WO2017139996A1 - Preparation method of three-dimensional carbon nanotube/nitrogen-doped graphene/sulfur electrode slice - Google Patents

Preparation method of three-dimensional carbon nanotube/nitrogen-doped graphene/sulfur electrode slice Download PDF

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WO2017139996A1
WO2017139996A1 PCT/CN2016/074195 CN2016074195W WO2017139996A1 WO 2017139996 A1 WO2017139996 A1 WO 2017139996A1 CN 2016074195 W CN2016074195 W CN 2016074195W WO 2017139996 A1 WO2017139996 A1 WO 2017139996A1
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electrode sheet
electrode slice
solution
sulfur
electrode
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Chinese (zh)
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肖丽芳
钟玲珑
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肖丽芳
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • 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
    • 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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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

Definitions

  • the invention relates to the synthesis of nano materials, in particular to a preparation method of a cathode material for a lithium sulfur battery.
  • the lithium-sulfur battery is a battery system in which lithium metal is used as a negative electrode and elemental sulfur is used as a positive electrode.
  • Lithium-sulfur batteries have two discharge platforms (about 2.4V and 2.1V), but their electrochemical reaction mechanism is complicated. Lithium-sulfur batteries have the advantages of high specific energy (2600Wh/kg), high specific capacity (1675mAh/g), low cost, etc., and are considered to be promising new generation batteries.
  • problems such as low utilization rate of active materials, low cycle life and poor safety, which seriously restricts the development of lithium-sulfur batteries.
  • Elemental sulfur is an electron and ion insulator, and the room temperature conductivity is low (5 ⁇ 10 -30 S ⁇ cm -1 ). Since there is no ionic sulfur, it is used as The activation of the positive electrode material is difficult; (2) the high polylithium polysulfide Li 2 S n (8>n ⁇ 4) generated during the electrode reaction is easily dissolved in the electrolyte, forming a concentration difference between the positive and negative electrodes. Under the action of the concentration gradient, it migrates to the negative electrode, and the high poly lithium polysulfide is reduced by the lithium metal to the oligomeric lithium polysulfide.
  • the oligomeric lithium polysulfide aggregates at the negative electrode, eventually forming a concentration difference between the two electrodes, and then migrating to the positive electrode to be oxidized to a highly polylithium polysulfide. This phenomenon is known as the shuttle effect, which reduces the utilization of sulfur active substances.
  • insoluble Li 2 S and Li 2 S 2 are deposited on the surface of the lithium negative electrode, which further deteriorates the performance of the lithium-sulfur battery; (3) the final product of the reaction, Li 2 S, is also an electronic insulator, which is deposited on the sulfur electrode, and lithium slow ion mobility in the solid state lithium sulfide, the slow electrochemical reaction kinetics; different density (4) sulfur and Li 2 S final product when sulfur is expanded to about 79% of the volume of lithium, Li 2 easily lead The powdering of S causes safety problems in lithium-sulfur batteries.
  • the above-mentioned shortcomings restrict the development of lithium-sulfur batteries, which is also the key issue that needs to be solved in the research of lithium-sulfur batteries.
  • the technical problem to be solved by the present invention is to provide a three-dimensional structure lithium-sulfur battery cathode material, and directly prepare a lithium-sulfur battery positive electrode sheet, the method for preparing three-dimensional carbon materials including sulfur nanoparticles, carbon nanotubes, partial reduction Nitrogen-doped graphene, nano-sulfur particles deposited on carbon nanotubes and nitrogen-doped graphite
  • the three-dimensional surface formed by the olefin which improves the conductivity of sulfur and prevents the dissolution of polysulfide of the discharge product.
  • the invention provides a preparation process of a three-dimensional carbon nanotube/nitrogen-doped graphene/sulfur electrode sheet as follows:
  • Carbon nanotubes, graphite oxide, and polyacrylonitrile were added to N-methylpyrrolidone, and the mixture was uniformly stirred, and ultrasonically reacted for 30 to 120 minutes, and then the mixed slurry was applied onto an aluminum foil, and vacuum-dried to obtain an electrode sheet.
  • the obtained electrode sheet is placed in an ammonia-protected muffle furnace, and the temperature is slowly raised to 400-500 ° C at a rate of 3-5 ° C / min, and the reaction is carried out for 0.5-5 hours, and naturally cooled.
  • the mass ratio of the carbon nanotubes, graphene and polyacrylonitrile in the step (1) is 1:1.6-2.4:0.8-1.2, the ultrasonic reaction time is 30-120 minutes, the diameter of the carbon nanotubes is 20-100 nm, and the length is 1-20um;
  • the reaction gas is ammonia gas
  • the temperature rise rate of the muffle furnace is 3-5 ° C / min
  • the reaction temperature is 400-500 ° C
  • the reaction time is 0.5-5 hours
  • the reaction is naturally cooled.
  • the concentration of the Na 2 S 2 O 3 solution in the step (3) is 0.5-2 mol/L; the static moment of the electrode sheet inserted into the Na 2 S 2 O 3 solution is 30-60 minutes; the amount of hydrochloric acid added is just such that the pH of the solution is 6.5. -7.5.
  • the invention adopts the above technical solution, and has the advantages that the graphite oxide is reduced to graphene at a high temperature, and at the same time, nitrogen is still partially retained on the graphene, and the existence of the oxygen atom can be in the process of charging and discharging.
  • the lithium ion reaction provides energy, and on the other hand, the oxygen atoms are able to attract the movement of polysulfides and reduce the shuttle effect.
  • the preparation method comprises the steps of reducing graphite oxide, nitrogen doping and polyacrylonitrile ring forming to improve the reaction efficiency; (2) polyacrylonitrile between the graphene layer and the layer and The graphene and the carbon nanotubes undergo a ring-forming reaction and cross-link together, so that the one-dimensional carbon nanotubes and the two-dimensional graphene form a three-dimensional space, and then the sulfur is stored in the three-dimensional space by in situ reduction. (3) High-conductivity carbon nanotubes and graphene materials can effectively improve the electrical conductivity of the electrode sheets; (4) During the charging and discharging process, the three-dimensional structure is favorable for the lithium ions and electrons to shuttle in the multi-dimensional conduction path.
  • the fully reduced nitrogen-doped graphene contains a part of nitrogen atoms and oxygen atoms, which has an adsorption effect on sulfur, can effectively reduce the shuttle effect and improve the cycle life of the lithium-sulfur battery; 6)
  • the electrode sheet prepared by the invention can be directly used for the positive electrode of the lithium sulfur battery, and no need to add a conductive agent and a binder, thereby greatly reducing the cost of the electrode.
  • 1 is an SEM image of a three-dimensional carbon nanotube/nitrogen-doped graphene/sulfur electrode sheet prepared by the present invention.
  • Electrode preparation and performance test the prepared electrode sheet was used as the positive electrode, the lithium metal plate was used as the counter electrode, CEL GARD 2400 was used as the separator, and 1 mol/L of LiTFSI/DOL-DME (volume ratio 1:1) was used as the electrolyte, 1 mol/ L LiNO3 is an additive, assembled into a button-type battery in a filled glove box, and a constant current charge and discharge test is performed using a Land battery test system.
  • the charge and discharge voltage range is 1-3V, the current density is 1C, and the performance is shown in Table 1.
  • FIG. 1 is an SEM image of a positive electrode material prepared by the present invention. It can be seen from the figure that the positive electrode material has a large number of open three-dimensional pore-like structures, which can provide an ion transport channel and improve the electrical energy of the material. Chemical properties.

Abstract

<sb /> <sb /> <sb />A three-dimensional carbon nanotube/nitrogen-doped graphene/sulfur electrode slice comprises the following steps of: step (1): adding carbon nanotubes, graphite oxide and polyacrylonitrile to N-methyl pyrrolidone, performing ultrasonic treatment, coating an aluminium foil with mixed slurry, and performing vacuum drying to obtain an electrode slice; step (2): putting the obtained electrode slice into a muffle furnace under the protection of ammonia gas, heating to 400-500℃, and naturally cooling; and step (3): completely inserting the electrode slice obtained in the step (2) into a Na2S2O3 solution, and slowly dropwise adding hydrochloric acid to the solution until the PH value of the solution reaches 6.5-7.5, and then taking out the electrode slice, and drying the electrode slice to obtain a positive plate. The prepared electrode slice can be directly applied to the positive electrode of a lithium-sulfur battery without adding a conductive agent and a binder, thus greatly lowering the cost of the electrode.

Description

一种三维碳纳米管/氮掺杂石墨烯/硫电极片的制备方法Method for preparing three-dimensional carbon nanotube/nitrogen-doped graphene/sulfur electrode sheet 技术领域Technical field
本发明涉及纳米材料合成，特别涉及一种锂硫电池正极材料的制备方法。The invention relates to the synthesis of nano materials, in particular to a preparation method of a cathode material for a lithium sulfur battery.
背景技术Background technique
锂硫电池是以金属锂为负极，单质硫为正极的电池体系。锂硫电池的具有两个放电平台(约为2.4V和2.1V)，但其电化学反应机理比较复杂。锂硫电池具有比能量高(2600Wh/kg)、比容量高(1675mAh/g)、成本低等优点，被认为是很有发展前景的新一代电池。但是目前其存在着活性物质利用率低、循环寿命低和安全性差等问题，这严重制约着锂硫电池的发展。造成上述问题的主要原因有以下几个方面：(1)单质硫是电子和离子绝缘体，室温电导率低(5×10-30S·cm-1)，由于没有离子态的硫存在，因而作为正极材料活化困难；(2)在电极反应过程中产生的高聚态多硫化锂Li2Sn(8＞n≥4)易溶于电解液中，在正负极之间形成浓度差，在浓度梯度的作用下迁移到负极，高聚态多硫化锂被金属锂还原成低聚态多硫化锂。随着以上反应的进行，低聚态多硫化锂在负极聚集，最终在两电极之间形成浓度差，又迁移到正极被氧化成高聚态多硫化锂。这种现象被称为飞梭效应，降低了硫活性物质的利用率。同时不溶性的Li2S和Li2S2沉积在锂负极表面，更进一步恶化了锂硫电池的性能；(3)反应最终产物Li2S同样是电子绝缘体，会沉积在硫电极上，而锂离子在固态硫化锂中迁移速度慢，使电化学反应动力学速度变慢；(4)硫和最终产物Li2S的密度不同，当硫被锂化后体积膨胀大约79％，易导致Li2S的粉化，引起锂硫电池的安全问题。上述不足制约着锂硫电池的发展，这也是目前锂硫电池研究需要解决的重点问题。The lithium-sulfur battery is a battery system in which lithium metal is used as a negative electrode and elemental sulfur is used as a positive electrode. Lithium-sulfur batteries have two discharge platforms (about 2.4V and 2.1V), but their electrochemical reaction mechanism is complicated. Lithium-sulfur batteries have the advantages of high specific energy (2600Wh/kg), high specific capacity (1675mAh/g), low cost, etc., and are considered to be promising new generation batteries. However, at present, there are problems such as low utilization rate of active materials, low cycle life and poor safety, which seriously restricts the development of lithium-sulfur batteries. The main causes of the above problems are as follows: (1) Elemental sulfur is an electron and ion insulator, and the room temperature conductivity is low (5 × 10 -30 S·cm -1 ). Since there is no ionic sulfur, it is used as The activation of the positive electrode material is difficult; (2) the high polylithium polysulfide Li 2 S n (8>n≥4) generated during the electrode reaction is easily dissolved in the electrolyte, forming a concentration difference between the positive and negative electrodes. Under the action of the concentration gradient, it migrates to the negative electrode, and the high poly lithium polysulfide is reduced by the lithium metal to the oligomeric lithium polysulfide. As the above reaction proceeds, the oligomeric lithium polysulfide aggregates at the negative electrode, eventually forming a concentration difference between the two electrodes, and then migrating to the positive electrode to be oxidized to a highly polylithium polysulfide. This phenomenon is known as the shuttle effect, which reduces the utilization of sulfur active substances. At the same time, insoluble Li 2 S and Li 2 S 2 are deposited on the surface of the lithium negative electrode, which further deteriorates the performance of the lithium-sulfur battery; (3) the final product of the reaction, Li 2 S, is also an electronic insulator, which is deposited on the sulfur electrode, and lithium slow ion mobility in the solid state lithium sulfide, the slow electrochemical reaction kinetics; different density (4) sulfur and Li 2 S final product when sulfur is expanded to about 79% of the volume of lithium, Li 2 easily lead The powdering of S causes safety problems in lithium-sulfur batteries. The above-mentioned shortcomings restrict the development of lithium-sulfur batteries, which is also the key issue that needs to be solved in the research of lithium-sulfur batteries.
技术问题technical problem
本发明要解决的技术问题是提供一种三维结构锂硫电池正极材料，同时直接制备成锂硫电池正极片的方法，该方法制备出三维的碳材料包括硫纳米颗粒、碳纳米管、部分还原的氮掺杂石墨烯，纳米硫颗粒沉积在碳纳米管和氮掺杂石墨 烯形成的三维空间表面，该设计能改善硫的导电性，而且能够阻止放电产物多硫化物的溶解。The technical problem to be solved by the present invention is to provide a three-dimensional structure lithium-sulfur battery cathode material, and directly prepare a lithium-sulfur battery positive electrode sheet, the method for preparing three-dimensional carbon materials including sulfur nanoparticles, carbon nanotubes, partial reduction Nitrogen-doped graphene, nano-sulfur particles deposited on carbon nanotubes and nitrogen-doped graphite The three-dimensional surface formed by the olefin, which improves the conductivity of sulfur and prevents the dissolution of polysulfide of the discharge product.
问题的解决方案Problem solution
技术解决方案Technical solution
本发明提供一种三维碳纳米管/氮掺杂石墨烯/硫电极片的制备工艺流程如下：The invention provides a preparation process of a three-dimensional carbon nanotube/nitrogen-doped graphene/sulfur electrode sheet as follows:
(1)将碳纳米管、氧化石墨和聚丙烯腈加入到N-甲基吡咯烷酮，搅拌均匀后超声反应30-120分钟，然后混合浆料涂覆到铝箔上，真空干燥得到电极片。(1) Carbon nanotubes, graphite oxide, and polyacrylonitrile were added to N-methylpyrrolidone, and the mixture was uniformly stirred, and ultrasonically reacted for 30 to 120 minutes, and then the mixed slurry was applied onto an aluminum foil, and vacuum-dried to obtain an electrode sheet.
(2)将得到的电极片放入氨气保护的马弗炉内，以3-5℃/min的速度缓慢升温到400-500℃，反应0.5-5小时，自然冷却。(2) The obtained electrode sheet is placed in an ammonia-protected muffle furnace, and the temperature is slowly raised to 400-500 ° C at a rate of 3-5 ° C / min, and the reaction is carried out for 0.5-5 hours, and naturally cooled.
(3)将(2)得到的电极片完全***0.5-2mol/L的Na2S2O3溶液中，静止30-60分钟，然后向溶液中缓慢的滴加1mol/L的盐酸，直到溶液PH＝6.5-7.5，拿出电极片，干燥后得到正极片。(3) Insert the electrode sheet obtained in (2) completely into a 0.5-2 mol/L Na 2 S 2 O 3 solution, stand still for 30-60 minutes, and then slowly add 1 mol/L hydrochloric acid to the solution until the solution PH = 6.5-7.5, take out the electrode sheet, and dry to obtain a positive electrode sheet.
步骤(1)中碳纳米管、石墨烯和聚丙烯腈的质量比为1∶1.6-2.4∶0.8-1.2，超声反应时间为30-120分钟，碳纳米管的直径为20-100nm，长度为1-20um；The mass ratio of the carbon nanotubes, graphene and polyacrylonitrile in the step (1) is 1:1.6-2.4:0.8-1.2, the ultrasonic reaction time is 30-120 minutes, the diameter of the carbon nanotubes is 20-100 nm, and the length is 1-20um;
步骤(2)反应中反应通入气体为氨气，马弗炉的升温速度为3-5℃/min；反应温度为400-500℃；反应时间0.5-5小时；反应完成后自然冷却。In the step (2), the reaction gas is ammonia gas, the temperature rise rate of the muffle furnace is 3-5 ° C / min; the reaction temperature is 400-500 ° C; the reaction time is 0.5-5 hours; and the reaction is naturally cooled.
步骤(3)中Na2S2O3溶液的浓度为0.5-2mol/L；电极片***Na2S2O3溶液静止时间为30-60分钟；盐酸的加入量刚好使溶液的PH＝6.5-7.5。The concentration of the Na 2 S 2 O 3 solution in the step (3) is 0.5-2 mol/L; the static moment of the electrode sheet inserted into the Na 2 S 2 O 3 solution is 30-60 minutes; the amount of hydrochloric acid added is just such that the pH of the solution is 6.5. -7.5.
发明的有益效果Advantageous effects of the invention
有益效果Beneficial effect
本发明采用以上技术方案，其优点在于，氧化石墨在高温下还原为石墨烯，氮掺杂的同时石墨烯上还残留部分氧原子，这部分氧原子的存在一方面可以在充放电过程中与锂离子反应提供能量，另一方面氧原子能够吸引多硫化物的移动，减少飞梭效应。The invention adopts the above technical solution, and has the advantages that the graphite oxide is reduced to graphene at a high temperature, and at the same time, nitrogen is still partially retained on the graphene, and the existence of the oxygen atom can be in the process of charging and discharging. The lithium ion reaction provides energy, and on the other hand, the oxygen atoms are able to attract the movement of polysulfides and reduce the shuttle effect.
本发明具有如下有益效果：(1)该制备方法将氧化石墨还原、氮掺杂以及聚丙烯腈成环反应一步完成，提高反应效率；(2)聚丙烯腈在石墨烯层与层之间以及石墨烯与碳纳米管之间发生成环反应而交联在一起，使一维的碳纳米管和二维的石墨烯形成一个三维空间，再通过原位还原使硫存储在这个三维空间中 ；(3)高电导率的碳纳米管和石墨烯材料能有效提高电极片的电导率；(4)在充放电过程中，三维结构的构造有利于锂离子和电子在多维度传导路径中穿梭，提高离子和电子传导率；(5)为充分还原的氮掺杂石墨烯含有部分氮原子和氧原子，对硫有吸附作用，能有效减少飞梭效应，提高锂硫电池的循环寿命；(6)本发明制备的电极片可直接用于锂硫电池的正极，不需要再添加导电剂和粘结剂，大大降低了电极的成本。The invention has the following beneficial effects: (1) the preparation method comprises the steps of reducing graphite oxide, nitrogen doping and polyacrylonitrile ring forming to improve the reaction efficiency; (2) polyacrylonitrile between the graphene layer and the layer and The graphene and the carbon nanotubes undergo a ring-forming reaction and cross-link together, so that the one-dimensional carbon nanotubes and the two-dimensional graphene form a three-dimensional space, and then the sulfur is stored in the three-dimensional space by in situ reduction. (3) High-conductivity carbon nanotubes and graphene materials can effectively improve the electrical conductivity of the electrode sheets; (4) During the charging and discharging process, the three-dimensional structure is favorable for the lithium ions and electrons to shuttle in the multi-dimensional conduction path. (5) The fully reduced nitrogen-doped graphene contains a part of nitrogen atoms and oxygen atoms, which has an adsorption effect on sulfur, can effectively reduce the shuttle effect and improve the cycle life of the lithium-sulfur battery; 6) The electrode sheet prepared by the invention can be directly used for the positive electrode of the lithium sulfur battery, and no need to add a conductive agent and a binder, thereby greatly reducing the cost of the electrode.
对附图的简要说明Brief description of the drawing
附图说明DRAWINGS
图1是本发明制备的三维碳纳米管/氮掺杂石墨烯/硫电极片的SEM图。1 is an SEM image of a three-dimensional carbon nanotube/nitrogen-doped graphene/sulfur electrode sheet prepared by the present invention.
发明实施例Invention embodiment
本发明的实施方式Embodiments of the invention
下面结合附图，对本发明的较优的实施例作进一步的详细说明：The preferred embodiments of the present invention are further described in detail below with reference to the accompanying drawings:
实施例1Example 1
(1)将1g直径为20nm长度为1um碳纳米管、1g氧化石墨、1g聚丙烯腈加入到100mL的N-甲基吡咯烷酮，搅拌均匀后超声反应30分钟，然后混合浆料涂覆到铝箔上，真空干燥得到电极片。(1) Add 1 g of carbon nanotubes having a diameter of 20 nm, 1 g of graphite oxide, 1 g of polyacrylonitrile to 100 mL of N-methylpyrrolidone, stir well, and then ultrasonically react for 30 minutes, and then apply the mixed slurry to the aluminum foil. The electrode sheet was obtained by vacuum drying.
(2)将得到的电极片放入氨气保护的马弗炉内，以3℃/min的速度缓慢升温到400℃，反应5小时，自然冷却。(2) The obtained electrode sheet was placed in an ammonia-protected muffle furnace, and the temperature was slowly raised to 400 ° C at a rate of 3 ° C/min, and reacted for 5 hours to be naturally cooled.
(3)将(2)得到的电极片完全***2mol/L的Na2S2O3溶液中，静止30分钟，然后向溶液中缓慢的滴加1mol/L的盐酸，直到溶液PH＝7.5，拿出电极片，干燥后得到正极片。(3) The electrode sheet obtained in (2) was completely inserted into a 2 mol/L Na 2 S 2 O 3 solution, allowed to stand for 30 minutes, and then 1 mol/L hydrochloric acid was slowly added dropwise to the solution until the solution pH = 7.5. The electrode sheet was taken out and dried to obtain a positive electrode sheet.
实施例2Example 2
(1)将1g直径为100nm长度为20um碳纳米管、0.8g氧化石墨、1.2g聚丙烯腈加入到100mL的N-甲基吡咯烷酮，搅拌均匀后超声反应120分钟，然后混合浆料涂覆到铝箔上，真空干燥得到电极片。(1) 1 g of 100 nm carbon nanotubes having a length of 100 nm, 0.8 g of graphite oxide, and 1.2 g of polyacrylonitrile were added to 100 mL of N-methylpyrrolidone, stirred uniformly, and ultrasonically reacted for 120 minutes, and then mixed slurry was applied thereto. On an aluminum foil, it was vacuum dried to obtain an electrode sheet.
(2)将得到的电极片放入惰性气体保护的马弗炉内，以5℃/min的速度缓慢升温到500℃，反应0.5小时，自然冷却。 (2) The obtained electrode sheet was placed in an inert gas-protected muffle furnace, and the temperature was slowly raised to 500 ° C at a rate of 5 ° C / min, and reacted for 0.5 hour, and naturally cooled.
(3)将(2)得到的电极片完全***0.5mol/L的Na2S2O3溶液中，静止60分钟，然后向溶液中缓慢的滴加1mol/L的盐酸，直到溶液PH＝6.5，拿出电极片，干燥后得到正极片。(3) the electrode sheet (2) to give the fully inserted 0.5mol / L of Na 2 S 2 O 3 solution, stationary for 60 min then was slowly added dropwise 1mol / L hydrochloric acid to the solution, the solution until PH = 6.5 Take out the electrode sheet and dry it to obtain a positive electrode sheet.
实施例3Example 3
(1)将1g直径为30nm长度为10um碳纳米管、1.2g氧化石墨、0.8g聚丙烯腈加入到100mL的N-甲基吡咯烷酮，搅拌均匀后超声反应60分钟，然后混合浆料涂覆到铝箔上，真空干燥得到电极片。(1) Add 1 g of carbon nanotubes having a diameter of 30 nm to 10 um, 1.2 g of graphite oxide, and 0.8 g of polyacrylonitrile to 100 mL of N-methylpyrrolidone, stir well, and then ultrasonically react for 60 minutes, then apply the mixed slurry to On an aluminum foil, it was vacuum dried to obtain an electrode sheet.
(2)将得到的电极片放入氨气保护的马弗炉内，以4℃/min的速度缓慢升温到450℃，反应1小时，自然冷却。(2) The obtained electrode sheet was placed in an ammonia-protected muffle furnace, and the temperature was slowly raised to 450 ° C at a rate of 4 ° C/min, and reacted for 1 hour to be naturally cooled.
(3)将(2)得到的电极片完全***1mol/L的Na2S2O3溶液中，静止50分钟，然后向溶液中缓慢的滴加1mol/L的盐酸，直到溶液PH＝7，拿出电极片，干燥后得到正极片。(3) The electrode sheet obtained in (2) was completely inserted into a 1 mol/L Na 2 S 2 O 3 solution, and allowed to stand for 50 minutes, and then 1 mol/L hydrochloric acid was slowly added dropwise to the solution until the solution PH=7. The electrode sheet was taken out and dried to obtain a positive electrode sheet.
实施例4Example 4
(1)将1g直径为50nm长度为5um碳纳米管、0.9g氧化石墨、1.1g聚丙烯腈加入到100mL的N-甲基吡咯烷酮，搅拌均匀后超声反应90分钟，然后混合浆料涂覆到铝箔上，真空干燥得到电极片。(1) 1 g of 50 nm long carbon nanotubes, 0.9 g of graphite oxide, 1.1 g of polyacrylonitrile were added to 100 mL of N-methylpyrrolidone, stirred uniformly, and ultrasonically reacted for 90 minutes, and then the mixed slurry was applied thereto. On an aluminum foil, it was vacuum dried to obtain an electrode sheet.
(2)将得到的电极片放入氨气保护的马弗炉内，以3.5℃/min的速度缓慢升温到420℃，反应2小时，自然冷却。(2) The obtained electrode sheet was placed in an ammonia-protected muffle furnace, and the temperature was slowly raised to 420 ° C at a rate of 3.5 ° C / min, and reacted for 2 hours to be naturally cooled.
(3)将(2)得到的电极片完全***1.5mol/L的Na2S2O3溶液中，静止40分钟，然后向溶液中缓慢的滴加1mol/L的盐酸，直到溶液PH＝7.3，拿出电极片，干燥后得到正极片。(3) The electrode sheet obtained in (2) was completely inserted into a 1.5 mol/L Na 2 S 2 O 3 solution, and allowed to stand for 40 minutes, and then 1 mol/L hydrochloric acid was slowly added dropwise to the solution until the solution PH = 7.3. Take out the electrode sheet and dry it to obtain a positive electrode sheet.
实施例5Example 5
(1)将1g直径为70nm长度为15um碳纳米管、1.1g氧化石墨、0.9g聚丙烯腈加入到100mL的N-甲基吡咯烷酮，搅拌均匀后超声反应100分钟，然后混合浆料涂 覆到铝箔上，真空干燥得到电极片。(1) Add 1 g of carbon nanotubes having a diameter of 70 nm to 15 um, 1.1 g of graphite oxide, and 0.9 g of polyacrylonitrile to 100 mL of N-methylpyrrolidone, stir well, and then ultrasonically react for 100 minutes, then mix the slurry. It was coated on an aluminum foil and vacuum dried to obtain an electrode sheet.
(2)将得到的电极片放入氨气保护的马弗炉内，以4.5℃/min的速度缓慢升温到470℃，反应3小时，自然冷却。(2) The obtained electrode sheet was placed in an ammonia-protected muffle furnace, and the temperature was slowly raised to 470 ° C at a rate of 4.5 ° C / min, and reacted for 3 hours to be naturally cooled.
(3)将(2)得到的电极片完全***1.2mol/L的Na2S2O3溶液中，静止35分钟，然后向溶液中缓慢的滴加1mol/L的盐酸，直到溶液PH＝6.7，拿出电极片，干燥后得到正极片。(3) The electrode sheet obtained in (2) was completely inserted into a 1.2 mol/L Na 2 S 2 O 3 solution, and allowed to stand for 35 minutes, and then 1 mol/L hydrochloric acid was slowly added dropwise to the solution until the solution PH=6.7. Take out the electrode sheet and dry it to obtain a positive electrode sheet.
电极的制备及性能测试；将制备的电极片作为正极，金属锂片为对电极，CEL GARD 2400为隔膜，1mol/L的LiTFSI/DOL-DME(体积比1∶1)为电解液，1mol/L的LiNO3为添加剂，在充满Ar手套箱内组装成扣式电池，采用Land电池测试***进行恒流充放电测试。充放电电压范围为1-3V，电流密度为1C，性能如表1所示。Electrode preparation and performance test; the prepared electrode sheet was used as the positive electrode, the lithium metal plate was used as the counter electrode, CEL GARD 2400 was used as the separator, and 1 mol/L of LiTFSI/DOL-DME (volume ratio 1:1) was used as the electrolyte, 1 mol/ L LiNO3 is an additive, assembled into a button-type battery in a filled glove box, and a constant current charge and discharge test is performed using a Land battery test system. The charge and discharge voltage range is 1-3V, the current density is 1C, and the performance is shown in Table 1.
表1Table 1
[Table 1][Table 1]
Figure PCTCN2016074195-appb-000001
Figure PCTCN2016074195-appb-000001
图1为本发明制备出正极材料的SEM图，从图中可以看出从图中可以看出该正极材料具备大量开放的三维孔状结构，能够很好的提供离子传输通道，提高材料的电化学性能。1 is an SEM image of a positive electrode material prepared by the present invention. It can be seen from the figure that the positive electrode material has a large number of open three-dimensional pore-like structures, which can provide an ion transport channel and improve the electrical energy of the material. Chemical properties.
以上内容是结合具体的优选实施方式对本发明所作的进一步详细说明，不能认定本发明的具体实施只局限于这些说明。对于本发明所属技术领域的普通技术人员来说，在不脱离本发明构思的前提下，还可以做出若干简单推演或替换，都应当视为属于本发明的保护范围。 The above is a further detailed description of the present invention in connection with the specific preferred embodiments, and the specific embodiments of the present invention are not limited to the description. It will be apparent to those skilled in the art that the present invention may be made without departing from the spirit and scope of the invention.

Claims (5)

  1. 一种三维碳纳米管/氮掺杂石墨烯/硫电极片的制备方法，其特征在于，包括以下几个步骤：A method for preparing a three-dimensional carbon nanotube/nitrogen-doped graphene/sulfur electrode sheet, comprising the following steps:
    步骤(1)：将碳纳米管、氧化石墨和聚丙烯腈加入到N-甲基吡咯烷酮，搅拌均匀后超声反应30-120分钟，然后混合浆料涂覆到铝箔上，真空干燥得到电极片；Step (1): adding carbon nanotubes, graphite oxide and polyacrylonitrile to N-methylpyrrolidone, stirring uniformly, and ultrasonically reacting for 30-120 minutes, then applying the mixed slurry to an aluminum foil, and drying in vacuum to obtain an electrode sheet;
    步骤(2)：将得到的电极片放入氨气保护的马弗炉内，以3-5℃/min的速度缓慢升温到400-500℃，反应0.5-5小时，自然冷却；步骤(3)：将步骤(2)得到的电极片完全***Na2S2O3溶液中，静止30-60分钟，然后向溶液中缓慢的滴加盐酸，直到溶液PH＝6.5-7.5，拿出电极片，干燥后得到正极片。Step (2): The obtained electrode sheet is placed in an ammonia-protected muffle furnace, and slowly heated to 400-500 ° C at a rate of 3-5 ° C / min, reacted for 0.5-5 hours, and naturally cooled; step (3) ): The electrode sheet obtained in the step (2) is completely inserted into the Na 2 S 2 O 3 solution, and is allowed to stand for 30-60 minutes, and then hydrochloric acid is slowly added dropwise to the solution until the solution PH=6.5-7.5, and the electrode sheet is taken out. After drying, a positive electrode sheet was obtained.
  2. 如权利要求1所述的方法，其特征在于，所述步骤(1)中碳纳米管、石墨烯和聚丙烯腈的质量比为1∶1.6-2.4∶0.8-1.2，碳纳米管的直径为20-100nm，长度为1-20um。The method according to claim 1, wherein the mass ratio of the carbon nanotubes, graphene and polyacrylonitrile in the step (1) is 1:1.6-2.4:0.8-1.2, and the diameter of the carbon nanotubes is 20-100nm, length 1-20um.
  3. 如权利要求1所述的方法，其特征在于，所述步骤(2)反应温度为400-500℃。The method of claim 1 wherein said step (2) has a reaction temperature of from 400 to 500 °C.
  4. 如权利要求1所述的方法，其特征在于，所述Na2S2O3溶液的浓度为0.5-2mol/L。The method of claim 1 wherein the Na 2 S 2 O 3 solution has a concentration of from 0.5 to 2 mol/L.
  5. 如权利要求1所述的方法，其特征在于，所述步骤(3)中盐酸的浓度为1mol/L。 The method according to claim 1, wherein the concentration of hydrochloric acid in the step (3) is 1 mol/L.
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