N 4 precursor and 1 g of magnesium powder and mix them in argon Incubate at 700°C for 4h in an air atmosphere. The powder is washed three times with acetic acid and water and then vacuum dried at 60°C for 12h to obtain ND-CN;
  • Step 2 Add 1g of ND-CN to 40ml of ethylene glycol and magnetically stir for 30min and dissolve it, then add 1g of CN 2 H 4 S to dissolve to obtain solution B;
  • Step 4 Put solution C into a hydrothermal kettle and place it in a homogeneous hydrothermal reactor for a hydrothermal reaction at 200°C for 18 hours to obtain a turbid liquid precursor; the filling ratio of the hydrothermal kettle is 40%;
  • Step 5 Take out the turbid liquid precursor, wash it three times by alternating centrifugation with water and absolute ethanol, and dry it in a vacuum at 60° C. for 12 hours to obtain SnS/ND-CN as a negative electrode material for lithium-ion batteries.
  • a preparation method of SnS/ND-CN, a negative electrode material for lithium ion batteries includes the following steps:
  • Step 1 Place melamine in a porcelain boat and calcinate in a muffle furnace at 700°C for 3 hours to obtain gC 3 N 4 precursor; mix 2 g of gC 3 N 4 precursor and 1 g of magnesium powder and mix in argon Incubate at 800°C for 2h in an air atmosphere, to obtain the powder, wash it with acetic acid and water several times, and then vacuum dry at 80°C for 8h to obtain ND-CN;
  • Step 2 Add 1.5g of ND-CN to 50ml of ethylene glycol and magnetically stir for 30min and dissolve, then add 0.5g of CN 2 H 4 S to dissolve to obtain solution B;
  • Step 4 Put solution C into a hydrothermal kettle and place it in a homogeneous hydrothermal reactor for a hydrothermal reaction at 180°C for 20 hours to obtain a turbid liquid precursor; the filling ratio of the hydrothermal kettle is 50%;
  • Step 5 Take out the turbid liquid precursor, wash it three times by alternating centrifugation with water and absolute ethanol, and dry it in a vacuum at 60° C. for 12 hours to obtain SnS/ND-CN as a negative electrode material for lithium-ion batteries.
  • a preparation method of SnS/ND-CN, a negative electrode material for lithium ion batteries includes the following steps:
  • Step 1 Place melamine in a porcelain boat and calcinate in a muffle furnace at 600°C for 4 hours to obtain gC 3 N 4 precursor; mix 3 g of gC 3 N 4 precursor and 1 g of magnesium powder and mix in argon Incubate at 750°C for 3h in an air atmosphere, the powder is washed three times with acetic acid and water and then vacuum dried at 70°C for 10h to obtain ND-CN;
  • Step 2 Add 1.36g of ND-CN to 60ml of ethylene glycol and magnetically stir for 30min and dissolve it, then add 0.9g of CN 2 H 4 S to dissolve to obtain solution B;
  • Step 4 Put solution C into a hydrothermal kettle and place it in a homogeneous hydrothermal reactor for hydrothermal reaction at 160°C for 24 hours to obtain a turbid liquid precursor; the filling ratio of the hydrothermal kettle is 60%;
  • Step 5 Take out the turbid liquid precursor, wash it three times by alternating centrifugation with water and absolute ethanol, and dry it in a vacuum at 60° C. for 12 hours to obtain SnS/ND-CN as a negative electrode material for lithium-ion batteries.
  • SnS/ND-CN Take a sample of SnS/ND-CN as a negative electrode material for lithium-ion batteries.
  • the SnS and ND-CN in the sample are respectively compatible with SnS with PDF number 39-0354 and gC 3 N 4 with PDF number 75-1621
  • the diffraction peaks of the standard card can be well corresponded; as shown in Figure 2, the sample is in the shape of nanosheets, with ultra-thin thickness and good crystallinity.
  • the SnS nanosheets in the sample are loaded on ND-CN nanosheets; as shown in Figure 5, the sample has an initial capacity of 1457.6mAh ⁇ at a current density of 100mA ⁇ g -1 g -1 , keep at 492.3mAh ⁇ g -1 after 100 cycles, the coulombic efficiency is as high as 99%, and the cycle performance of the sample is excellent.
  • a preparation method of SnS/ND-CN, a negative electrode material for lithium ion batteries includes the following steps:
  • Step 1 Place melamine in a porcelain boat and calcinate in a muffle furnace at 650°C for 3.5 hours to obtain gC 3 N 4 precursor; mix 1 g of gC 3 N 4 precursor and 2 g of magnesium powder and mix them Incubate at 725°C for 3.5h in an argon atmosphere. The powder is washed three times with acetic acid and water and then vacuum dried at 65°C for 11h to obtain ND-CN;
  • Step 2 Add 1.2g of ND-CN to 50ml of ethylene glycol and magnetically stir for 20min and dissolve, then add 0.8g of CN 2 H 4 S to dissolve to obtain solution B;
  • Step 4 Put solution C into a hydrothermal kettle and place it in a homogeneous hydrothermal reactor for a hydrothermal reaction at 170°C for 22 hours to obtain a turbid liquid precursor; the filling ratio of the hydrothermal kettle is 40%;
  • Step 5 Take out the turbid liquid precursor, wash it three times by alternating centrifugation with water and absolute ethanol, and dry it in a vacuum at 70°C for 10 hours to obtain SnS/ND-CN as a negative electrode material for lithium-ion batteries.
  • a preparation method of SnS/ND-CN, a negative electrode material for lithium ion batteries includes the following steps:
  • Step 1 Place melamine in a porcelain boat and calcinate in a muffle furnace at 700°C for 3 hours to obtain gC 3 N 4 precursor; mix 1 g of gC 3 N 4 precursor and 3 g of magnesium powder and mix in argon Incubate at 775°C for 2.5 hours in an air atmosphere, and the obtained powder is washed with acetic acid and water three times and then vacuum dried at 75°C for 9 hours to obtain ND-CN;
  • Step 2 Add 1.4g of ND-CN to 60ml of ethylene glycol and magnetically stir for 40min and dissolve it, then add 0.7g of CN 2 H 4 S to dissolve to obtain solution B;
  • Step 4 Put solution C into a hydrothermal kettle and place it in a homogeneous hydrothermal reactor for a hydrothermal reaction at 190°C for 19 hours to obtain a turbid liquid precursor; the filling ratio of the hydrothermal kettle is 60%;
  • Step 5 Take out the turbid liquid precursor, wash it three times by alternating centrifugation with water and absolute ethanol, and dry it in a vacuum at 80°C for 8 hours to obtain SnS/ND-CN, a negative electrode material for lithium ion batteries.

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Abstract

本发明公开了一种锂离子电池负极材料SnS/ND-CN的制备方法，步骤1：将三聚氰胺置入耐高温容器内并置于煅烧炉中煅烧，得g-C 3N 4前驱体；将g-C 3N 4前驱体和镁粉混合并在惰性气体气氛中保温，得粉状体洗涤后干燥得ND-CN；步骤2：将ND-CN加入到乙二醇中搅拌并溶解后再加CN 2H 4S溶解得溶液B；步骤3：取SnCl 2·2H 2O和溶液B并将SnCl 2·2H 2O加入到溶液B中搅拌并溶解得溶液C；步骤4：将溶液C置入水热釜水热反应，得浑浊液态前驱体；步骤5：取出浑浊液态前驱体离心洗涤后干燥得锂离子电池负极材料SnS/ND-CN。其制备的电池负极材料应用于锂离子电池负极具有优异的循环稳定性。

Description

一种锂离子电池负极材料SnS/ND-CN的制备方法 技术领域
本发明属于锂离子电池负极材料制备方法技术领域，涉及一种锂离子电池负极材料SnS/ND-CN的制备方法。
背景技术
根据国家发布的《汽车产业中长期发展规划》，到2025年，锂离子动力电池能量密度需达到350Wh kg -1以上。目前市场上以石墨作为负极材料的动力锂离子电池的能量密度普遍在240Wh kg -1以下，并且石墨电极的容量已非常接近理论容量，提升空间有限。因此，开发新型高容量负极材料非常重要。SnS基材料由于具有高容量、低毒性、易制备等优点引起了科学家们的广泛关注。
SnS电极材料的研究较少，具有较低的嵌锂电位以及较高的理论容量(782mAh/g)。SnS是一种重要的IV-VI族化合物半导体材料，通过控制锡元素的浓度，既能展示出n-型半导体的性质，又能展示出p-型半导体的性质。单胞跨越两层，沿晶体的C轴堆叠，属正交晶系，晶胞系数a＝433pm、b＝1118pm、c＝398pm，晶体具有畸变NaCl型结构，在每一层中Sn原子和S原子是由较强的共价键结合的，而层与层之间的原子是由比较弱的范德华力结合的。SnS由于其独特的结构以及较高的理论容量而成为有潜力的锂离子电池负极材料。
SnS电极材料在充放电过程主要发生的电化学反应是转换反应和合金化反应，SnS电极材料的可逆容量主要来源于合金化反应，其中，SnS电极材料和锂金属发生嵌脱反应、转换反应等，根据化学反应的充放电电压平台的不同，以下是其电化学反应过程的反应表达式：
SnS+2Li ++2e -→Sn+Li 2S                                    (1)
Figure PCTCN2020089806-appb-000001
根据电化学反应充放电电压平台的不同，在1.0～1.5V之间，SnS首先与锂发生一个不可逆的置换反应，生成金属Sn和非晶态的Li 2S，如反应(1)所示，以及SEI膜的形成。而且，首次充放电过程中形成的SEI膜会产生较大的不可逆容量使得首次库伦效率较低。部分研究发现，在1.5V处，首先发生的是锂离子嵌入SnS层状结构发生反应但没有物相的转变(SnS+xLi ++xe -→Li XSnS)，在1.0V左右，Li xSnS与锂离子进行转换反应生成Sn单质和Li 2S(Li XSnS+(2-x)Li ++(2-x)e -→Sn+Li 2S)。而0.8V以下Sn单质和锂离子发生合金化反应。该反应是可逆的，Sn单质最多可结合4.4个锂离子，如反应(2)所示。SnS电极材料的可逆容量主要来源于这一步。另外，SEI膜的形成对电池的性能有较大的影响，稳定的SEI膜会使电化学性能很稳定，不稳定的SEI膜会导致性能衰减很快。
然而和大多数负极材料一样，将SnS作为锂离子电池负极材料存在两个较为严重的问题：一是电极在充放电过程中存在较大的体积膨胀，会使得电极粉化甚至从集流体上脱落，导致其较差的循环稳定性以及结构稳定性；而是其较差的导电性，从而影响电子的传递速率，导致其较缓慢的动力学反应导致其具有较差的电化学性能。
发明内容
本发明解决的技术问题在于提供一种制备成本低、操作方法简单和制备周期短的锂离子电池负极材料SnS/ND-CN的制备方法，其应用于锂离子电池负极具有优异的循环稳定性。
本发明是通过以下技术方案来实现：
一种锂离子电池负极材料SnS/ND-CN的制备方法，包括以下步骤：
步骤1：将三聚氰胺置入耐高温容器内并置于煅烧炉中在550～700℃下 煅烧，得g-C 3N 4前驱体；将1～3g的g-C 3N 4前驱体和1～3g的镁粉混合并在惰性气体气氛中700～800℃下保温，得粉状体洗涤后干燥得ND-CN；
步骤2：将1～1.5g的ND-CN加入到40～60ml乙二醇中搅拌并溶解后再加入0.5～1g的CN 2H 4S溶解得溶液B；
步骤3：按元素摩尔比Sn:S＝(0.5～2.0):(0.9～3.0)取SnCl 2·2H 2O和溶液B并将SnCl 2·2H 2O加入到溶液B中搅拌并溶解得溶液C；
步骤4：将溶液C置入水热釜在160～200℃下水热反应，得浑浊液态前驱体；
步骤5：取出浑浊液态前驱体离心洗涤后干燥得锂离子电池负极材料SnS/ND-CN。
进一步的，步骤1中耐高温容器为瓷舟；煅烧炉为马弗炉且煅烧时间为3～5h。
进一步的，步骤1中惰性气体为氩气且保温时间为2～4h。
进一步的，步骤1中洗涤为采用乙酸和水洗涤。
进一步的，步骤1中干燥为60～80℃下真空干燥8～12h。
进一步的，步骤2中搅拌为磁力搅拌20～40min。
进一步的，步骤3中搅拌为磁力搅拌20～40min。
进一步的，步骤4中水热釜的填充比为40～60％；水热反应时间为18～24h。
进一步的，步骤5中离心洗涤采用水和无水乙醇洗涤。
进一步的，步骤5中干燥为60～80℃下真空干燥8～12h。
与现有技术相比，本发明具有以下有益的技术效果：
本发明提供的一种锂离子电池负极材料SnS/ND-CN的制备方法，制备的SnS/ND-CN实现了SnS纳米化，形成纳米片状结构的SnS/ND-CN，其具 有较大的比表面积，增加了与电解液接触的机会和反应活性位点，有利于锂离子的迁移，以及缓解充放电过程中的体积变化，有利于提高材料的电化学性能同时还缩短了锂离子扩散路径，从而达到快充的目的；另外，通过水热反应温度的控制对SnS/ND-CN进行形貌调控，可以缓解其体积膨胀，稳定其结构；在制备的过程中SnS与碳材料进行负载或包覆，从而为其提供良好的电子传输通道，可以缓解其体积膨胀；SnS与活性组分进行复合，复合活性组分与锂离子反应提供了较高的理论比容量，在未参与反应时作为缓冲基体，缓冲体积膨胀，阻止团聚；从而达到提高其电化学性能的目的。
附图说明
图1为实施例3制备的锂离子电池负极材料SnS/ND-CN的XRD图；
图2为实施例3制备的锂离子电池负极材料SnS/ND-CN的SEM图；
图3为实施例3制备的锂离子电池负极材料SnS/ND-CN的TEM图；
图4为图3的局部图；
图5为实施例3制备的锂离子电池负极材料SnS/ND-CN的循环性能图。
具体实施方式
下面给出具体的实施例。
实施例1
一种锂离子电池负极材料SnS/ND-CN的制备方法，包括以下步骤：
步骤1：将三聚氰胺置入瓷舟内并置于马弗炉中在550℃下煅烧5h，得g-C 3N 4前驱体；将1g的g-C 3N 4前驱体和1g的镁粉混合并在氩气气氛中700℃下保温4h，得粉状体采用乙酸和水洗涤洗涤三次后在60℃下真空干燥12h，得ND-CN；
步骤2：将1g的ND-CN加入到40ml乙二醇中磁力搅拌30min并溶解 后再加入1g的CN 2H 4S溶解得溶液B；
步骤3：按元素摩尔比Sn:S＝0.5:0.9取SnCl 2·2H 2O和溶液B并将SnCl 2·2H 2O加入到溶液B中磁力搅拌30min并溶解得溶液C；
步骤4：将溶液C置入水热釜并置于均相水热反应仪中在200℃下水热反应18h，得浑浊液态前驱体；其中水热釜的填充比为40％；
步骤5：取出浑浊液态前驱体采用水和无水乙醇交替离心洗涤三次后在60℃下真空干燥12h，得锂离子电池负极材料SnS/ND-CN。
实施例2
一种锂离子电池负极材料SnS/ND-CN的制备方法，包括以下步骤：
步骤1：将三聚氰胺置入瓷舟内并置于马弗炉中在700℃下煅烧3h，得g-C 3N 4前驱体；将2g的g-C 3N 4前驱体和1g的镁粉混合并在氩气气氛中800℃下保温2h，得粉状体采用乙酸和水洗涤洗涤数次后在80℃下真空干燥8h，得ND-CN；
步骤2：将1.5g的ND-CN加入到50ml乙二醇中磁力搅拌30min并溶解后再加入0.5g的CN 2H 4S溶解得溶液B；
步骤3：按元素摩尔比Sn:S＝1:1.6取SnCl 2·2H 2O和溶液B并将SnCl 2·2H 2O加入到溶液B中磁力搅拌30min并溶解得溶液C；
步骤4：将溶液C置入水热釜并置于均相水热反应仪中在180℃下水热反应20h，得浑浊液态前驱体；其中水热釜的填充比为50％；
步骤5：取出浑浊液态前驱体采用水和无水乙醇交替离心洗涤三次后在60℃下真空干燥12h，得锂离子电池负极材料SnS/ND-CN。
实施例3
一种锂离子电池负极材料SnS/ND-CN的制备方法，包括以下步骤：
步骤1：将三聚氰胺置入瓷舟内并置于马弗炉中在600℃下煅烧4h，得g-C 3N 4前驱体；将3g的g-C 3N 4前驱体和1g的镁粉混合并在氩气气氛中750℃下保温3h，得粉状体采用乙酸和水洗涤洗涤三次后在70℃下真空干燥10h，得ND-CN；
步骤2：将1.36g ND-CN加入到60ml乙二醇中磁力搅拌30min并溶解后再加入0.9g的CN 2H 4S溶解得溶液B；
步骤3：按元素摩尔比Sn:S＝2:3取SnCl 2·2H 2O和溶液B并将SnCl 2·2H 2O加入到溶液B中磁力搅拌30min并溶解得溶液C；
步骤4：将溶液C置入水热釜并置于均相水热反应仪中在160℃下水热反应24h，得浑浊液态前驱体；其中水热釜的填充比为60％；
步骤5：取出浑浊液态前驱体采用水和无水乙醇交替离心洗涤三次后在60℃下真空干燥12h，得锂离子电池负极材料SnS/ND-CN。
取锂离子电池负极材料SnS/ND-CN样品，如图1所示，该样品中的SnS和ND-CN分别与PDF编号为39-0354的SnS和PDF编号为75-1621的g-C 3N 4的标准卡片衍射峰能很好地对应；如图2所示，该样品为纳米片状，厚度超薄，且结晶性较好。如图3和图4所示，该样品中的SnS纳米片负载在了ND-CN纳米片上；如图5所示，该样品在电流密度为100mA·g -1下，初始容量高达1457.6mAh·g -1，循环一百圈后保持在492.3mAh·g -1，库伦效率高达99％，样品的循环性能优异。
实施例4
一种锂离子电池负极材料SnS/ND-CN的制备方法，包括以下步骤：
步骤1：将三聚氰胺置入瓷舟内并置于马弗炉中在650℃下煅烧3.5h，得g-C 3N 4前驱体；将1g的g-C 3N 4前驱体和2g的镁粉混合并在氩气气氛中725℃ 下保温3.5h，得粉状体采用乙酸和水洗涤洗涤三次后在65℃下真空干燥11h，得ND-CN；
步骤2：将1.2g ND-CN加入到50ml乙二醇中磁力搅拌20min并溶解后再加入0.8g的CN 2H 4S溶解得溶液B；
步骤3：按元素摩尔比Sn:S＝0.5:3取SnCl 2·2H 2O和溶液B并将SnCl 2·2H 2O加入到溶液B中磁力搅拌20min并溶解得溶液C；
步骤4：将溶液C置入水热釜并置于均相水热反应仪中在170℃下水热反应22h，得浑浊液态前驱体；其中水热釜的填充比为40％；
步骤5：取出浑浊液态前驱体采用水和无水乙醇交替离心洗涤三次后在70℃下真空干燥10h，得锂离子电池负极材料SnS/ND-CN。
实施例5
一种锂离子电池负极材料SnS/ND-CN的制备方法，包括以下步骤：
步骤1：将三聚氰胺置入瓷舟内并置于马弗炉中在700℃下煅烧3h，得g-C 3N 4前驱体；将1g的g-C 3N 4前驱体和3g的镁粉混合并在氩气气氛中775℃下保温2.5h，得粉状体采用乙酸和水洗涤洗涤三次后在75℃下真空干燥9h，得ND-CN；
步骤2：将1.4g ND-CN加入到60ml乙二醇中磁力搅拌40min并溶解后再加入0.7g的CN 2H 4S溶解得溶液B；
步骤3：按元素摩尔比Sn:S＝2:0.9取SnCl 2·2H 2O和溶液B并将SnCl 2·2H 2O加入到溶液B中磁力搅拌40min并溶解得溶液C；
步骤4：将溶液C置入水热釜并置于均相水热反应仪中在190℃下水热反应19h，得浑浊液态前驱体；其中水热釜的填充比为60％；
步骤5：取出浑浊液态前驱体采用水和无水乙醇交替离心洗涤三次后在 80℃下真空干燥8h，得锂离子电池负极材料SnS/ND-CN。
以上给出的实施例是实现本发明较优的例子，本发明不限于上述实施例。本领域的技术人员根据本发明技术方案的技术特征所做出的任何非本质的添加、替换，均属于本发明的保护范围。

Claims (10)

  1. 一种锂离子电池负极材料SnS/ND-CN的制备方法，其特征在于，包括以下步骤：
    步骤1：将三聚氰胺置入耐高温容器内并置于煅烧炉中在550～700℃下煅烧，得g-C 3N 4前驱体；将1～3g的g-C 3N 4前驱体和1～3g的镁粉混合并在惰性气体气氛中700～800℃下保温，得粉状体洗涤后干燥得ND-CN；
    步骤2：将1～1.5g的ND-CN加入到40～60ml乙二醇中搅拌并溶解后再加入0.5～1g的CN 2H 4S溶解得溶液B；
    步骤3：按元素摩尔比Sn:S＝(0.5～2.0):(0.9～3.0)取SnCl 2·2H 2O和溶液B并将SnCl 2·2H 2O加入到溶液B中搅拌并溶解得溶液C；
    步骤4：将溶液C置入水热釜在160～200℃下水热反应，得浑浊液态前驱体；
    步骤5：取出浑浊液态前驱体离心洗涤后干燥得锂离子电池负极材料SnS/ND-CN。
  2. 根据权利要求1所述的一种锂离子电池负极材料SnS/ND-CN的制备方法，其特征在于，所述步骤1中耐高温容器为瓷舟；煅烧炉为马弗炉且煅烧时间为3～5h。
  3. 根据权利要求1所述的一种锂离子电池负极材料SnS/ND-CN的制备方法，其特征在于，所述步骤1中惰性气体为氩气且保温时间为2～4h。
  4. 根据权利要求1所述的一种锂离子电池负极材料SnS/ND-CN的制备方法，其特征在于，所述步骤1中洗涤为采用乙酸和水洗涤。
  5. 根据权利要求1所述的一种锂离子电池负极材料SnS/ND-CN的制备方法，其特征在于，所述步骤1中干燥为60～80℃下真空干燥8～12h。
  6. 根据权利要求1所述的一种锂离子电池负极材料SnS/ND-CN的制备 方法，其特征在于，所述步骤2中搅拌为磁力搅拌20～40min。
  7. 根据权利要求1所述的一种锂离子电池负极材料SnS/ND-CN的制备方法，其特征在于，所述步骤3中搅拌为磁力搅拌20～40min。
  8. 根据权利要求1所述的一种锂离子电池负极材料SnS/ND-CN的制备方法，其特征在于，所述步骤4中水热釜的填充比为40～60％；水热反应时间为18～24h。
  9. 根据权利要求1所述的一种锂离子电池负极材料SnS/ND-CN的制备方法，其特征在于，所述步骤5中离心洗涤采用水和无水乙醇洗涤。
  10. 根据权利要求1所述的一种锂离子电池负极材料SnS/ND-CN的制备方法，其特征在于，所述步骤5中干燥为60～80℃下真空干燥8～12h。
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