WO2018032321A1

WO2018032321A1 - Method for manufacturing graphene foam positive electrode for lithium-sulfur battery

Info

Publication number: WO2018032321A1
Application number: PCT/CN2016/095453
Authority: WO
Inventors: 肖丽芳; 钟玲珑
Original assignee: 肖丽芳
Priority date: 2016-08-16
Filing date: 2016-08-16
Publication date: 2018-02-22

Abstract

A method for manufacturing a graphene foam positive electrode for a lithium-sulfur battery. The method comprises the followings steps: step (1) adding a graphite oxide and a polyacrylonitrile into a ball mill to perform ball milling for 30-60 minutes, then adding a ball-milled mixture into a mixed solution of an ethanol and water for ultrasonic dispersion to form a suspension with a concentration of 1-20 g/L; step (2) immersing a nickel foam in the suspension for 10-60 minutes, steam-drying the solvent and adding a gas mixture of hydrogen and nitrogen to protect a reaction within a muffle furnace for 1-10 hours at 800-1,100°C, then reacting to completion followed by natural cooling; step (3) immersing a product from the previous step in a 1-3 mol/L hydrochloric acid, performing a reaction for 5-10 hours at 60-80°C, then reacting to completion to obtain a graphene foam; and step (4) coating an elemental sulfur powder on a surface of the graphene foam, placing the foam in a sealed container, reacting for 1-5 hours at 120-180°C, cooling, then rolling to obtain an electrode. The manufacturing method is easy to perform and directly provides a positive electrode for a lithium-sulfur battery, thereby simplifying a technique for manufacturing positive electrodes.

Description

发明名称：一种泡沫石墨烯锂硫电池正极片的制备方法技术领域 Title: Preparation method of positive electrode sheet of foamed graphene lithium sulfur battery

[0001] 本发明属于锂硫电池技术领域，特别是涉及一种泡沫石墨烯锂硫电池正极片的制备方法。 [0001] The invention belongs to the technical field of lithium sulfur batteries, and in particular relates to a method for preparing a positive electrode sheet of a foamed graphene lithium sulfur battery.

背景技术 Background technique

[0002] 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 2.4 V和 2.1 V) ，但其电化学反应机理比较复杂。锂硫电池具有比能量高（2600 Wh/kg) 、比容量高（1675 mAh/g) 、成本低等优点，被认为是很有发展前景的新一代电池。 [0002] A lithium-sulfur battery is a battery system in which lithium metal is used as a negative electrode and elemental sulfur is a positive electrode. Lithium-sulfur batteries have two discharge platforms (approximately 2.4 V and 2.1 V), but their electrochemical reaction mechanisms are complex. Lithium-sulfur batteries have the advantages of high specific energy (2600 Wh/kg), high specific capacity (1675 mAh/g), and low cost, and are considered to be promising new generation batteries.

[0003] 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（5xl0

-i ) ，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 Li ₂Sn (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。同吋不溶性的 Li ₂8和 Li ₂S ₂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 Li ₂S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 Li ₂S的密度不同，当硫被锂化后体积膨胀大约 79%，易导致 ₂8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。 [0003] 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 reasons for the above problems are as follows: (1) Elemental sulfur is an electron and ion insulator, and the room temperature conductivity is low (5xl0)

-i), since there is no ionic sulfur present, it is difficult to activate as a positive electrode material; (2) Lithium polysulfide Li ₂ Sn (8 >n>4) produced during the electrode reaction is easily soluble in the electrolyte In the middle, a concentration difference is formed between the positive and negative electrodes, and migrates to the negative electrode under the action of a concentration gradient, and the high poly lithium polysulfide is reduced by the metal lithium 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. The same insoluble Li ₂ 8 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. Lithium ions migrate slowly in solid lithium sulfide, which slows the electrochemical reaction kinetics. (4) The density of sulfur and the final product Li ₂ S is different. When the sulfur is lithiated, the volume expands by about 79%, which easily leads to ₂ The powdering of 8 causes safety problems of 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

[0004] 本发明要解决的技术问题是提供一种泡沫石墨烯锂硫电池正极片的制备方法，其目的在于提高锂硫电池的正极容量，改善电池的循环寿命，解决传统锂硫电池在充放电过程中的中间产物多硫化物溶于电解液，使锂硫电池的正极容量急剧下降，导致电池的循环寿命变差的问题。 [0004] The technical problem to be solved by the present invention is to provide a method for preparing a positive electrode sheet of a foamed graphene lithium-sulfur battery, which aims to improve the positive electrode capacity of the lithium-sulfur battery, improve the cycle life of the battery, and solve the traditional lithium-sulfur electricity. The intermediate product polysulfide in the charge and discharge process is dissolved in the electrolyte, so that the positive electrode capacity of the lithium-sulfur battery is drastically lowered, resulting in a problem that the cycle life of the battery is deteriorated.

问题的解决方案 Problem solution

技术解决方案 Technical solution

[0005] 本发明提供一种泡沫石墨烯锂硫电池正极片的制备方法的制备方法为： [0005] The present invention provides a preparation method of a method for preparing a positive electrode sheet of a foamed graphene lithium-sulfur battery:

[0006] 步骤（1) 将氧化石墨和聚丙烯晴加入到球磨机中球磨 30-60min，然后将球磨后的混合物加入到乙醇与水的混合溶液中超声分散，形成浓度 l-20g/L的悬浮液 [0006] Step (1) Adding graphite oxide and polypropylene fine to a ball mill for 30-60 min, and then adding the ball-milled mixture to a mixed solution of ethanol and water to ultrasonically disperse to form a suspension having a concentration of l-20 g/L. Liquid

[0007] 步骤（2) 将泡沫镍在上述悬浮液中浸泡 10-60min，蒸干溶剂，再放入氢氮混合气保护的马弗炉内 800-1100°C反应 l-10h，反应完全后自然冷却。 [0007] Step (2) Soaking nickel foam in the above suspension for 10-60 min, evaporating the solvent, and then placing in a hydrogen-nitrogen mixed gas-protected muffle furnace at 800-1100 ° C for 1-10 h, after completion of the reaction. Naturally cooled.

[0008] 步骤（3) 将上述的产物浸渍于 l-3mol/L的盐酸中， 60-80°C反应 5-10h，反应完全后得到泡沫石墨烯。 [0008] Step (3) The above product is immersed in l-3 mol/L hydrochloric acid, and reacted at 60-80 ° C for 5-10 h, and after completion of the reaction, foamed graphene is obtained.

[0009] 步骤（4) 将单质硫粉涂抹在泡沫石墨烯的表面，置于密封的容器内， 120-180 [0009] Step (4) Applying elemental sulfur powder to the surface of the foamed graphene, placed in a sealed container, 120-180

°C反应 l-5h 冷却后锟压得到电极片。 °C reaction l-5h After cooling, the electrode sheet was obtained by rolling.

[0010] 进一步地所述步骤（1) 中球磨吋间为 30-60min; [0010] Further, in the step (1), the ball mill is 30-60 min;

[0011] 进一步地所述步骤（1) 中聚丙烯晴的质量为氧化石墨质量的 0.01-5%。 [0011] Further, the mass of the polypropylene fine in the step (1) is 0.01-5% of the mass of the graphite oxide.

[0012] 进一步地所述步骤（1) 中乙醇与水的混合溶液中乙醇与水的体积比为 0.25-4 [0012] Further, the volume ratio of ethanol to water in the mixed solution of ethanol and water in the step (1) is 0.25-4

[0013] 进一步地所述步骤（1) 在氧化石墨悬浮液的浓度为 l-20g/L的悬浮液。 [0013] Further, the step (1) is a suspension having a concentration of the graphite oxide suspension of from 1 to 20 g/L.

[0014] 进一步地所述步骤（2) 中泡沫镍浸泡在氧化石墨悬浮液中的吋间为 10-60mi n° [0014] Further, in the step (2), the foamed nickel is immersed in the graphite oxide suspension at a ratio of 10-60 mi n°

[0015] 进一步地所述步骤（2) 中马弗炉内的气氛为含体积浓度 5%氢气的氢氮混合气。 [0015] Further, in the step (2), the atmosphere in the muffle furnace is a hydrogen-nitrogen mixed gas containing a volume concentration of 5% hydrogen.

[0016] 进一步地所述步骤（2) 在马弗炉内的反应温度为 800-1100°C，反应吋间为 1- 10h。 [0016] Further, the reaction temperature in the step (2) in the muffle furnace is 800-1100 ° C, and the reaction time is 1-10 h.

[0017] 进一步地所述步骤（3) 中盐酸浓度为 l-3mol/L。 [0017] Further, the concentration of hydrochloric acid in the step (3) is l-3 mol/L.

[0018] 进一步地所述步骤（3) 在盐酸中的反应温度为 60-80°C，反应吋间为 5-10h。 [0018] Further, the reaction temperature in the step (3) in hydrochloric acid is 60-80 ° C, and the reaction time is 5-10 h.

[0019] 进一步地所述步骤（4) 中硫的质量为泡沫石墨烯的质量的 0.5-5倍。 [0020] 进一步地，所述步骤（4) 中反应温度为 120-180°C，反应吋间为 l-5h。 [0019] Further, the mass of sulfur in the step (4) is 0.5-5 times the mass of the foamed graphene. [0020] Further, the reaction temperature in the step (4) is 120-180 ° C, and the reaction time is 1-5 h.

[0021] 进一步地，所述步骤（4) 中得到的电极片的厚度为 100-500um。 [0021] Further, the electrode sheet obtained in the step (4) has a thickness of 100-500 um.

发明的有益效果 Advantageous effects of the invention

有益效果 Beneficial effect

[0022] 本发明具有如下有益效果：（1) 本发明制备方法简单，可直接得到锂硫电池正极片，简化了正极制备工艺；（2) 泡沫石墨烯既可以作为集流体起到支撑和导电作用又可以作为正极材料提供储硫空间；（3) 泡沫石墨烯具有较大的比表面积和孔容，能制备高载硫量的正极，同吋能有效抑制穿梭效应，提高锂硫电池寿命。 [0022] The present invention has the following beneficial effects: (1) The preparation method of the invention is simple, and the positive electrode sheet of the lithium sulfur battery can be directly obtained, which simplifies the preparation process of the positive electrode; (2) the foamed graphene can serve as a current collector to support and conduct electricity. The function can also provide the sulfur storage space as the positive electrode material; (3) Foam graphene has a large specific surface area and pore volume, can prepare a positive electrode with high sulfur content, and can effectively inhibit the shuttle effect and improve the life of the lithium sulfur battery.

对附图的简要说明 Brief description of the drawing

附图说明 DRAWINGS

[0023] 图 1是本发明实施例 1锂硫电池电极片的循环寿命图。 1 is a cycle life diagram of a lithium-sulfur battery electrode sheet according to Embodiment 1 of the present invention.

本发明的实施方式 Embodiments of the invention

[0024] 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： [0024] The preferred embodiments of the present invention are further described in detail below with reference to the accompanying drawings:

[0025] 实施例 1 Embodiment 1

[0026] (1) 将 10g氧化石墨和 O.OOlg聚丙烯晴加入到球磨机中球磨 30min，然后将球磨后的混合物加入到乙醇与水体积比为 0.25的混合溶液中超声分散，形成浓度 lg /L的悬浮液。 [0026] (1) 10 g of graphite oxide and O. OOlg polypropylene were added to a ball mill for ball milling for 30 min, and then the ball milled mixture was ultrasonically dispersed in a mixed solution of ethanol and water volume ratio of 0.25 to form a concentration of lg / A suspension of L.

[0027] (2) 将泡沫镍在上述悬浮液中浸泡 10min，蒸干溶剂，再放入含 5%氢气的氢氮混合气保护的马弗炉内 800°C反应 10h，反应完全后自然冷却。 [0027] (2) The nickel foam was soaked in the above suspension for 10 min, and the solvent was evaporated to dryness, and then placed in a muffle furnace protected by a hydrogen-nitrogen mixed gas containing 5% hydrogen at 800 ° C for 10 hours, and the reaction was completely cooled. .

[0028] (3) 将上述的产物浸渍于 lmol/L的盐酸中， 60°C反应 10h，反应完全后得到泡沫石墨烯。 (3) The above product was immersed in 1 mol/L hydrochloric acid, and reacted at 60 ° C for 10 hours, and the reaction was completed to obtain a foamed graphene.

[0029] (4) 将 5g单质硫粉涂抹在泡沫石墨烯的表面，置于密封的容器内， [0029] (4) Applying 5 g of elemental sulfur powder to the surface of the foamed graphene, and placing it in a sealed container.

120°C反应 5h，冷却后锟压得到电极片。 The reaction was carried out at 120 ° C for 5 hours, and after cooling, it was pressed to obtain an electrode sheet.

[0030] [0030]

[0031] 实施例 2 [0032] ( 1) 将 lOg氧化石墨和 0.5g聚丙烯晴加入到球磨机中球磨 60min，然后将球磨后的混合物加入到乙醇与水体积比为 4的混合溶液中超声分散，形成浓度 20g/L的悬浮液。 Embodiment 2 [0032] (1) 10 g of graphite oxide and 0.5 g of polypropylene were added to a ball mill for ball milling for 60 min, and then the ball milled mixture was added to a mixed solution of ethanol and water volume ratio of 4 to ultrasonically disperse to form a concentration of 20 g / L Suspension.

[0033] (2) 将泡沫镍在上述悬浮液中浸泡 60min，蒸干溶剂，再放入含 5%氢气的氢氮混合气保护的马弗炉内 1100°C反应 lh，反应完全后自然冷却。 [0033] (2) The nickel foam was soaked in the above suspension for 60 min, and the solvent was evaporated to dryness, and then placed in a muffle furnace protected by a hydrogen-nitrogen mixed gas containing 5% hydrogen at 1100 ° C for 1 h, and the reaction was completely cooled. .

[0034] (3) 将上述的产物浸渍于 3mol/L的盐酸中， 80°C反应 5h，反应完全后得到泡沫石墨烯。 (3) The above product was immersed in 3 mol/L hydrochloric acid, and reacted at 80 ° C for 5 hours, and the reaction was completed to obtain a foamed graphene.

[0035] (4) 将 50g单质硫粉涂抹在泡沫石墨烯的表面，置于密封的容器内， 180°C反应 lh，冷却后锟压得到电极片。 [0035] (4) 50 g of elemental sulfur powder was applied to the surface of the foamed graphene, placed in a sealed container, reacted at 180 ° C for 1 h, and cooled to obtain an electrode sheet.

[0036] [0036]

[0037] 实施例 3 Example 3

[0038] ( 1) 将 10g氧化石墨和 O.lg聚丙烯晴加入到球磨机中球磨 45min，然后将球磨后的混合物加入到乙醇与水体积比为 0.5的混合溶液中超声分散，形成浓度 3g/L 的悬浮液。 [0038] (1) 10 g of graphite oxide and O.lg polypropylene were added to a ball mill for ball milling for 45 min, and then the ball milled mixture was ultrasonically dispersed in a mixed solution of ethanol and water volume ratio of 0.5 to form a concentration of 3 g / A suspension of L.

[0039] (2) 将泡沫镍在上述悬浮液中浸泡 30min，蒸干溶剂，再放入含 5%氢气的氢氮混合气保护的马弗炉内 900°C反应 5h，反应完全后自然冷却。 [0039] (2) The nickel foam was soaked in the above suspension for 30 min, the solvent was evaporated, and then placed in a hydrogen-nitrogen mixed gas-protected muffle furnace containing 5% hydrogen at 900 ° C for 5 h, and the reaction was completely cooled. .

[0040] (3) 将上述的产物浸渍于 2mol/L的盐酸中， 75°C反应 7h，反应完全后得到泡沫石墨烯。 (3) The above product was immersed in 2 mol/L hydrochloric acid, and reacted at 75 ° C for 7 hours, and the reaction was completed to obtain a foamed graphene.

[0041] (4) 将 10g单质硫粉涂抹在泡沫石墨烯的表面，置于密封的容器内， 150°C反应 3h，冷却后锟压得到电极片。 [0041] (4) 10 g of elemental sulfur powder was applied to the surface of the foamed graphene, placed in a sealed container, and reacted at 150 ° C for 3 hours, and cooled and then pressed to obtain an electrode sheet.

[0042] 实施例 4 Embodiment 4

[0043] ( 1) 将 10g氧化石墨和 3g聚丙烯晴加入到球磨机中球磨 40min，然后将球磨后的混合物加入到乙醇与水体积比为 2的混合溶液中超声分散，形成浓度 10g/L的悬浮液。 [0043] (1) 10 g of graphite oxide and 3 g of polypropylene were added to a ball mill for ball milling for 40 min, and then the ball milled mixture was ultrasonically dispersed in a mixed solution of ethanol and water volume ratio 2 to form a concentration of 10 g/L. suspension.

[0044] (2) 将泡沫镍在上述悬浮液中浸泡 50min，蒸干溶剂，再放入含 5%氢气的氢氮混合气保护的马弗炉内 1000°C反应 3h，反应完全后自然冷却。 [0044] (2) Soaking nickel foam in the above suspension for 50 min, evaporating the solvent, and then reacting in a muffle furnace protected by a hydrogen-nitrogen mixed gas containing 5% hydrogen at 1000 ° C for 3 h, and cooling naturally after completion of the reaction. .

[0045] (3) 将上述的产物浸渍于 1.5mol/L的盐酸中， 65°C反应 9h，反应完全后得到泡沫石墨烯。 [0046] (4) 将 20g单质硫粉涂抹在泡沫石墨烯的表面，置于密封的容器内， 160°C反应 2h，冷却后锟压得到电极片。 (3) The above product was immersed in 1.5 mol/L hydrochloric acid, and reacted at 65 ° C for 9 hours, and the reaction was completed to obtain foamed graphene. [0046] (4) 20 g of elemental sulfur powder was applied to the surface of the foamed graphene, placed in a sealed container, reacted at 160 ° C for 2 h, cooled and then pressed to obtain an electrode sheet.

[0047] 实施例 5 Example 5

[0048] (1) 将 10g氧化石墨和 lg聚丙烯晴加入到球磨机中球磨 40min，然后将球磨后的混合物加入到乙醇与水体积比为 1的混合溶液中超声分散，形成浓度 5g/L的悬浮液。 [0048] (1) 10 g of graphite oxide and lg polypropylene were added to a ball mill for ball milling for 40 min, and then the ball milled mixture was added to a mixed solution of ethanol and water volume ratio 1 to ultrasonically disperse to form a concentration of 5 g / L suspension.

[0049] (2) 将泡沫镍在上述悬浮液中浸泡 20min，蒸干溶剂，再放入含 5%氢气的氢氮混合气保护的马弗炉内 950°C反应 80h，反应完全后自然冷却。 [0049] (2) The nickel foam was soaked in the above suspension for 20 min, the solvent was evaporated, and then placed in a muffle furnace protected with 5% hydrogen in a hydrogen-nitrogen mixed gas atmosphere at 950 ° C for 80 h, and the reaction was allowed to cool naturally. .

[0050] (3) 将上述的产物浸渍于 2.5mol/L的盐酸中， 75°C反应 4h，反应完全后得到泡沫石墨烯。 (3) The above product was immersed in 2.5 mol/L hydrochloric acid, and reacted at 75 ° C for 4 hours, and the reaction was completed to obtain a foamed graphene.

[0051] (4) 将 30g单质硫粉涂抹在泡沫石墨烯的表面，置于密封的容器内， 140°C反应 4h，冷却后锟压得到电极片。 [0051] (4) 30 g of elemental sulfur powder was applied to the surface of the foamed graphene, placed in a sealed container, reacted at 140 ° C for 4 h, and cooled to obtain an electrode sheet.

[0052] 其效果如表 1所示，由表 1可知：本发明制备的锂硫电池电极片质量比容量达到了 1290-1410 mAh/g。 The effect is shown in Table 1. It can be seen from Table 1 that the mass ratio capacity of the lithium-sulfur battery electrode sheets prepared by the present invention reaches 1290-1410 mAh/g.

[0053] 由图 1可知：本发明制备的锂硫电池电极片充放电 300次，性能保持良好。 It can be seen from FIG. 1 that the electrode sheet of the lithium sulfur battery prepared by the invention is charged and discharged 300 times, and the performance is kept good.

[0054] [0054]

[0055] 表 1 Table 1

[] [表 1] [] [Table 1]

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. General technique for the technical field to which the present invention pertains A person skilled in the art can make some simple deductions or substitutions without departing from the spirit and scope of the invention.

Claims

权利要求书 Claim

[权利要求 1] 一种泡沫石墨烯锂硫电池正极片的制备方法，其特征在于，包括以下几个步骤： [Claim 1] A method for preparing a positive electrode sheet of a foamed graphene lithium-sulfur battery, comprising the following steps:

步骤（1) 将氧化石墨和聚丙烯晴加入到球磨机中球磨 30-60min，然后将球磨后的混合物加入到乙醇与水的混合溶液中超声分散，形成浓度 l-20g/L的悬浮液； Step (1) adding graphite oxide and polypropylene fine to a ball mill for 30-60 minutes, and then adding the ball-milled mixture to a mixed solution of ethanol and water to form a suspension having a concentration of l-20 g/L;

步骤（2) 将泡沫镍在上述悬浮液中浸泡 10-60min，蒸干溶剂，再放入氢氮混合气保护的马弗炉内 800-1100°C反应 l-10h，反应完全后自然冷却； Step (2) immersing the foamed nickel in the above suspension for 10-60 minutes, evaporating the solvent, and then placing it in a hydrogen-nitrogen mixed gas-protected muffle furnace at 800-1100 ° C for 1 to 10 hours, and then completely cooling after completion of the reaction;

步骤（3) 将上述的产物浸渍于 l-3mol/L的盐酸中， 60-80°C反应 5-10h Step (3) The above product is immersed in l-3mol/L hydrochloric acid, and reacted at 60-80 ° C for 5-10h.

，反应完全后得到泡沫石墨烯； After the reaction is completed, foamed graphene is obtained;

步骤（4) 将单质硫粉涂抹在泡沫石墨烯的表面，置于密封的容器内， 120-180°C反应 l-5h，冷却后锟压得到电极片。 Step (4) Applying elemental sulfur powder to the surface of the foamed graphene, placing it in a sealed container, reacting at 120-180 ° C for l-5 h, and cooling to obtain an electrode sheet.

[权利要求 2] 如权利要求 1所述的制备方法，其特征在于，所述步骤 ( 1) 中球磨吋间为 30-60min。 [Claim 2] The preparation method according to claim 1, wherein the ball mill in the step (1) is 30-60 min.

[权利要求 3] 如权利要求 1所述的制备方法，其特征在于，所述步骤 ( 1) 中聚丙烯晴的质量为氧化石墨质量的 0.01-5%。 [Claim 3] The preparation method according to claim 1, wherein the mass of the polypropylene in the step (1) is 0.01 to 5% by mass of the graphite oxide.

[权利要求 4] 如权利要求 1所述的制备方法，其特征在于，所述步骤 ( 1) 中乙醇与水的混合溶液中乙醇与水的体积比为 0.25-4。 [Claim 4] The preparation method according to claim 1, wherein a volume ratio of ethanol to water in the mixed solution of ethanol and water in the step (1) is 0.25-4.

[权利要求 5] 如权利要求 1所述的制备方法，其特征在于，所述步骤 ( 1) 在氧化石墨悬浮液的浓度为 l-20g/L的悬浮液。 [Claim 5] The preparation method according to claim 1, wherein the step (1) is a suspension having a concentration of the lintstone ink suspension of from 1 to 20 g/L.

[权利要求 6] 如权利要求 1所述的制备方法，其特征在于，所述步骤 (2) 中泡沫镍浸泡在氧化石墨悬浮液中的吋间为 10-60min。 [Claim 6] The preparation method according to claim 1, wherein the foamed nickel is immersed in the graphite oxide suspension in the step (2) for 10-60 minutes.

[权利要求 7] 如权利要求 1所述的制备方法，其特征在于，所述步骤 (2) 中马弗炉内的气氛为含体积浓度 5%氢气的氢氮混合气；所述步骤（2) 在马弗炉内的反应温度为 800-1100°C，反应吋间为 l-10h。 [Claim 7] The preparation method according to claim 1, wherein the atmosphere in the muffle furnace in the step (2) is a hydrogen-nitrogen mixed gas containing a volume concentration of 5% hydrogen; The reaction temperature in the muffle furnace is 800-1100 ° C, and the reaction time is l-10 h.

[权利要求 8] 如权利要求 1所述的制备方法，其特征在于，所述步骤（3) 中盐酸浓度为 l-3mol/L; 在盐酸中的反应温度为 60-80°C，反应吋间为 5-10h。 [Claim 8] The preparation method according to claim 1, wherein the concentration of hydrochloric acid in the step (3) is 1-3 mol/L; the reaction temperature in hydrochloric acid is 60-80 ° C, and the reaction 吋The interval is 5-10h.

[权利要求 9] 如权利要求 1所述的制备方法，其特征在于，所述步骤（4) 中硫的质量为泡沫石墨烯的质量的 0.5-5倍。 [Claim 9] The preparation method according to claim 1, wherein the quality of sulfur in the step (4) is 0.5 to 5 times the mass of the foamed graphene.

[权利要求 10] 如权利要求 1所述的制备方法，其特征在于，所述步骤（4) 中反应温度为 120-180°C，反应吋间为 l-5h; 中得到的电极片的厚度为 100-500u [Claim 10] The preparation method according to claim 1, wherein the reaction temperature in the step (4) is 120-180 ° C, and the reaction enthalpy is 1 - 5 h; For 100-500u