CN110571436A - Preparation method of three-dimensional porous carbon-supported sheet-like molybdenum disulfide current collector for lithium metal anode - Google Patents

Preparation method of three-dimensional porous carbon-supported sheet-like molybdenum disulfide current collector for lithium metal anode Download PDF

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CN110571436A
CN110571436A CN201910785543.1A CN201910785543A CN110571436A CN 110571436 A CN110571436 A CN 110571436A CN 201910785543 A CN201910785543 A CN 201910785543A CN 110571436 A CN110571436 A CN 110571436A
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dimensional porous
molybdenum disulfide
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何春年
汤林生
赵乃勤
师春生
刘恩佐
马丽颖
沙军威
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Tianjin University
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    • HELECTRICITY
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    • HELECTRICITY
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    • HELECTRICITY
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Abstract

The invention relates to a preparation method of a three-dimensional porous carbon loaded flaky molybdenum disulfide current collector for a lithium metal cathode, which comprises the following steps: (1) adding a molybdenum source, a sulfur source, a carbon source and a salt template into deionized water for dissolving to prepare a uniform and transparent precursor solution; (2) freeze drying to obtain dry solid powder, and grinding to obtain a mixed powder precursor; (3) is arranged in a hearth of the tubular furnace; heating to 500-750 ℃ in an inert gas atmosphere, preserving heat for a period of time, and then rapidly cooling to obtain a calcined product; (4) carrying out suction filtration, removing NaCl, and drying to obtain the three-dimensional porous carbon loaded flaky molybdenum disulfide material; (5) and preparing the three-dimensional porous carbon loaded flaky molybdenum disulfide composite current collector.

Description

用于锂金属负极的三维多孔碳负载片状二硫化钼集流体的制 备方法Fabrication of three-dimensional porous carbon-supported sheet-like molybdenum disulfide current collectors for lithium metal anodes backup method

技术领域technical field

本发明属于锂金属电池电极材料技术领域,具体涉及一种三维多孔碳负载二硫化钼集流体的制备方法,能有效抑制锂金属沉积脱附过程中锂枝晶的产生,和锂金属无序沉积问题以及进一步产生死锂造成电池容量衰减的问题。The invention belongs to the technical field of lithium metal battery electrode materials, and in particular relates to a preparation method of a three-dimensional porous carbon-supported molybdenum disulfide current collector, which can effectively inhibit the generation of lithium dendrites during the deposition and desorption of lithium metal, and prevent the disordered deposition of lithium metal. problems and further production of dead lithium causing battery capacity fading.

背景技术Background technique

随着电动汽车,家用电子产品以及国家电网的快速发展,人们对高能量密度可充电电池的要求越来越高,传统的锂离子电池由于其工作原理、原料和现代科学技术等问题,已不能满足人们的储能需求。在这种背景下,锂金属具有最高的理论比容量(3860mAh g-1)、最低电化学电位(3.04V vs.标准氢电极)和极低的密度(0.53g cm-3)等优点,成为最有希望的下一代高能量密度电池负极材料,特别是对锂-硫和锂-氧电池系统来说。然而,一些问题如形成不稳定固态电解质膜导致锂金属和电解液反复消耗,降低电池的库伦效率和使用寿命,不可控锂枝晶生长可能会刺破电池隔膜造成电池短路,巨大的体积膨胀会破坏电池结构等会引发严重的安全和可循环利用问题,阻碍了锂金属负极的实际应用。With the rapid development of electric vehicles, household electronic products and the national grid, people have higher and higher requirements for high-energy-density rechargeable batteries. Traditional lithium-ion batteries cannot be Meet people's energy storage needs. In this context, Li metal has the advantages of the highest theoretical specific capacity (3860mAh g -1 ), the lowest electrochemical potential (3.04V vs. standard hydrogen electrode), and the extremely low density (0.53g cm -3 ), becoming the The most promising anode materials for next-generation high-energy-density batteries, especially for lithium-sulfur and lithium-oxygen battery systems. However, some problems such as the formation of an unstable solid electrolyte membrane lead to repeated consumption of lithium metal and electrolyte, which reduces the coulombic efficiency and service life of the battery, the uncontrollable growth of lithium dendrites may puncture the battery separator and cause the battery to short circuit, and the huge volume expansion will Destruction of the battery structure, etc. will cause serious safety and recyclability issues, hindering the practical application of lithium metal anodes.

引导锂金属的有序沉积,抑制锂枝晶的生长和锂沉积脱附过程中的体积膨胀可以有效提高锂金属负极的库伦效率和循环寿命。近年来,在三维多孔集流体上负载亲锂种子被广泛用于锂金属负极。一方面三维集流体具有高比表面积可以有效降低电极的局部电流密度从而使锂金属沉积更加均匀;另一方面,多孔结构有足够的空间储存锂,抑制锂枝晶的生长。而亲锂种子可以引导锂金属在整个集流体内部均匀沉积。但目前研究都主要是负载颗粒状亲锂材料或者二次负载片状亲锂材料,与基体的结合并不强,在锂金属沉积脱附过程中,可能会从基体脱落甚至团聚,亲锂材料的不均匀分布反而会促进锂金属的不均匀沉积,降低电池的库伦效率和使用寿命。Guiding the ordered deposition of Li metal, suppressing the growth of Li dendrites and volume expansion during Li deposition and desorption can effectively improve the Coulombic efficiency and cycle life of Li metal anodes. In recent years, lithiophilic seeds supported on three-dimensional porous current collectors have been widely used for Li metal anodes. On the one hand, the high specific surface area of the three-dimensional current collector can effectively reduce the local current density of the electrode and make the lithium metal deposition more uniform; on the other hand, the porous structure has enough space to store lithium and inhibit the growth of lithium dendrites. The lithiophilic seeds can guide the uniform deposition of Li metal inside the entire current collector. However, the current research mainly focuses on supporting granular lithiophilic materials or secondary supporting flaky lithiophilic materials, which are not strongly bonded to the matrix. During the deposition and desorption of lithium metal, they may fall off or even agglomerate from the matrix. The uneven distribution of lithium metal will promote the uneven deposition of lithium metal, reducing the coulombic efficiency and service life of the battery.

因此通过一步法制备具有大比表面积的三维多孔碳集流体负载片状二硫化钼亲锂材料可以有效解决该问题。利用片状结构来提高亲锂材料和基体的接触面积来提高结合力,使得电极的结构在长循环中得以保持。亲锂材料促进锂金属的均匀沉积,三维多孔集流体提供大比表面积降低相对电流密度和孔洞来储存锂,最终得到电化学性能优异的锂金属电池负极材料。Therefore, the preparation of three-dimensional porous carbon current collector-supported sheet-like molybdenum disulfide lithiophilic materials with large specific surface area by one-step method can effectively solve this problem. The sheet-like structure is used to increase the contact area between the lithiophilic material and the substrate to improve the binding force, so that the structure of the electrode can be maintained during long cycles. The lithiophilic material promotes the uniform deposition of lithium metal, and the three-dimensional porous current collector provides a large specific surface area to reduce the relative current density and pores to store lithium, and finally obtain a lithium metal battery anode material with excellent electrochemical performance.

发明内容SUMMARY OF THE INVENTION

针对现有技术的不足,本发明拟解决的技术问题是,提供一种可有效引导锂金属在集流体内部均匀沉积并抑制锂枝晶产生的三维多孔碳负载二硫化钼集流体用于锂金属电池,可有效提高电池的库伦效率和循环稳定性。技术方案如下:In view of the deficiencies of the prior art, the technical problem to be solved by the present invention is to provide a three-dimensional porous carbon-supported molybdenum disulfide current collector that can effectively guide the uniform deposition of lithium metal in the current collector and suppress the generation of lithium dendrites for lithium metal The battery can effectively improve the coulombic efficiency and cycle stability of the battery. The technical solution is as follows:

一种用于锂金属负极的三维多孔碳负载片状二硫化钼集流体的制备方法,包括下列步骤:A method for preparing a three-dimensional porous carbon-supported sheet-like molybdenum disulfide current collector for lithium metal negative electrodes, comprising the following steps:

(1)以蔗糖、葡萄糖、柠檬酸、淀粉中的一种或几种混合为碳源,以钼酸铵为钼源,以硫脲为硫源,以硫酸钠、氯化钠、碳酸钠、硅酸钠中的一种或几种混合为模板,以钼源中的钼原子、硫源中的硫原子、碳源中的碳原子的摩尔比为1:(2~10):(50~500)计,将钼源、硫源、碳源和盐模板加入去离子水中溶解,配成均一透明的前驱体溶液;(1) Mix one or more of sucrose, glucose, citric acid and starch as carbon source, use ammonium molybdate as molybdenum source, use thiourea as sulfur source, use sodium sulfate, sodium chloride, sodium carbonate, One or more of the sodium silicates are mixed as templates, and the molar ratio of molybdenum atoms in the molybdenum source, sulfur atoms in the sulfur source, and carbon atoms in the carbon source is 1: (2~10): (50~ 500), adding molybdenum source, sulfur source, carbon source and salt template into deionized water to dissolve, to prepare a uniform and transparent precursor solution;

(2)将上一步制备的前驱体溶液进行冷冻干燥,得到干燥固体粉末,研磨后得到混合粉末前驱体;(2) freeze-drying the precursor solution prepared in the previous step to obtain a dry solid powder, and grind to obtain a mixed powder precursor;

(3)将上一步得到的混合粉末前驱体置于管式炉炉膛内;在惰性气体氛围下,以1~10℃的升温速度升温至500~750℃,保温一段时间,之后快速降温冷却,得到煅烧产物;(3) placing the mixed powder precursor obtained in the previous step in the hearth of the tubular furnace; in an atmosphere of inert gas, the temperature is raised to 500-750°C at a heating rate of 1-10°C, kept for a period of time, and then rapidly cooled for cooling. to obtain a calcined product;

(4)使用去离子水将上一步得到的煅烧产物进行抽滤,除去NaCl,干燥后制得三维多孔碳负载片状二硫化钼材料;(4) using deionized water to carry out suction filtration of the calcined product obtained in the previous step, removing NaCl, and drying to obtain a three-dimensional porous carbon-supported sheet molybdenum disulfide material;

(5)将步骤(4)中制备的三维多孔碳负载片状二硫化钼材料与聚偏氟乙烯(PVDF)以8:(1~2)的质量配比混合,再加入适量氮甲基吡咯烷酮(NMP)配成浆料,混合均匀后涂抹在铜箔上后,烘干后制得三维多孔碳负载片状二硫化钼复合集流体。(5) Mix the three-dimensional porous carbon-supported sheet molybdenum disulfide material prepared in step (4) with polyvinylidene fluoride (PVDF) in a mass ratio of 8:(1-2), and then add an appropriate amount of nitrogen methyl pyrrolidone (NMP) into a slurry, mixed evenly, smeared on the copper foil, and dried to obtain a three-dimensional porous carbon-supported sheet-like molybdenum disulfide composite current collector.

步骤(3)中降温速度平均为50~100℃/min。In step (3), the cooling rate is 50-100°C/min on average.

与现有技术相比,本发明方法具有以下优势:(1)三维多孔碳负载片状二硫化钼复合材料是利用一步法制备的,且三维碳与片状二硫化钼之间接触面积非常大,所以三维碳与二硫化钼之间的结合非常紧密,使得二硫化钼在锂金属电池循环过程中不易发生位置和形状的变化;(2)二硫化钼可以有效改善三维碳基体的亲锂性,促进锂金属在整个三维集流体内部均匀沉积;(3)三维多孔结构可容纳大量的锂金属,从而可以减缓锂金属负极在充放电过程中的体积变化,得到体积稳定的锂金属负极;(4)三维孔结构增大了电极的比表面积,降低了电极的有效电流密度,从而有效抑制锂枝晶的产生。Compared with the prior art, the method of the present invention has the following advantages: (1) The three-dimensional porous carbon-supported sheet-like molybdenum disulfide composite material is prepared by a one-step method, and the contact area between the three-dimensional carbon and the sheet-like molybdenum disulfide is very large , so the combination between the three-dimensional carbon and molybdenum disulfide is very close, so that the position and shape of molybdenum disulfide are not easily changed during the cycling process of lithium metal batteries; (2) molybdenum disulfide can effectively improve the lithophilicity of the three-dimensional carbon matrix. , to promote the uniform deposition of lithium metal inside the entire three-dimensional current collector; (3) the three-dimensional porous structure can accommodate a large amount of lithium metal, which can slow down the volume change of the lithium metal anode during charging and discharging, and obtain a volume-stable lithium metal anode; ( 4) The three-dimensional pore structure increases the specific surface area of the electrode and reduces the effective current density of the electrode, thereby effectively inhibiting the generation of lithium dendrites.

附图说明Description of drawings

图1为本发明实施例1所制得的MoS2@3DC粉末SEM图像;Fig. 1 is the SEM image of MoS 2 @3DC powder prepared in Example 1 of the present invention;

图2为本发明实施例1所制备的MoS2@3DC粉末的TEM图像;2 is a TEM image of MoS 2 @3DC powder prepared in Example 1 of the present invention;

图3为在本发明实施例1所制备的MoS2@3DC集流体上沉积2.0mAh cm-2和5.0mAhcm-2的锂金属后的SEM图像;Fig. 3 is the SEM image after depositing 2.0mAh cm -2 and 5.0mAhcm -2 lithium metal on the MoS 2 @3DC current collector prepared in Example 1 of the present invention;

图4为实施例1所制得的MoS2@3DC集流体用于负载锂金属的循环库伦效率。FIG. 4 shows the cyclic Coulomb efficiency of the MoS 2 @3DC current collector prepared in Example 1 for supporting lithium metal.

本发明未述及之处适用于现有技术。What is not described in the present invention applies to the prior art.

以下给出本发明制备方法的具体实施例。这些实施例仅用于详细说明本发明制备方法,并不限制本申请权利要求的保护范围。Specific examples of the preparation method of the present invention are given below. These examples are only used to illustrate the preparation method of the present invention in detail, and do not limit the protection scope of the claims of the present application.

具体实施方式Detailed ways

下面首先介绍本发明的技术路线:Below first introduce the technical route of the present invention:

MoS2@3DC复合集流体的制备方法采用以下工艺: The preparation method of MoS2@3DC composite current collector adopts the following process:

(1)以蔗糖、葡萄糖、柠檬酸、淀粉中的一种或几种混合为碳源,以钼酸铵为钼源,以硫脲为硫源,以硫酸钠、氯化钠、碳酸钠、硅酸钠中的一种或几种混合为模板,以钼源中的钼原子、硫源中的硫原子、碳源中的碳原子的摩尔比为1:(2~10):(50~500)计,将钼源、硫源、碳源和盐模板加入去离子水中溶解,配成溶液搅拌3小时以上,得到均一透明的前驱体溶液;(1) Mix one or more of sucrose, glucose, citric acid and starch as carbon source, use ammonium molybdate as molybdenum source, use thiourea as sulfur source, use sodium sulfate, sodium chloride, sodium carbonate, One or more of the sodium silicates are mixed as templates, and the molar ratio of molybdenum atoms in the molybdenum source, sulfur atoms in the sulfur source, and carbon atoms in the carbon source is 1: (2~10): (50~ 500), adding molybdenum source, sulfur source, carbon source and salt template into deionized water to dissolve, dubbing the solution and stirring for more than 3 hours to obtain a uniform and transparent precursor solution;

(2)将上一步制备的前驱体溶液置于冰箱中-20℃条件下冷冻48h以上或用液氮快速冷冻,之后置于真空冷冻干燥机中-50℃,20Pa条件下冷冻干燥48h左右,得到干燥固体粉末,研磨后得到混合粉末前驱体;(2) The precursor solution prepared in the previous step was placed in a refrigerator at -20°C for more than 48 hours or quickly frozen with liquid nitrogen, and then placed in a vacuum freeze dryer at -50°C and freeze-dried at 20Pa for about 48 hours. The dry solid powder is obtained, and the mixed powder precursor is obtained after grinding;

(3)将上一步得到的粉末前驱体取10g左右平铺于石英舟,再将石英舟置于管式炉炉膛内;以N2、He或Ar中的一种或混合气体作为惰性气体源,先以流量500ccm通入惰性气体10~20分钟以排除空气,再以惰性气体作为载气,流量固定在50~500ccm,以1~10℃的升温速度升温至500~750℃,保温1~2h,之后快速降温冷却(降温速度平均为50~100℃/min),得到煅烧产物;(3) take about 10g of the powder precursor obtained in the previous step and spread it on a quartz boat, and then place the quartz boat in the furnace chamber of the tubular furnace; use one of N 2 , He or Ar or a mixed gas as an inert gas source , first pass the inert gas at a flow rate of 500 ccm for 10 to 20 minutes to remove the air, and then use the inert gas as the carrier gas, the flow rate is fixed at 50 ~ 500 ccm, and the temperature is raised to 500 ~ 750 ° C at a heating rate of 1 ~ 10 ° C, and the temperature is kept for 1 ~ 2h, then rapid cooling and cooling (the average cooling rate is 50-100°C/min) to obtain a calcined product;

(4)使用去离子水将上一步得到的煅烧产物进行抽滤,除去NaCl,后在70℃真空干燥箱中干燥得到三维多孔碳负载片状二硫化钼材料;(4) using deionized water to perform suction filtration on the calcined product obtained in the previous step to remove NaCl, and then drying in a 70°C vacuum drying oven to obtain a three-dimensional porous carbon-supported sheet molybdenum disulfide material;

(5)将步骤(4)中制备的三维多孔碳负载片状二硫化钼材料与聚偏氟乙烯(PVDF)以8:(1~2)的质量配比混合,再加入适量氮甲基吡咯烷酮(NMP)配成浆料,磁力搅拌4h以上,使用厚度为100~1000mm的刮刀均匀涂抹在铜箔上后,使用加热台在50℃~80℃下烘干,使用裁片机裁成圆片,得到三维多孔碳负载片状二硫化钼复合集流体。(5) Mix the three-dimensional porous carbon-supported sheet molybdenum disulfide material prepared in step (4) with polyvinylidene fluoride (PVDF) in a mass ratio of 8:(1-2), and then add an appropriate amount of nitrogen methyl pyrrolidone (NMP) into slurry, stir magnetically for more than 4 hours, spread evenly on the copper foil with a scraper with a thickness of 100-1000 mm, use a heating table to dry at 50 ℃ ~ 80 ℃, and use a cutting machine to cut into discs , a three-dimensional porous carbon-supported sheet-like molybdenum disulfide composite current collector was obtained.

(6)将步骤(5)中制备的三维多孔碳负载片状二硫化钼复合集流体组装成电池,对电极为锂片,首先在0.01V-3V的电压范围内以0.05mA cm-2的电流密度循环5圈,以形成稳定的SEI膜,然后以1.0~10.0mA cm-2的电流密度沉积金属锂0.2~10h,拆开电池,即可得到不同容量的金属锂负极。(6) Assembling the three-dimensional porous carbon-supported sheet-like molybdenum disulfide composite current collector prepared in step (5) into a battery, the counter electrode is a lithium sheet, and firstly in the voltage range of 0.01V-3V at 0.05mA cm -2 The current density was cycled for 5 times to form a stable SEI film, and then metal lithium was deposited at a current density of 1.0-10.0 mA cm -2 for 0.2-10 h, and the battery was disassembled to obtain metal lithium negative electrodes of different capacities.

实施例1Example 1

(1)称取0.3532g钼酸铵、0.3654g硫脲、1.4g柠檬酸、17.55g氯化钠,将混合物溶于100ml去离子水中,磁力搅拌4h得到均匀溶液。将混合均匀的液体倒入培养皿中,随后将培养皿置于冰箱冷冻室-20℃条件下冷冻24h;将冷冻后的样品放于冷冻干燥机内冻干,冻干条件为:-50℃,20Pa,冻干时间24h。将冻干后的样品研磨得到前驱体复合粉末(粉末粒径~100目);取10g至于方舟中,将方舟放入管式炉中,通入500ccm的氩气15min排除空气,再调整为200ccm,并以10℃/min的升温速度升至750℃,保温2h,保温结束后快速冷却至室温,将煅烧后的粉末置于500ml烧杯中,加入400ml去离子水,磁力搅拌30min,使氯化钠全部溶解于水中,随后抽滤,反复三遍后将抽滤后的样品放入70℃真空烘箱中干燥3h,得到三维多孔碳负载二硫化钼复合材料。(1) Weigh 0.3532g of ammonium molybdate, 0.3654g of thiourea, 1.4g of citric acid, and 17.55g of sodium chloride, dissolve the mixture in 100ml of deionized water, and magnetically stir for 4h to obtain a homogeneous solution. Pour the evenly mixed liquid into the petri dish, and then place the petri dish in the freezer of the refrigerator at -20°C for 24 hours; put the frozen samples in a freeze-drying machine for freeze-drying, and freeze-drying conditions are: -50°C , 20Pa, lyophilization time 24h. Grind the freeze-dried sample to obtain the precursor composite powder (powder particle size ~ 100 mesh); take 10 g of the ark, put the ark into a tube furnace, pass 500 ccm of argon for 15 minutes to remove the air, and then adjust to 200 ccm , and raised to 750°C at a heating rate of 10°C/min, kept for 2h, and quickly cooled to room temperature after the heat preservation, placed the calcined powder in a 500ml beaker, added 400ml of deionized water, and magnetically stirred for 30min to make the chlorination All sodium was dissolved in water, followed by suction filtration. After repeated three times, the suction-filtered sample was placed in a 70°C vacuum oven to dry for 3 hours to obtain a three-dimensional porous carbon-supported molybdenum disulfide composite material.

(2)用所制得的粉末材料,聚偏氟乙烯质量比为8:1计,再加入适量NMP混合搅拌4h,用250mm的刮刀涂于铜箔上,并在80℃下烘干,得到集流体。(2) Using the obtained powder material, the mass ratio of polyvinylidene fluoride is 8:1, then adding an appropriate amount of NMP, mixing and stirring for 4 hours, and applying a 250mm spatula on the copper foil, and drying at 80 ° C to obtain collector.

(3)使用MoS2@3DC的锂金属负极的制备。用上述制备的集流体作为阴极,用锂金属作为阳极,组装成半电池,在MoS2@3DC集流体上沉积2.0mAh cm-2的金属锂,拆开电池,即可得到相应的锂金属负极。( 3 ) Preparation of Li metal anode using MoS2@3DC. Using the above-prepared current collector as the cathode and lithium metal as the anode, a half-cell was assembled, 2.0 mAh cm -2 of metallic lithium was deposited on the MoS 2 @3DC current collector, and the battery was disassembled to obtain the corresponding lithium metal negative electrode .

(4)锂金属二次电池的组装。将上述制备得到的锂金属负极与合适的硫正极组装成锂硫电池或与合适的LMO(L为锂,M为过渡金属,O为氧)组装成Li-LMO电池。在本实施例中,采用锂金属作为对电极组装成金属锂半电池。(4) Assembly of the lithium metal secondary battery. The lithium metal negative electrode prepared above is assembled with a suitable sulfur positive electrode to form a lithium-sulfur battery or a Li-LMO battery with a suitable LMO (L is lithium, M is a transition metal, and O is oxygen). In this embodiment, a lithium metal half-cell is assembled by using lithium metal as the counter electrode.

(5)锂金属二次电池的电化学测试。首先在0.01V-3V的电压范围内以0.05mA cm-2的电流密度循环5圈,以得到稳定的SEI膜,然后以1.0mA cm-2的电流密度按2.0mAh cm-2的容量进行充放电循环,截止电压为0.5V。(5) Electrochemical test of lithium metal secondary battery. The stable SEI film was first cycled at a current density of 0.05mA cm -2 for 5 cycles in the voltage range of 0.01V-3V, and then charged at a capacity of 2.0mAh cm -2 at a current density of 1.0mA cm -2 . Discharge cycle with a cut-off voltage of 0.5V.

实施例2Example 2

与实施例1不同的是:(1)称取0.3532g钼酸铵、0.30g硫脲、1.4g柠檬酸、17.55g氯化钠,将混合物溶于100ml去离子水中,磁力搅拌4h得到均匀溶液。将混合均匀的液体倒入培养皿中,随后将培养皿置于冰箱冷冻室-20℃条件下冷冻24h;将冷冻后的样品放于冷冻干燥机内冻干,冻干条件为:-50℃,20Pa,冻干时间24h。将冻干后的样品研磨得到前驱体复合粉末(粉末粒径~100目);取10g至于方舟中,将方舟放入管式炉中,通入500ccm的氩气15min排除空气,再调整为200ccm,并以10℃/min的升温速度升至750℃,保温2h,保温结束后快速冷却至室温,将煅烧后的粉末置于500ml烧杯中,加入400ml去离子水,磁力搅拌30min,使氯化钠全部溶解于水中,随后抽滤,反复三遍后将抽滤后的样品放入70℃真空烘箱中干燥3h,得到三维多孔碳负载二硫化钼复合材料。其余同实施例1,这里不再赘述。Different from Example 1: (1) Weigh 0.3532g of ammonium molybdate, 0.30g of thiourea, 1.4g of citric acid, and 17.55g of sodium chloride, dissolve the mixture in 100ml of deionized water, and magnetically stir for 4h to obtain a uniform solution . Pour the evenly mixed liquid into the petri dish, and then place the petri dish in the freezer of the refrigerator at -20°C for 24 hours; put the frozen samples in a freeze-drying machine for freeze-drying, and freeze-drying conditions are: -50°C , 20Pa, lyophilization time 24h. Grind the freeze-dried sample to obtain the precursor composite powder (powder particle size ~ 100 mesh); take 10 g of the ark, put the ark into a tube furnace, pass 500 ccm of argon for 15 minutes to remove the air, and then adjust to 200 ccm , and raised to 750°C at a heating rate of 10°C/min, kept for 2h, and quickly cooled to room temperature after the heat preservation, placed the calcined powder in a 500ml beaker, added 400ml of deionized water, and magnetically stirred for 30min to make the chlorination All sodium was dissolved in water, followed by suction filtration. After repeated three times, the suction-filtered sample was placed in a 70°C vacuum oven to dry for 3 hours to obtain a three-dimensional porous carbon-supported molybdenum disulfide composite material. The rest are the same as in Embodiment 1, and are not repeated here.

所得集流体存在三维多孔结构,但是碳壁上有许多颗粒,猜测是钼酸铵分解所得氧化钼未完全被硫脲硫化所遗留的。The obtained current collector has a three-dimensional porous structure, but there are many particles on the carbon wall. It is speculated that the molybdenum oxide obtained by the decomposition of ammonium molybdate is not completely left by thiourea vulcanization.

实施例3Example 3

与实施例1不同的是:(1)称取0.3532g钼酸铵、0.3654g g硫脲、1g柠檬酸、17.55g氯化钠,将混合物溶于100ml去离子水中,磁力搅拌4h得到均匀溶液。将混合均匀的液体倒入培养皿中,随后将培养皿置于冰箱冷冻室-20℃条件下冷冻24h;将冷冻后的样品放于冷冻干燥机内冻干,冻干条件为:-50℃,20Pa,冻干时间24h。将冻干后的样品研磨得到前驱体复合粉末(粉末粒径~100目);取10g至于方舟中,将方舟放入管式炉中,通入500ccm的氩气15min排除空气,再调整为200ccm,并以10℃/min的升温速度升至750℃,保温2h,保温结束后快速冷却至室温,将煅烧后的粉末置于500ml烧杯中,加入400ml去离子水,磁力搅拌30min,使氯化钠全部溶解于水中,随后抽滤,反复三遍后将抽滤后的样品放入70℃真空烘箱中干燥3h,得到三维多孔碳负载二硫化钼复合材料。其余同实施例1,这里不再赘述。Different from Example 1: (1) Weigh 0.3532g of ammonium molybdate, 0.3654g of thiourea, 1g of citric acid, and 17.55g of sodium chloride, dissolve the mixture in 100ml of deionized water, and magnetically stir for 4h to obtain a uniform solution. Pour the evenly mixed liquid into the petri dish, and then place the petri dish in the freezer of the refrigerator at -20°C for 24 hours; put the frozen samples in a freeze-drying machine for freeze-drying, and freeze-drying conditions are: -50°C , 20Pa, lyophilization time 24h. Grind the freeze-dried sample to obtain the precursor composite powder (powder particle size ~ 100 mesh); take 10 g of the ark, put the ark into a tube furnace, pass 500 ccm of argon for 15 minutes to remove the air, and then adjust to 200 ccm , and the temperature was raised to 750°C at a heating rate of 10°C/min, kept for 2 hours, and then quickly cooled to room temperature after the heat preservation. The calcined powder was placed in a 500ml beaker, 400ml of deionized water was added, and magnetic stirring was performed for 30min to make the chlorination All sodium was dissolved in water, followed by suction filtration. After repeated three times, the suction-filtered sample was placed in a 70°C vacuum oven to dry for 3 hours to obtain a three-dimensional porous carbon-supported molybdenum disulfide composite material. The rest are the same as in Embodiment 1, and are not repeated here.

所得集流体存在三维多孔结构,也没有颗粒状物质存在,但是三维结构破碎不完整。The obtained current collector has a three-dimensional porous structure and no particulate matter, but the three-dimensional structure is incompletely broken.

实施例4Example 4

与实施例1不同的是:(1)称取1.4g柠檬酸、17.55g氯化钠,将混合物溶于100ml去离子水中,磁力搅拌4h得到均匀溶液。将混合均匀的液体倒入培养皿中,随后将培养皿置于冰箱冷冻室-20℃条件下冷冻24h;将冷冻后的样品放于冷冻干燥机内冻干,冻干条件为:-50℃,20Pa,冻干时间24h。将冻干后的样品研磨得到前驱体复合粉末(粉末粒径~100目);取10g至于方舟中,将方舟放入管式炉中,通入500ccm的氩气15min排除空气,再调整为200ccm,并以10℃/min的升温速度升至750℃,保温2h,保温结束后快速冷却至室温,将煅烧后的粉末置于500ml烧杯中,加入400ml去离子水,磁力搅拌30min,使氯化钠全部溶解于水中,随后抽滤,反复三遍后将抽滤后的样品放入70℃真空烘箱中干燥3h,得到三维多孔碳负载二硫化钼复合材料。其余同实施例1,这里不再赘述。The difference from Example 1 is: (1) Weigh 1.4 g of citric acid and 17.55 g of sodium chloride, dissolve the mixture in 100 ml of deionized water, and stir magnetically for 4 hours to obtain a uniform solution. Pour the evenly mixed liquid into the petri dish, and then place the petri dish in the freezer of the refrigerator at -20°C for 24 hours; put the frozen samples in a freeze-drying machine for freeze-drying, and freeze-drying conditions are: -50°C , 20Pa, lyophilization time 24h. Grind the freeze-dried sample to obtain the precursor composite powder (powder particle size ~ 100 mesh); take 10 g of the ark, put the ark into a tube furnace, pass 500 ccm of argon for 15 minutes to remove the air, and then adjust to 200 ccm , and raised to 750°C at a heating rate of 10°C/min, kept for 2h, and quickly cooled to room temperature after the heat preservation, placed the calcined powder in a 500ml beaker, added 400ml of deionized water, and magnetically stirred for 30min to make the chlorination All sodium was dissolved in water, followed by suction filtration. After repeated three times, the suction-filtered sample was placed in a 70°C vacuum oven to dry for 3 hours to obtain a three-dimensional porous carbon-supported molybdenum disulfide composite material. The rest are the same as in Embodiment 1, and are not repeated here.

所得集流体存在三维多孔结构,但是根据XRD测试显示其中没有MoS2存在,记为3DC。The obtained current collector has a three - dimensional porous structure, but no MoS2 is present in it according to the XRD test, denoted as 3DC.

Claims (3)

1.一种用于锂金属负极的三维多孔碳负载片状二硫化钼集流体的制备方法,包括下列步骤:1. a preparation method for a three-dimensional porous carbon-supported sheet molybdenum disulfide current collector for lithium metal negative electrode, comprising the following steps: (1)以蔗糖、葡萄糖、柠檬酸、淀粉中的一种或几种混合为碳源,以钼酸铵为钼源,以硫脲为硫源,以硫酸钠、氯化钠、碳酸钠、硅酸钠中的一种或几种混合为模板,以钼源中的钼原子、硫源中的硫原子、碳源中的碳原子的摩尔比为1:(2~10):(50~500)计,将钼源、硫源、碳源和盐模板加入去离子水中溶解,配成均一透明的前驱体溶液。(1) Mix one or more of sucrose, glucose, citric acid and starch as carbon source, use ammonium molybdate as molybdenum source, use thiourea as sulfur source, use sodium sulfate, sodium chloride, sodium carbonate, One or more of the sodium silicates are mixed as templates, and the molar ratio of molybdenum atoms in the molybdenum source, sulfur atoms in the sulfur source, and carbon atoms in the carbon source is 1: (2~10): (50~ 500), molybdenum source, sulfur source, carbon source and salt template were added into deionized water to dissolve, to prepare a uniform and transparent precursor solution. (2)将上一步制备的前驱体溶液进行冷冻干燥,得到干燥固体粉末,研磨后得到混合粉末前驱体;(2) freeze-drying the precursor solution prepared in the previous step to obtain a dry solid powder, and grind to obtain a mixed powder precursor; (3)将上一步得到的混合粉末前驱体置于管式炉炉膛内;在惰性气体氛围下,以1~10℃的升温速度升温至500~750℃,保温一段时间,之后快速降温冷却,得到煅烧产物;(3) placing the mixed powder precursor obtained in the previous step in the hearth of the tubular furnace; in an atmosphere of inert gas, the temperature is raised to 500-750°C at a heating rate of 1-10°C, kept for a period of time, and then rapidly cooled for cooling. to obtain a calcined product; (4)使用去离子水将上一步得到的煅烧产物进行抽滤,除去NaCl,干燥后制得三维多孔碳负载片状二硫化钼材料;(4) using deionized water to carry out suction filtration of the calcined product obtained in the previous step, removing NaCl, and drying to obtain a three-dimensional porous carbon-supported sheet molybdenum disulfide material; (5)将步骤(4)中制备的三维多孔碳负载片状二硫化钼材料与聚偏氟乙烯(PVDF)以8:(1~2)的质量配比混合,再加入适量氮甲基吡咯烷酮(NMP)配成浆料,混合均匀后涂抹在铜箔上后,烘干后制得三维多孔碳负载片状二硫化钼复合集流体。(5) Mix the three-dimensional porous carbon-supported sheet molybdenum disulfide material prepared in step (4) with polyvinylidene fluoride (PVDF) in a mass ratio of 8:(1-2), and then add an appropriate amount of nitrogen methyl pyrrolidone (NMP) into a slurry, mixed evenly, smeared on the copper foil, and dried to obtain a three-dimensional porous carbon-supported sheet-like molybdenum disulfide composite current collector. 2.根据权利要求1所述的制备方法,其特征在于,步骤(3)中降温速度平均为50~100℃/min。2 . The preparation method according to claim 1 , wherein the cooling rate in step (3) is an average of 50-100° C./min. 3 . 3.利用权利要求1制备的三维多孔碳负载片状二硫化钼复合集流体组装成电池,对电极为锂片。3. The three-dimensional porous carbon-supported sheet molybdenum disulfide composite current collector prepared by claim 1 is assembled into a battery, and the counter electrode is a lithium sheet.
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CN114520327A (en) * 2020-11-20 2022-05-20 中国科学院大连化学物理研究所 A kind of preparation method and application of mesoporous molybdenum disulfide/carbon composite material
CN114520327B (en) * 2020-11-20 2023-11-07 中国科学院大连化学物理研究所 Preparation method and application of mesoporous molybdenum disulfide/carbon composite material
CN113314695A (en) * 2021-04-30 2021-08-27 天津大学 Method for improving performance of carbon fluoride battery material by salt template method
CN113735173A (en) * 2021-09-08 2021-12-03 北京航空航天大学 A kind of molybdenum sulfide-molybdenum nitride composite material and its preparation method and application
CN113903912A (en) * 2021-09-30 2022-01-07 常熟理工学院 A kind of preparation method of carbon-supported titanium carbide material, product obtained therefrom and application
CN114678508A (en) * 2022-04-13 2022-06-28 电子科技大学长三角研究院(湖州) Carbon-based supported metal sulfide composite material and preparation method and application thereof
CN115000370A (en) * 2022-06-02 2022-09-02 烟台大学 Molybdenum dioxide confinement growth and modification three-dimensional porous carbon composite electrode material and preparation method thereof

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Application publication date: 20191213