CN110311119A - A preparation method of lithium-ion battery negative electrode material SnS/ND-CN - Google Patents
A preparation method of lithium-ion battery negative electrode material SnS/ND-CN Download PDFInfo
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 48
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 20
- 239000012705 liquid precursor Substances 0.000 claims abstract description 16
- 239000002243 precursor Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000000843 powder Substances 0.000 claims abstract description 10
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- 239000010405 anode material Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000000034 method Methods 0.000 description 6
- 229910018091 Li 2 S Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 238000005275 alloying Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000003487 electrochemical reaction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 230000002427 irreversible effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 239000012300 argon atmosphere Substances 0.000 description 1
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- 239000011248 coating agent Substances 0.000 description 1
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- 238000009830 intercalation Methods 0.000 description 1
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- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
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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‑C3N4前驱体；将g‑C3N4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CN2H4S溶解得溶液B；步骤3：取SnCl2·2H2O和溶液B并将SnCl2·2H2O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。The invention discloses a preparation method of SnS/ND-CN, a lithium-ion battery negative electrode material. Step 1: putting melamine into a high-temperature resistant container and calcining in a calciner to obtain a g-C 3 N 4 precursor; Mix the g‑C 3 N 4 precursor with magnesium powder and keep it warm in an inert gas atmosphere to obtain a powder that is washed and dried to obtain ND‑CN; Step 2: Add ND‑CN to ethylene glycol, stir and dissolve Add CN 2 H 4 S to dissolve to obtain solution B; step 3: take SnCl 2 2H 2 O and solution B, add SnCl 2 2H 2 O to solution B, stir and dissolve to obtain solution C; step 4: dissolve solution C Put it into a hydrothermal kettle for hydrothermal reaction to obtain a turbid liquid precursor; step 5: take out the turbid liquid precursor, centrifuge and wash it, then dry it to obtain SnS/ND‑CN, a negative electrode material for lithium-ion batteries. The battery negative electrode material prepared by it is applied to the lithium ion battery negative electrode and has excellent cycle stability.
Description
技术领域technical field
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。The invention belongs to the technical field of preparation methods of negative electrode materials of lithium ion batteries, and relates to a preparation method of SnS/ND-CN, a negative electrode material of lithium ion batteries.
背景技术Background technique
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。According to the "Medium and Long-Term Development Plan for the Automobile Industry" issued by the state, by 2025, the energy density of lithium-ion power batteries must reach more than 350Wh kg -1 . At present, the energy density of power lithium-ion batteries using graphite as the negative electrode material in the market is generally below 240Wh kg -1 , and the capacity of graphite electrodes is very close to the theoretical capacity, with limited room for improvement. Therefore, it is very important to develop new high-capacity anode materials. SnS-based materials have attracted extensive attention of scientists due to their advantages such as high capacity, low toxicity, and easy preparation.
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。The research on SnS electrode material is less, and it has a lower lithium intercalation potential and a higher theoretical capacity (782mAh/g). SnS is an important IV-VI compound semiconductor material. By controlling the concentration of tin element, it can display the properties of n-type semiconductor and p-type semiconductor. The unit cell spans two layers and is stacked along the C axis of the crystal. It belongs to the orthorhombic crystal system. The unit cell coefficients are a=433pm, b=1118pm, c=398pm. The crystal has a distorted NaCl structure. In each layer, Sn atoms and S Atoms are bound by stronger covalent bonds, while atoms between layers are bound by weaker van der Waals forces. SnS has become a potential lithium-ion battery anode material due to its unique structure and high theoretical capacity.
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：The main electrochemical reactions of SnS electrode materials in the charging and discharging process are conversion reactions and alloying reactions. The reversible capacity of SnS electrode materials mainly comes from alloying reactions. , according to the different charging and discharging voltage platforms of the chemical reaction, the following is the reaction expression of the electrochemical reaction process:
SnS+2Li++2e-→Sn+Li2S (1)SnS+2Li + +2e - →Sn+Li 2 S (1)
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Li2S，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-→LiXSnS)，在1.0V左右，LixSnS与锂离子进行转换反应生成Sn单质和Li2S(LiXSnS+(2-x)Li++(2-x)e-→Sn+Li2S)。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。According to the different charging and discharging voltage platforms of the electrochemical reaction, between 1.0 and 1.5V, SnS first undergoes an irreversible substitution reaction with lithium to generate metal Sn and amorphous Li 2 S, as shown in reaction (1), And the formation of SEI film. Moreover, the SEI film formed during the initial charge-discharge process will produce a large irreversible capacity, making the initial Coulombic efficiency low. Some studies have found that at 1.5V, the first thing that happens is that lithium ions intercalate into the SnS layered structure to react but there is no phase transition (SnS+xLi + +xe - → Li X SnS), and at about 1.0V, Li x SnS The conversion reaction with lithium ions generates Sn simple substance and Li 2 S (Li X SnS+(2-x)Li ++ (2-x)e - →Sn+Li 2 S). And below 0.8V, Sn elemental alloying reaction occurs with lithium ions. This reaction is reversible, and Sn can combine up to 4.4 lithium ions, as shown in reaction (2). The reversible capacity of SnS electrode material mainly comes from this step. In addition, the formation of the SEI film has a great influence on the performance of the battery. A stable SEI film will make the electrochemical performance very stable, and an unstable SEI film will cause the performance to decay quickly.
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。However, like most anode materials, there are two serious problems in using SnS as the anode material of lithium-ion batteries: one is that the electrode has a large volume expansion during charging and discharging, which will cause the electrode to pulverize or even fall off from the current collector. , leading to its poor cycle stability and structural stability; but its poor electrical conductivity, which affects the electron transfer rate, resulting in its slower kinetics and poor electrochemical performance.
发明内容Contents of the invention
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。The technical problem solved by the present invention is to provide a preparation method of SnS/ND-CN, a lithium ion battery negative electrode material with low preparation cost, simple operation method and short preparation cycle, which has excellent cycle stability when applied to lithium ion battery negative electrode.
本发明是通过以下技术方案来实现：The present invention is achieved through the following technical solutions:
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：A preparation method of lithium-ion battery negative electrode material SnS/ND-CN, comprising the following steps:
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-C3N4前驱体；将1～3g的g-C3N4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；Step 1: Put melamine into a high-temperature resistant container and place it in a calciner for calcination at 550-700°C to obtain a gC 3 N 4 precursor; mix 1-3 g of gC 3 N 4 precursor and 1-3 g of magnesium Mix the powder and keep it warm at 700-800°C in an inert gas atmosphere to obtain the powder, which is washed and dried to obtain 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CN2H4S溶解得溶液B；Step 2: Add 1-1.5g of ND-CN into 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;
步骤3：按元素摩尔比Sn:S＝(0.5～2.0):(0.9～3.0)取SnCl2·2H2O和溶液B并将SnCl2·2H2O加入到溶液B中搅拌并溶解得溶液C；Step 3: According to the element molar ratio Sn:S=(0.5～2.0):(0.9～3.0), take SnCl 2 2H 2 O and solution B, add SnCl 2 2H 2 O to solution B, stir and dissolve to obtain a solution 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；Step 4: Put solution C into a hydrothermal kettle for hydrothermal reaction at 160-200°C to obtain a turbid liquid precursor;
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。Step 5: Take out the turbid liquid precursor, centrifuge and wash it, then dry it to obtain SnS/ND-CN, the anode material for lithium-ion batteries.
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。Further, in step 1, the high temperature resistant container is a porcelain boat; the calcination furnace is a muffle furnace and the calcination time is 3-5 hours.
进一步的，步骤1中惰性气体为氩气且保温时间为2～4h。Further, in step 1, the inert gas is argon and the holding time is 2-4 hours.
进一步的，步骤1中洗涤为采用乙酸和水洗涤。Further, the washing in step 1 is washing with acetic acid and water.
进一步的，步骤1中干燥为60～80℃下真空干燥8～12h。Further, the drying in step 1 is vacuum drying at 60-80° C. for 8-12 hours.
进一步的，步骤2中搅拌为磁力搅拌20～40min。Further, the stirring in step 2 is magnetic stirring for 20-40 minutes.
进一步的，步骤3中搅拌为磁力搅拌20～40min。Further, the stirring in step 3 is magnetic stirring for 20-40 minutes.
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。Further, the filling ratio of the hydrothermal kettle in step 4 is 40-60%; the hydrothermal reaction time is 18-24 hours.
进一步的，步骤5中离心洗涤采用水和无水乙醇洗涤。Further, the centrifugal washing in step 5 is washed with water and absolute ethanol.
进一步的，步骤5中干燥为60～80℃下真空干燥8～12h。Further, the drying in step 5 is vacuum drying at 60-80° C. for 8-12 hours.
与现有技术相比，本发明具有以下有益的技术效果：Compared with the prior art, the present invention has the following beneficial technical effects:
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。The present invention provides a method for preparing SnS/ND-CN, a lithium-ion battery negative electrode material. The prepared SnS/ND-CN realizes the nanosizing of SnS and forms SnS/ND-CN with a nanosheet structure, which has a larger The specific surface area increases the chance of contact with the electrolyte and the reactive active sites, which is conducive to the migration of lithium ions and eases the volume change during charge and discharge, which is conducive to improving the electrochemical performance of the material and shortening the diffusion path of lithium ions. , so as to achieve the purpose of fast charging; in addition, controlling the morphology of SnS/ND-CN through the control of the hydrothermal reaction temperature can alleviate 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 transport channel, which can relieve its volume expansion; SnS is composited with the active component, and the composite active component reacts with lithium ions to provide a higher theoretical specific capacity. Buffer matrix, buffer volume expansion, prevent agglomeration; thus achieve the purpose of improving its electrochemical performance.
附图说明Description of drawings
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；Fig. 1 is the XRD figure of the negative electrode material SnS/ND-CN of the lithium ion battery prepared in embodiment 3;
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；Fig. 2 is the SEM figure of the negative electrode material SnS/ND-CN of the lithium ion battery prepared by embodiment 3;
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；Fig. 3 is the TEM figure of the lithium-ion battery negative electrode material SnS/ND-CN prepared in embodiment 3;
图4为图3的局部图；Fig. 4 is a partial diagram of Fig. 3;
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。FIG. 5 is a graph of the cycle performance of the negative electrode material SnS/ND-CN for lithium ion batteries prepared in Example 3.
具体实施方式Detailed ways
下面给出具体的实施例。Specific examples are given below.
实施例1Example 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：A preparation method of lithium-ion battery negative electrode material SnS/ND-CN, comprising the following steps:
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-C3N4前驱体；将1g的g-C3N4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；Step 1: Put melamine into a porcelain boat and place it in a muffle furnace for calcination at 550°C for 5 hours to obtain a gC 3 N 4 precursor; mix 1 g of gC 3 N 4 precursor with 1 g of magnesium powder and heat Keep warm at 700°C for 4 hours in an air atmosphere, wash the obtained powder three times with acetic acid and water, and then vacuum-dry at 60°C for 12 hours to obtain 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CN2H4S溶解得溶液B；Step 2: Add 1g of ND-CN to 40ml of ethylene glycol, stir magnetically for 30min and dissolve, then add 1g of CN 2 H 4 S to dissolve to obtain solution B;
步骤3：按元素摩尔比Sn:S＝0.5:0.9取SnCl2·2H2O和溶液B并将SnCl2·2H2O加入到溶液B中磁力搅拌30min并溶解得溶液C；Step 3: Take SnCl 2 2H 2 O and solution B according to the element molar ratio Sn:S=0.5:0.9, add SnCl 2 2H 2 O to solution B and magnetically stir for 30 minutes and dissolve to obtain solution 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％；Step 4: Put solution C into a hydrothermal kettle and place it in a homogeneous hydrothermal reactor for hydrothermal reaction at 200°C for 18 hours to obtain a turbid liquid precursor; the filling ratio of the hydrothermal kettle is 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。Step 5: Take out the turbid liquid precursor, alternately centrifuge and wash it with water and absolute ethanol three times, and then vacuum-dry it at 60°C for 12 hours to obtain SnS/ND-CN, a negative electrode material for lithium-ion batteries.
实施例2Example 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：A preparation method of lithium-ion battery negative electrode material SnS/ND-CN, comprising the following steps:
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-C3N4前驱体；将2g的g-C3N4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；Step 1: Put melamine into a porcelain boat and place it in a muffle furnace for calcination at 700°C for 3 hours to obtain a gC 3 N 4 precursor; mix 2 g of gC 3 N 4 precursor with 1 g of magnesium powder and Keep warm at 800°C for 2 hours in an air atmosphere, wash the obtained powder several times with acetic acid and water, and then vacuum-dry at 80°C for 8 hours to obtain 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CN2H4S溶解得溶液B；Step 2: Add 1.5g of ND-CN to 50ml of ethylene glycol, stir magnetically for 30min and dissolve, then add 0.5g of CN 2 H 4 S to dissolve to obtain solution B;
步骤3：按元素摩尔比Sn:S＝1:1.6取SnCl2·2H2O和溶液B并将SnCl2·2H2O加入到溶液B中磁力搅拌30min并溶解得溶液C；Step 3: Take SnCl 2 ·2H 2 O and solution B according to the element molar ratio Sn:S=1:1.6, add SnCl 2 ·2H 2 O to solution B and magnetically stir for 30 minutes and dissolve to obtain solution 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％；Step 4: Put solution C into a hydrothermal kettle and place it in a homogeneous hydrothermal reactor for hydrothermal reaction at 180°C for 20 hours to obtain a turbid liquid precursor; the filling ratio of the hydrothermal kettle is 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。Step 5: Take out the turbid liquid precursor, alternately centrifuge and wash it with water and absolute ethanol three times, and then vacuum-dry it at 60°C for 12 hours to obtain SnS/ND-CN, a negative electrode material for lithium-ion batteries.
实施例3Example 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：A preparation method of lithium-ion battery negative electrode material SnS/ND-CN, comprising the following steps:
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-C3N4前驱体；将3g的g-C3N4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；Step 1: Put melamine into a porcelain boat and place it in a muffle furnace for calcination at 600°C for 4 hours to obtain a gC 3 N 4 precursor; mix 3 g of gC 3 N 4 precursor with 1 g of magnesium powder and Incubate at 750°C for 3 hours in an air atmosphere, wash the obtained powder three times with acetic acid and water, and then vacuum-dry at 70°C for 10 hours to obtain 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CN2H4S溶解得溶液B；Step 2: Add 1.36g ND-CN to 60ml ethylene glycol and stir magnetically for 30min and dissolve, then add 0.9g CN 2 H 4 S to dissolve to obtain solution B;
步骤3：按元素摩尔比Sn:S＝2:3取SnCl2·2H2O和溶液B并将SnCl2·2H2O加入到溶液B中磁力搅拌30min并溶解得溶液C；Step 3: Take SnCl 2 2H 2 O and solution B according to the elemental molar ratio Sn:S=2:3, add SnCl 2 2H 2 O to solution B and magnetically stir for 30 minutes and dissolve to obtain solution 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％；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%;
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。Step 5: Take out the turbid liquid precursor, alternately centrifuge and wash it with water and absolute ethanol three times, and then vacuum-dry it at 60°C for 12 hours to obtain SnS/ND-CN, a negative electrode material for lithium-ion batteries.
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-C3N4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。Take the SnS/ND-CN sample of lithium-ion battery negative electrode material, as shown in Figure 1, the SnS and ND-CN in this sample are respectively combined 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 to; as shown in Figure 2, the sample is in the shape of nano flakes with ultra-thin thickness and good crystallinity. As shown in Figure 3 and Figure 4, the SnS nanosheets in this sample are loaded on the ND-CN nanosheets; as shown in Figure 5, the initial capacity of this sample is as high as 1457.6mAh · g -1 , remained at 492.3mAh·g -1 after 100 cycles, the coulombic efficiency was as high as 99%, and the cycle performance of the sample was excellent.
实施例4Example 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：A preparation method of lithium-ion battery negative electrode material SnS/ND-CN, comprising the following steps:
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-C3N4前驱体；将1g的g-C3N4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；Step 1: Put melamine into a porcelain boat and place it in a muffle furnace for calcination at 650°C for 3.5 hours to obtain a gC 3 N 4 precursor; mix 1 g of gC 3 N 4 precursor with 2 g of magnesium powder and place in Incubate at 725°C for 3.5h in an argon atmosphere, wash the obtained powder three times with acetic acid and water, and then vacuum-dry at 65°C for 11h to obtain ND-CN;
步骤2：将1.2gND-CN加入到50ml乙二醇中磁力搅拌20min并溶解后再加入0.8g的CN2H4S溶解得溶液B；Step 2: Add 1.2g ND-CN to 50ml ethylene glycol and stir magnetically for 20min and dissolve, then add 0.8g CN 2 H 4 S to dissolve to obtain solution B;
步骤3：按元素摩尔比Sn:S＝0.5:3取SnCl2·2H2O和溶液B并将SnCl2·2H2O加入到溶液B中磁力搅拌20min并溶解得溶液C；Step 3: Take SnCl 2 ·2H 2 O and solution B according to the element molar ratio Sn:S=0.5:3, add SnCl 2 ·2H 2 O to solution B and magnetically stir for 20 minutes and dissolve to obtain solution 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％；Step 4: Put solution C into a hydrothermal kettle and place it in a homogeneous hydrothermal reactor for hydrothermal reaction at 170°C for 22 hours to obtain a turbid liquid precursor; the filling ratio of the hydrothermal kettle is 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。Step 5: Take out the turbid liquid precursor, alternately centrifuge and wash it with water and absolute ethanol three times, and then vacuum-dry it at 70°C for 10 hours to obtain SnS/ND-CN, a negative electrode material for lithium-ion batteries.
实施例5Example 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：A preparation method of lithium-ion battery negative electrode material SnS/ND-CN, comprising the following steps:
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-C3N4前驱体；将1g的g-C3N4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；Step 1: Put melamine into a porcelain boat and place it in a muffle furnace for calcination at 700°C for 3 hours to obtain a gC 3 N 4 precursor; mix 1 g of gC 3 N 4 precursor with 3 g of magnesium powder and Keep warm at 775°C for 2.5h in air atmosphere, wash the obtained powder three times with acetic acid and water, and then vacuum-dry at 75°C for 9h to obtain ND-CN;
步骤2：将1.4gND-CN加入到60ml乙二醇中磁力搅拌40min并溶解后再加入0.7g的CN2H4S溶解得溶液B；Step 2: Add 1.4g ND-CN to 60ml ethylene glycol and stir magnetically for 40min and dissolve, then add 0.7g CN 2 H 4 S to dissolve to obtain solution B;
步骤3：按元素摩尔比Sn:S＝2:0.9取SnCl2·2H2O和溶液B并将SnCl2·2H2O加入到溶液B中磁力搅拌40min并溶解得溶液C；Step 3: Take SnCl 2 ·2H 2 O and solution B according to the element molar ratio Sn:S=2:0.9, add SnCl 2 ·2H 2 O to solution B and magnetically stir for 40 minutes and dissolve to obtain solution 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％；Step 4: Put solution C into a hydrothermal kettle and place it in a homogeneous hydrothermal reactor for hydrothermal reaction at 190°C for 19 hours to obtain a turbid liquid precursor; the filling ratio of the hydrothermal kettle is 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。Step 5: Take out the turbid liquid precursor, alternately centrifuge and wash it with water and absolute ethanol three times, and then vacuum-dry it at 80°C for 8 hours to obtain SnS/ND-CN, a negative electrode material for lithium-ion batteries.
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。The above-mentioned embodiments are preferred examples for realizing the present invention, and the present invention is not limited to the above-mentioned embodiments. Any non-essential additions and substitutions made by those skilled in the art according to the technical features of the technical solution of the present invention shall fall within the protection scope of the present invention.
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