WO2017139992A1 - Preparation method for three-dimensional carbon nanotube/graphene/sulphur electrode - Google Patents
Preparation method for three-dimensional carbon nanotube/graphene/sulphur electrode Download PDFInfo
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- 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
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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 method for directly preparing a carbon nanotube/graphene/sulfur composite material and simultaneously preparing a positive electrode sheet of a lithium sulfur battery, which is prepared by coating a carbon nanotube/graphene having a three-dimensional structure.
- Sulfur nanoparticles improve the conductivity of sulfur and prevent the dissolution of polysulfides of discharge products.
- the invention provides a preparation process of a three-dimensional carbon nanotube/graphene/sulfur electrode sheet as follows:
- the obtained electrode sheet is placed in an inert gas-protected muffle furnace, slowly heated to 400-500 ° C at a rate of 3-5 ° C / min, reacted for 30-60 minutes, and naturally cooled;
- the mass ratio of carbon nanotubes, graphene and polyacrylonitrile in step (1) is 1:0.8-1.2:0.8-1.2, 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 concentration of the electrode sheet inserted into the Na 2 S 2 O 3 solution is 0.5-2 mol/L; the amount of hydrochloric acid added is just such that the pH of the solution is 6.5-7.5.
- the invention has the following beneficial effects: (1) polyacrylonitrile is cyclically reacted between the graphene layer and the layer and between the graphene and the carbon nanotube to crosslink together, so that the one-dimensional carbon nanotube and the two-dimensional Graphene forms a three-dimensional space, and then sulfur is stored in this three-dimensional space by in-situ reduction; (2) high conductivity carbon nanotubes and graphene materials can effectively improve the electrical conductivity of the electrode sheets; (3) in charge During the discharge process, the structure of the three-dimensional structure facilitates the shuttle of lithium ions and electrons in the multi-dimensional conduction path, and improves the ion and electron conductivity; (4)
- the electrode sheet prepared by the invention can be directly used for the positive electrode of the lithium-sulfur battery, and does not need The addition of a conductive agent and a binder greatly reduces the cost of the electrode.
- 1 is an SEM image of a three-dimensional carbon nanotube/graphene/sulfur electrode sheet prepared by the present invention.
- Electrode preparation and performance test prepared electrode sheet as positive electrode, metal lithium plate as counter electrode, CELGARD 2400 as separator, 1 mol/L LiTFSI/DOL-DME (volume ratio 1:1) as electrolyte, 1 mol/L
- the LiNO3 is an additive, assembled into a button-type battery in a St-filled glove box, and subjected to a constant current charge and discharge test using a Land battery test system.
- the charge and discharge voltage range is 1-3V
- the current density is 1C
- 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
Provided in the present invention is a preparation method for a three-dimensional carbon nanotube/graphene/sulphur electrode, comprising the following steps: (1) adding carbon nanotubes, graphene, and polyacrylonitrile to N-methylpyrrolidone, implementing an ultrasonic reaction, mixing the slurry and coating same onto aluminium foil, and vacuum drying to obtain an electrode; (2) placing the obtained electrode into an inert gas protected muffle furnace, slowly heating to 400-500°C, and cooling naturally; (3) fully inserting the electrode obtained in step (2) into an Na2S2O3 solution, and leaving to stand for 30 to 60 minutes, then slowly dropping hydrochloric acid into the solution until the solution pH = 7, removing the electrode, and drying same to obtain a positive electrode. An electrode prepared by means of the present invention can be directly used as a positive electrode of a lithium-sulphur battery, without the need to add a conductive agent and a binding agent, thus greatly reducing electrode costs.
Description
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.
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.
本发明要解决的技术问题是提供一种碳纳米管/石墨烯/硫复合材料，同时直接制备成锂硫电池正极片的方法，该方法制备出三维结构的碳纳米管/石墨烯，包覆硫纳米颗粒，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 method for directly preparing a carbon nanotube/graphene/sulfur composite material and simultaneously preparing a positive electrode sheet of a lithium sulfur battery, which is prepared by coating a carbon nanotube/graphene having a three-dimensional structure. Sulfur nanoparticles improve the conductivity of sulfur and prevent the dissolution of polysulfides of discharge products.
问题的解决方案
Problem solution
本发明提供一种三维碳纳米管/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/graphene/sulfur electrode sheet as follows:
(1)将碳纳米管、石墨烯、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) adding carbon nanotubes, graphene, 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;
(2)将得到的电极片放入惰性气体保护的马弗炉内，以3-5℃/min的速度缓慢升温到400-500℃，反应30-60分钟，自然冷却；(2) The obtained electrode sheet is placed in an inert gas-protected muffle furnace, slowly heated to 400-500 ° C at a rate of 3-5 ° C / min, reacted for 30-60 minutes, and naturally cooled;
(3)将(2)得到的电极片完全插入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) completely insert the electrode sheet obtained in (2) into the 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. The electrode sheet was taken out and dried to obtain a positive electrode sheet.
步骤(1)中碳纳米管、石墨烯、聚丙烯腈的质量比为1∶0.8-1.2∶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 carbon nanotubes, graphene and polyacrylonitrile in step (1) is 1:0.8-1.2:0.8-1.2, 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(3)中电极片插入Na2S2O3溶液的浓度为0.5-2mol/L；盐酸的加入量刚好使溶液的PH＝6.5-7.5。In the step (3), the concentration of the electrode sheet inserted into the Na 2 S 2 O 3 solution is 0.5-2 mol/L; 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
本发明具有如下有益效果：(1)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；(2)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；(3)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；(4)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) polyacrylonitrile is cyclically reacted between the graphene layer and the layer and between the graphene and the carbon nanotube to crosslink together, so that the one-dimensional carbon nanotube and the two-dimensional Graphene forms a three-dimensional space, and then sulfur is stored in this three-dimensional space by in-situ reduction; (2) high conductivity carbon nanotubes and graphene materials can effectively improve the electrical conductivity of the electrode sheets; (3) in charge During the discharge process, the structure of the three-dimensional structure facilitates the shuttle of lithium ions and electrons in the multi-dimensional conduction path, and improves the ion and electron conductivity; (4) The electrode sheet prepared by the invention can be directly used for the positive electrode of the lithium-sulfur battery, and does not need The addition of a conductive agent and a binder greatly reduces the cost of the electrode.
对附图的简要说明Brief description of the drawing
图1是本发明制备的三维碳纳米管/石墨烯/硫电极片的SEM图。1 is an SEM image of a three-dimensional carbon nanotube/graphene/sulfur electrode sheet prepared by the present invention.
发明实施例Invention embodiment
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石墨烯、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 length of 20 nm, 1 g of graphene, 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惰性气体保护的马弗炉内，以3℃/min的速度缓慢升温到400℃，反应60分钟，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 400 ° C at a rate of 3 ° C/min, and reacted for 60 minutes to be naturally cooled.
(3)将(2)得到的电极片完全插入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＝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 2mol / L of Na 2 S 2 O 3 solution, stationary for 30 min then was slowly added dropwise 1mol / L hydrochloric acid to the solution, the solution until PH = 6.5, 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石墨烯、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 graphene, 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30分钟，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 30 minutes to be naturally cooled.
(3)将(2)得到的电极片完全插入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＝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 0.5 mol/L Na 2 S 2 O 3 solution, and allowed to stand for 60 minutes, and then 1 mol/L hydrochloric acid was slowly added dropwise to the solution until the solution PH=7.5. 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石墨烯、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 graphene, 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惰性气体保护的马弗炉内，以4℃/min的速度缓慢升温到450℃，反应45分钟，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 450 ° C at a rate of 4 ° C/min, and reacted for 45 minutes to be naturally cooled.
(3)将(2)得到的电极片完全插入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＝6.8，拿出电极片，干燥后得到正极片。(3) the electrode sheet (2) to give the fully inserted 1mol / L of Na 2 S 2 O 3 solution, stationary for 50 min then added dropwise 1mol / L hydrochloric acid to the solution slowly, until the solution PH = 6.8, 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石墨烯、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) Add 1 g of 50 nm long carbon nanotubes, 0.9 g of graphene, 1.1 g of polyacrylonitrile to 100 mL of N-methylpyrrolidone, stir well, and then ultrasonically react for 90 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惰性气体保护的马弗炉内，以3.5℃/min的速度缓慢升温到420℃，反应50分钟，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 420 ° C at a rate of 3.5 ° C / min, and reacted for 50 minutes to be naturally cooled.
(3)将(2)得到的电极片完全插入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，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. 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石墨烯、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) 1 g of a 70 nm-length carbon nanotube, a length of 15 um of carbon nanotubes, 1.1 g of graphene, and 0.9 g of polyacrylonitrile were added to 100 mL of N-methylpyrrolidone, stirred uniformly, and ultrasonically reacted for 100 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惰性气体保护的马弗炉内，以4.5℃/min的速度缓慢升温到470℃，反应40分钟，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 470 ° C at a rate of 4.5 ° C / min, and reacted for 40 minutes to be naturally cooled.
(3)将(2)得到的电极片完全插入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＝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 1.2 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 = 7.3. 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，CELGARD 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电池测试系统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; prepared electrode sheet as positive electrode, metal lithium plate as counter electrode, CELGARD 2400 as separator, 1 mol/L LiTFSI/DOL-DME (volume ratio 1:1) as electrolyte, 1 mol/L The LiNO3 is an additive, assembled into a button-type battery in a St-filled glove box, and subjected to a constant current charge and discharge test 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]
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 (4)
- 一种三维碳纳米管/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/graphene/sulfur electrode sheet, comprising the following steps:(1)将碳纳米管、石墨烯和聚丙烯腈加入到N-甲基吡咯烷酮，搅拌均匀后超声反应30-120分钟，然后混合涂覆到铝箔上，真空干燥得到电极片；(1) adding carbon nanotubes, graphene and polyacrylonitrile to N-methylpyrrolidone, stirring uniformly, ultrasonically reacting for 30-120 minutes, then mixing and coating onto aluminum foil, and vacuum drying 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3-5℃/min的速度缓慢升温到400-500℃，反应30-60分钟，自然冷却；(2) The obtained electrode sheet is placed in an inert gas-protected muffle furnace, slowly heated to 400-500 ° C at a rate of 3-5 ° C / min, reacted for 30-60 minutes, and naturally cooled;(3)将(2)得到的电极片完全插入Na2S2O3溶液中，静止30-60分钟，然后向溶液中缓慢滴加盐酸，直到溶液PH＝6.5-7.5，拿出电极片，干燥后得到正极片。(3) The electrode sheet obtained in (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.
- 如权利要求1所述的制备方法，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∶0.8-1.2∶0.8-1.2，碳纳米管的直径为20-100nm，长度为1-20um。The preparation method according to claim 1, wherein the mass ratio of the carbon nanotubes, graphene and polyacrylonitrile in the step (1) is 1:0.8-1.2:0.8-1.2, and the diameter of the carbon nanotubes It is 20-100 nm and has a length of 1-20 um.
- 如权利要求1所述的制备方法，其特征在于，所述步骤(3)中Na2S2O3溶液的浓度为0.5-2mol/L。The preparation method according to claim 1, wherein the concentration of the Na 2 S 2 O 3 solution in the step (3) is from 0.5 to 2 mol/L.
- 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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| CN114956035A (en) * | 2022-04-29 | 2022-08-30 | 中国地质大学（武汉） | Ultramicropore carbon material, sulfur positive electrode material and application research thereof in lithium-sulfur battery |
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| US20150086881A1 (en) * | 2013-09-23 | 2015-03-26 | Aruna Zhamu | Large-grain graphene thin film current collector and secondary batteries containing same |
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| CN111653729A (en) * | 2020-05-20 | 2020-09-11 | 佛山科学技术学院 | Lithium-sulfur battery composite positive electrode and preparation method thereof |
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| CN114956035A (en) * | 2022-04-29 | 2022-08-30 | 中国地质大学（武汉） | Ultramicropore carbon material, sulfur positive electrode material and application research thereof in lithium-sulfur battery |
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