WO2017139987A1

WO2017139987A1 - Method for preparing graphene/zirconia hollow sphere/sulfur composite material

Info

Publication number: WO2017139987A1
Application number: PCT/CN2016/074182
Authority: WO
Inventors: 肖丽芳; 钟玲珑
Original assignee: 肖丽芳
Priority date: 2016-02-21
Filing date: 2016-02-21
Publication date: 2017-08-24

Abstract

A method for preparing a graphene/zirconia hollow sphere or a sulfur composite material, the method comprising the following steps: (1) weighing and adding a nano calcium carbonate powder to an anhydrous ethanol, and carrying out ultrasonic treatment to form a suspension; (2) weighing and dissolving zirconium dichloride and yttrium chloride in deionized water, and preparing into an aqueous solution; (3) adding the aqueous solution obtained from step (2) into the suspension in water bath, and adding an ammonia water adjustment value to obtain a white solid; (4) placing the white solid in a muffle furnace, following cool down, placing the white solid in an acetate solution, stirring the mixture solution and removing calcium carbonate to obtain hollow zirconia; and (5) adding the obtained hollow zirconia, elemental sulfur and graphene into the carbon disulfide to obtain the composite material. By using the sulfur-based material to coat the graphene/zirconia hollow sphere or the zirconia hollow sphere in the sulfur composite material, the dissolving of a discharging product polysulfide may be prevented, the volume expansion may be reduced, and the electrochemical performance thereof may be improved.

Description

一种石墨烯 /二氧化锆空心球 /硫复合材料的制备方法技术领域 Method for preparing graphene/zirconia hollow sphere/sulfur composite material

[0001] 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。 [0001] The present invention relates to nanomaterial synthesis, and in particular to a method for preparing a lithium sulfur battery cathode material.

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。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（5x10 -^30S-cm ，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 ₂S _n (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 ₂8和 ₂ S 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 Li ^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。技术问题 [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 (about 2.4 V and 2.1 V), but their electrochemical reaction mechanism is complicated. 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. 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 ionic insulator, and the room temperature conductivity is low (5x10 - ^30S -cm. Since there is no ionic sulfur, it is difficult to activate as a positive electrode material; 2) Lithium polysulfide Li ₂ S _n (8 >n>4) produced during the electrode reaction is easily soluble in the electrolyte, forming a concentration difference between the positive and negative electrodes, and migrating under the action of a concentration gradient To the negative electrode, the high polylithium polysulfide is reduced to lithium oligomeric lithium sulfide by the metal lithium. 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. The positive electrode is oxidized to a highly polylithium polysulfide. This phenomenon is called the shuttle effect, which reduces the utilization of sulfur active materials. The insoluble ₂₈ 8 and ₂ S ₂ deposits on the surface of the lithium negative electrode, further worsening. The performance of the lithium-sulfur battery; (3) The final product of the reaction, Li 2S, is also an electronic insulator, which is deposited on the sulfur electrode, and the lithium ion migrates slowly in the 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 the powdering of Li ^, which causes the safety problem of the lithium-sulfur battery. The above-mentioned deficiency restricts the lithium-sulfur battery. Development, this is also the key issue that needs to be solved in lithium-sulfur battery research.

[0003] 本发明要解决的技术问题是提供一种石墨烯 /二氧化锆空心球 /硫复合材料，制备方法简单，导电性良好的石墨烯提供导电网络，空心结构的二氧化锆包覆着硫基材料，能够阻止放电产物多硫化物的溶解并缓解体积膨胀，提高材料的电化学性能。问题的解决方案 [0003] The technical problem to be solved by the present invention is to provide a graphene/zirconia hollow sphere/sulfur composite material, which has a simple preparation method, a conductive conductive graphene provides a conductive network, and a hollow structure of zirconium dioxide coated A sulfur-based material that prevents the dissolution of polysulfide in the discharge product and relieves volume expansion, improving the electrochemical performance of the material. Problem solution

技术解决方案 Technical solution

[0004] 本发明提供一种石墨烯 /二氧化锆空心球 /硫复合材料的制备工艺流程如下： [0005] (1) 称取一定量的纳米碳酸钙粉末加入到无水乙醇中，超声形成悬浮液。 [0004] The present invention provides a graphene / zirconia hollow sphere / sulfur composite material preparation process is as follows: [0005] (1) Weigh a certain amount of nano calcium carbonate powder into anhydrous ethanol, ultrasonic formation suspension.

[0006] (2) 称取一定量的二氯氧锆和氯化钇溶于去离子水中，配制成水溶液。 [0006] (2) Weigh a certain amount of zirconium oxychloride and cerium chloride dissolved in deionized water to prepare an aqueous solution.

[0007] (3) 将（2) 得到的水溶液在 90°C水浴中缓慢加入到悬浮液中，然后加入氨水调节值，再加入一定量的表面活性剂聚乙二醇，将反应混合物继续搅拌后，在室温下陈化后得到白色沉淀，过滤、洗涤、干燥，得到白色固体。 [0007] (3) The aqueous solution obtained in (2) is slowly added to the suspension in a water bath at 90 ° C, then the ammonia water adjustment value is added, and a certain amount of surfactant polyethylene glycol is added to further stir the reaction mixture. Thereafter, a white precipitate was obtained after aging at room temperature, filtered, washed and dried to give a white solid.

[0008] (4) 将得到的白色固体放入马弗炉中，在空气气氛中，高温煅烧除去有机杂质，冷却后放入醋酸溶液中搅拌除去碳酸钙，过滤、水洗、干燥后得到空心二氧化锆。 [0008] (4) The obtained white solid is placed in a muffle furnace, and the organic impurities are removed by calcination at a high temperature in an air atmosphere, cooled, placed in an acetic acid solution, and stirred to remove calcium carbonate, filtered, washed with water, and dried to obtain a hollow second. Zirconia.

[0009] (5) 将得到的空心二氧化锆、硫单质、石墨烯加入到二硫化碳中，超声分散 [0009] (5) The obtained hollow zirconium dioxide, sulfur elemental, graphene is added to carbon disulfide, ultrasonically dispersed

，形成悬浮液，然后蒸干溶剂，得到复合材料。 , forming a suspension, and then evaporating the solvent to obtain a composite material.

[0010] 步骤（1) 中纳米碳酸钙的粒径为 40-100nm，超声吋间为 20-60分钟。 [0010] The particle size of the nanometer calcium carbonate in the step (1) is 40-100 nm, and the ultrasonic volume is 20-60 minutes.

[0011] 步骤（2) 中二氯氧锆：氯化钇：碳酸钙的质量比为 1 : 0.2-0.8： 0.5-5。 [0011] Step (2) Zirconium oxychloride: Barium chloride: The mass ratio of calcium carbonate is 1: 0.2-0.8: 0.5-5.

[0012] 步骤（3) 中将（2) 得到的水溶液加入到悬浮液的吋间为 3-5小吋，氨水调节 P[0012] In step (3), the aqueous solution obtained in (2) is added to the suspension of the suspension for 3-5 hours, and the ammonia water is adjusted.

H为 9-11，二氯氧锆与聚乙二醇的质量比为 1:0.5-5，搅拌反应吋间 3-10小吋，陈化吋间 12-24小吋。 H is 9-11, the mass ratio of zirconyl oxychloride to polyethylene glycol is 1:0.5-5, the stirring reaction is 3-10 hours, and the aging time is 12-24 hours.

[0013] 步骤（4) 中升温速率为 l-5°C/min，高温煅烧温度为 500-550°C，反应吋间 3-7小吋；醋酸溶液体积浓度为 5-10%，搅拌反应吋间 0.5-5小吋。 [0013] In step (4), the heating rate is l-5 ° C / min, the high temperature calcination temperature is 500-550 ° C, the reaction time is 3-7 吋; the acetic acid solution volume concentration is 5-10%, stirring reaction 0.5-5 hours in the daytime.

[0014] 步骤（5) 空心二氧化锆、硫单质、石墨烯的质量比为 15-30:60-80: 5-10; 超声分散吋间为 0.5-5小吋；蒸干溶剂的温度为 40-60°C。 [0014] Step (5) hollow zirconium dioxide, sulfur elemental, graphene mass ratio of 15-30:60-80: 5-10; ultrasonic dispersion between 0.5-5 吋 of the daytime; evaporation of the solvent temperature is 40-60 ° C.

发明的有益效果 Advantageous effects of the invention

有益效果 Beneficial effect

[0015] 本发明具有如下有益效果：（1) 石墨烯具有超高的电导率，通过该方法制备出的石墨烯 /二氧化锆空心球 /硫复合材料能够有效的提高锂硫电池正极材料的电子导电率和离子导电率；（2) 石墨烯 /二氧化锆空心球 /硫复合材料中二氧化锆空心球的包覆着硫基材料，能抑制放电产物多硫化物的溶解以及缓解体积膨胀，提高其电化学性能。 [0015] The present invention has the following beneficial effects: (1) Graphene has an ultra-high electrical conductivity, and the graphene/zirconia hollow sphere/sulfur composite prepared by the method can effectively improve the cathode material of the lithium-sulfur battery. Electron conductivity and ionic conductivity; (2) The zirconia hollow sphere in the graphene/zirconia hollow sphere/sulphur composite is coated with a sulfur-based material, which can inhibit the dissolution of the polysulfide of the discharge product and alleviate the volume expansion. , improve its electrochemical performance.

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

附图说明 DRAWINGS

[0016] 图 1是本发明制备的石墨烯 /二氧化锆空心球 /硫复合材料的 SEM图。 1 is an SEM image of a graphene/zirconia hollow sphere/sulfur composite prepared by the present invention.

本发明的实施方式 Embodiments of the invention

[0017] 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： [0017] The preferred embodiments of the present invention are further described in detail below with reference to the accompanying drawings:

[0018] 实施例 1 Embodiment 1

[0019] (1) 称取 lOOmg的纳米碳酸钙粉末加入到无水乙醇中，超声 20分钟形成悬浮液。 [0019] (1) 100 mg of the nano calcium carbonate powder was weighed and added to absolute ethanol, and sonicated for 20 minutes to form a suspension.

[0020] (2) 称取 200mg二氯氧锆和 40mg氯化钇溶于去 lOOmL离子水中，配制成水溶液。 [0020] (2) Weigh 200 mg of zirconium oxychloride and 40 mg of cerium chloride dissolved in 100 mL of ionic water to prepare an aqueous solution.

[0021] (3) 将（2) 得到的水溶液在 90°C水浴中缓慢加入到悬浮液中，加入吋间为 3 小吋，然后加入氨水调节值，再加入 lOOmg聚乙二醇，将反应混合物继续搅拌后，在室温下陈化一点吋间得到白色沉淀，过滤、洗涤、干燥，得到白色固体。将反应混合物继续搅拌 3小吋后，在室温下陈化 12小吋得到白色沉淀，过滤、洗涤、干燥，得到白色固体。 [0021] (3) The aqueous solution obtained in (2) is slowly added to the suspension in a 90 ° C water bath, added to the crucible for 3 hours, then added to the ammonia water adjustment value, and then added 100 mg of polyethylene glycol, the reaction After the mixture was further stirred, it was aged at room temperature to give a white precipitate, which was filtered, washed and dried to give a white solid. After the reaction mixture was further stirred for 3 hours, it was aged 12 hrs at room temperature to give a white precipitate, which was filtered, washed and dried to give a white solid.

[0022] (4) 将得到的白色固体放入马弗炉中，在空气气氛中，以 rC/min的速率升温至 500°C，高温煅烧反应 7小吋，冷却后放入体积浓度为 5%醋酸溶液中搅拌反应 5 小吋，过滤、水洗、干燥后得到空心二氧化锆。 [0022] (4) The obtained white solid was placed in a muffle furnace, heated to 500 ° C at a rate of rC / min in an air atmosphere, calcined at a high temperature for 7 hours, and cooled to a volume concentration of 5 The reaction was stirred for 5 hours in a % acetic acid solution, filtered, washed with water, and dried to obtain a hollow zirconium dioxide.

[0023] (5) 将 15mg空心二氧化锆、 80mg硫单质、 5mg石墨烯加入到二硫化碳中，超声分散 0.5小吋，形成悬浮液，然后 40°C蒸干溶剂，得到复合材料。 [0023] (5) 15 mg of hollow zirconia, 80 mg of sulfur simple substance, and 5 mg of graphene were added to carbon disulfide, ultrasonically dispersed for 0.5 Å to form a suspension, and then the solvent was evaporated to dryness at 40 ° C to obtain a composite material.

[0024] [0024]

[0025] 实施例 2 [0025] Example 2

[0026] (1) 称取 lOOmg的纳米碳酸钙粉末加入到无水乙醇中，超声 60分钟形成悬浮液。 (1) 100 mg of the nano calcium carbonate powder was weighed and added to absolute ethanol, and sonicated for 60 minutes to form a suspension.

[0027] (2) 称取 20mg二氯氧锆和 16mg氯化钇溶于去 lOOmL离子水中，配制成水溶液 [0028] (3) 将（2) 得到的水溶液在 90°C水浴中缓慢加入到悬浮液中，加入吋间为 5 小吋，然后加入氨水调节值，再加入 lOOmg聚乙二醇，将反应混合物继续搅拌 10 小吋后，在室温下陈化 24小吋得到白色沉淀，过滤、洗涤、干燥，得到白色固体。 [0027] (2) Weigh 20mg of zirconium oxychloride and 16mg of cerium chloride dissolved in 100mL of ionic water, formulated into an aqueous solution [0028] (3) The aqueous solution obtained in (2) is slowly added to the suspension in a 90 ° C water bath, added to the crucible for 5 hours, then added to the ammonia water adjustment value, and then added 100 mg of polyethylene glycol, the reaction After the mixture was further stirred for 10 hours, it was aged 24 hours at room temperature to give a white precipitate which was filtered, washed and dried to give a white solid.

[0029] (4) 将得到的白色固体放入马弗炉中，在空气气氛中，以 5°C/min的速率升温至 550°C，煅烧反应 3小吋，冷却后放入体积浓度为 10%醋酸溶液中搅拌反应 0.5 小吋，过滤、水洗、干燥后得到空心二氧化锆。 [0029] (4) The obtained white solid was placed in a muffle furnace, heated to 550 ° C at a rate of 5 ° C / min in an air atmosphere, calcined for 3 hours, and cooled to a volume concentration of The reaction was stirred for 0.5 hour in a 10% acetic acid solution, filtered, washed with water, and dried to obtain a hollow zirconium dioxide.

[0030] (5) 将 30mg空心二氧化锆、 60mg硫单质、 10mg石墨烯加入到二硫化碳中，超声分散 5小吋，形成悬浮液，然后 60°C蒸干溶剂，得到复合材料。 [0030] (5) 30 mg of hollow zirconium dioxide, 60 mg of sulfur simple substance, and 10 mg of graphene were added to carbon disulfide, ultrasonically dispersed for 5 hours to form a suspension, and then the solvent was evaporated to dryness at 60 ° C to obtain a composite material.

[0031] [0031]

[0032] 实施例 3 Example 3

[0033] (1) 称取 lOOmg的纳米碳酸钙粉末加入到无水乙醇中，超声 30分钟形成悬浮液。 [0033] (1) 100 mg of the nano calcium carbonate powder was weighed and added to absolute ethanol, and ultrasonicated for 30 minutes to form a suspension.

[0034] (2) 称取 lOOmg二氯氧锆和 40mg氯化钇溶于去 lOOmL离子水中，配制成水溶液。 [0034] (2) Weighing 100 mg of zirconium oxychloride and 40 mg of cerium chloride dissolved in 100 mL of ionic water to prepare an aqueous solution.

[0035] (3) 将（2) 得到的水溶液在 90°C水浴中缓慢加入到悬浮液中，加入吋间为 4 小吋，然后加入氨水调节值，再加入 lOOmg聚乙二醇，将反应混合物继续搅拌 6 小吋后，在室温下陈化 15小吋得到白色沉淀，过滤、洗涤、干燥，得到白色固体。 [0035] (3) The aqueous solution obtained in (2) is slowly added to the suspension in a 90 ° C water bath, added to the crucible for 4 hours, then added to the ammonia water adjustment value, and then added 100 mg of polyethylene glycol, the reaction After the mixture was stirred for 6 hours, it was aged 15 hrs at room temperature to give a white precipitate which was filtered, washed and dried to give a white solid.

[0036] (4) 将得到的白色固体放入马弗炉中，在空气气氛中，以 3°C/min的速率升温至 525°C，煅烧反应 5小吋，冷却后放入体积浓度为 6%醋酸溶液中搅拌反应 4小吋，过滤、水洗、干燥后得到空心二氧化锆。 [0036] (4) The obtained white solid was placed in a muffle furnace, heated to 525 ° C at a rate of 3 ° C / min in an air atmosphere, calcined for 5 hours, cooled and placed in a volume concentration of The reaction was stirred for 4 hours in a 6% acetic acid solution, filtered, washed with water, and dried to obtain a hollow zirconium dioxide.

[0037] (5) 将 23mg空心二氧化锆、 70mg硫单质、 7mg石墨烯加入到二硫化碳中，超声分散 1小吋，形成悬浮液，然后 50°C蒸干溶剂，得到复合材料。 [0037] (5) 23 mg of hollow zirconia, 70 mg of sulfur, and 7 mg of graphene were added to carbon disulfide, and the suspension was ultrasonically dispersed for 1 hour to form a suspension, and then the solvent was evaporated to dryness at 50 ° C to obtain a composite material.

[0038] [0038]

[0039] 实施例 4 Example 4

[0040] (1) 称取 lOOmg的纳米碳酸钙粉末加入到无水乙醇中，超声 40分钟形成悬浮液。 [0041] (2) 称取 50mg二氯氧锆和 25mg氯化钇溶于去 lOOmL离子水中，配制成水溶液 [0040] (1) 100 mg of the nano calcium carbonate powder was weighed and added to absolute ethanol, and sonicated for 40 minutes to form a suspension. [0041] (2) Weigh 50mg of zirconium oxychloride and 25mg of cerium chloride dissolved in 100mL of ionic water, formulated into an aqueous solution

[0042] (3) 将（2) 得到的水溶液在 90°C水浴中缓慢加入到悬浮液中，加入吋间为 3.5 小吋，然后加入氨水调节值，再加入 lOOmg聚乙二醇，将反应混合物继续搅拌 9 小吋后，在室温下陈化 18小吋得到白色沉淀，过滤、洗涤、干燥，得到白色固体。 [0042] (3) The aqueous solution obtained in (2) is slowly added to the suspension in a 90 ° C water bath, added to the crucible for 3.5 hours, then added to the ammonia water adjustment value, and then added 100 mg of polyethylene glycol, the reaction After the mixture was stirred for 9 hours, it was aged 18 hrs at room temperature to give a white precipitate which was filtered, washed and dried to give a white solid.

[0043] (4) 将得到的白色固体放入马弗炉中，在空气气氛中，以 4°C/min的速率升温至 540°C，煅烧反应 6小吋，冷却后放入体积浓度为 8%醋酸溶液中搅拌反应 2小吋，过滤、水洗、干燥后得到空心二氧化锆。 [0043] (4) The obtained white solid was placed in a muffle furnace, heated to 540 ° C at a rate of 4 ° C / min in an air atmosphere, calcined for 6 hours, and cooled to a volume concentration of The reaction was stirred for 2 hours in an 8% acetic acid solution, filtered, washed with water, and dried to obtain a hollow zirconium dioxide.

[0044] (5) 将 20mg空心二氧化锆、 75mg硫单质、 5mg石墨烯加入到二硫化碳中，超声分散 2小吋，形成悬浮液，然后 45°C蒸干溶剂，得到复合材料。 (5) 20 mg of hollow zirconia, 75 mg of sulfur simple substance, and 5 mg of graphene were added to carbon disulfide, ultrasonically dispersed for 2 hours, and a suspension was formed, followed by evaporation of the solvent at 45 ° C to obtain a composite material.

[0045] [0045]

[0046] 实施例 5 Example 5

[0047] (1) 称取 lOOmg的纳米碳酸钙粉末加入到无水乙醇中，超声 50分钟形成悬浮液。 [0047] (1) 100 mg of the nano calcium carbonate powder was weighed and added to absolute ethanol, and ultrasonicated for 50 minutes to form a suspension.

[0048] (2) 称取 25mg二氯氧锆和 17.5mg氯化钇溶于去 lOOmL离子水中，配制成水溶液。 [0048] (2) Weigh 25 mg of zirconium oxychloride and 17.5 mg of cerium chloride dissolved in 100 mL of ionic water to prepare an aqueous solution.

[0049] (3) 将（2) 得到的水溶液在 90°C水浴中缓慢加入到悬浮液中，加入吋间为 4.5 小吋，然后加入氨水调节值，再加入 lOOmg聚乙二醇，将反应混合物继续搅拌 7 小吋后，在室温下陈化 20小吋得到白色沉淀，过滤、洗涤、干燥，得到白色固体。 [0049] (3) The aqueous solution obtained in (2) is slowly added to the suspension in a 90 ° C water bath, added to the crucible for 4.5 hours, then added to the ammonia water adjustment value, and then added 100 mg of polyethylene glycol, the reaction After the mixture was stirred for 7 hours, it was aged 20 hrs at room temperature to give a white precipitate which was filtered, washed and dried to give a white solid.

[0050] (4) 将得到的白色固体放入马弗炉中，在空气气氛中，以 2°C/min的速率升温至 510°C，煅烧反应 6小吋，冷却后放入体积浓度为 6%醋酸溶液中搅拌反应 4小吋 [0050] (4) The obtained white solid was placed in a muffle furnace, heated to 510 ° C at a rate of 2 ° C / min in an air atmosphere, calcined for 6 hours, and cooled to a volume concentration of Stirring reaction in 6% acetic acid solution for 4 hours

，过滤、水洗、干燥后得到空心二氧化锆。 After filtration, washing with water, drying to obtain hollow zirconium dioxide.

[0051] (5) 将 27mg空心二氧化锆、 65mg硫单质、 8mg石墨烯加入到二硫化碳中，超声分散 3小吋，形成悬浮液，然后 55°C蒸干溶剂，得到复合材料。 (5) 27 mg of hollow zirconium dioxide, 65 mg of sulfur simple substance, and 8 mg of graphene were added to carbon disulfide, and the mixture was ultrasonically dispersed for 3 hours to form a suspension, and then the solvent was evaporated to dryness at 55 ° C to obtain a composite material.

[0052] 电极的制备及性能测试；将电极材料、乙炔黑和 PVDF [0052] Electrode preparation and performance test; electrode material, acetylene black and PVDF

按质量比 80: 10： 10在 NMP中混合，涂覆在铝箔上为电极膜，金属锂片为对电极， CELGARD Mixed in NMP according to mass ratio of 80:10:10, coated on aluminum foil as electrode film, metal lithium sheet is used for electricity Extreme, CELGARD

2400为隔膜， lmol/L的 LiTFSI/DOL-DME (体积比 1： 1)为电解液， lmol/L的 LiN03 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。表 1 2400 is a diaphragm, 1 mol/L of LiTFSI/DOL-DME (volume ratio 1:1) is an electrolyte, and 1 mol/L of LiN03 is an additive. It is assembled into a button-type battery in a filled glove box, and is tested by a Land battery test system. Constant current charge and discharge test. The charge and discharge voltage range is 1-3V, the current density is 1C, and the performance is shown in Table 1. Table 1

[表 1] [Table 1]

[0054] [0054]

[0055] 图 1为本发明制备出正极材料的 SEM图，从图中可以看出二氧化锆包覆的硫化锂颗粒均匀的分布在石墨烯表面上，有利于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 that the zirconium dioxide-coated lithium sulfide particles are uniformly distributed on the surface of the graphene, which is advantageous for improving the electrochemical performance of the material.

[0056] 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 it is not intended that the specific embodiments of the invention are limited to the description. It will be apparent to those skilled in the art that the present invention may be practiced without departing from the spirit and scope of the invention.

[0057] [0057]

Claims

权利要求书 Claim

[权利要求 1] 一种石墨烯 /二氧化锆空心球 /硫复合材料的制备方法，其特征在于，包括以下几个步骤： [Claim 1] A method for preparing a graphene/zirconia hollow sphere/sulfur composite material, comprising the following steps:

步骤（1) ：称取纳米碳酸钙粉末加入到无水乙醇中，超声形成悬浮液； Step (1): Weighing the nano calcium carbonate powder into anhydrous ethanol and ultrasonically forming a suspension;

步骤（2) ：称取二氯氧锆和氯化钇溶于去离子水中，配制成水溶液步骤（3) ：将步骤（2) 得到的水溶液在水浴中缓慢加入到悬浮液中，然后加入氨水调节值，再加入表面活性剂聚乙二醇，将反应混合物继续搅拌后，在室温下陈化后得到白色沉淀，过滤、洗涤、干燥，得到白色固体； Step (2): Weigh zirconium oxychloride and cerium chloride dissolved in deionized water to prepare an aqueous solution. Step (3): slowly add the aqueous solution obtained in step (2) to the suspension in a water bath, and then add ammonia water. Adjusting the value, adding the surfactant polyethylene glycol, stirring the reaction mixture, and then aging at room temperature to obtain a white precipitate, which is filtered, washed and dried to obtain a white solid;

步骤（4) ：将得到的白色固体放入马弗炉中，在空气气氛中，煅烧除去有机杂质，冷却后放入醋酸溶液中搅拌除去碳酸钙，过滤、水洗、干燥后得到空心二氧化锆； Step (4): The obtained white solid is placed in a muffle furnace, and the organic impurities are removed by calcination in an air atmosphere, cooled, placed in an acetic acid solution, stirred to remove calcium carbonate, filtered, washed with water, and dried to obtain hollow zirconia. ;

步骤（5) ：将得到的空心二氧化锆、硫单质、石墨烯加入到二硫化碳中，超声分散，形成悬浮液，然后蒸干溶剂，得到复合材料。 Step (5): The obtained hollow zirconium dioxide, sulfur elemental, graphene is added to carbon disulfide, ultrasonically dispersed to form a suspension, and then the solvent is evaporated to obtain a composite material.

[权利要求 2] 如权利要求 1所述的方法，其特征在于，所述步骤（1) 中纳米碳酸钙的粒径为 40- lOOnm，超声吋间为 20-60分钟。 [Claim 2] The method according to claim 1, wherein the nanometer calcium carbonate in the step (1) has a particle diameter of 40 to 100 nm and an ultrasonic time of 20 to 60 minutes.

[权利要求 3] 如权利要求 1所述的方法，其特征在于，所述步骤（2) 中二氯氧锆：氯化钇：碳酸钙的质量比为 1 : 0.2-0.8： 0.5-5。 [Claim 3] The method according to claim 1, wherein the mass ratio of zirconium oxychloride: cerium chloride: calcium carbonate in the step (2) is 1: 0.2-0.8: 0.5-5.

[权利要求 4] 如权利要求 1所述的方法，其特征在于，所述步骤（3) 中将（2) 得到的水溶液加入到悬浮液的吋间为 3-5小吋。 [Claim 4] The method according to claim 1, wherein in the step (3), the aqueous solution obtained in (2) is added to the crucible of the suspension for 3-5 hours.

[权利要求 5] 如权利要求 1所述的方法，其特征在于，所述步骤 (3) 中氨水调节 P [Claim 5] The method according to claim 1, wherein the ammonia water adjustment in the step (3)

H为 9-11，二氯氧锆与聚乙二醇的质量比为 1:0.5-5，搅拌反应吋间 3-1 H is 9-11, the mass ratio of zirconyl oxychloride to polyethylene glycol is 1:0.5-5, stirring reaction time 3-1

0小吋，陈化吋间 12-24小吋。 0 small 吋, Chen Huan 12 12-24 hours.

[权利要求 6] 如权利要求 1所述的方法，其特征在于，所述步骤（3) 中水浴温度为 [Claim 6] The method according to claim 1, wherein the temperature of the water bath in the step (3) is

90。C。 90. C.

[权利要求 7] 如权利要求 1所述的方法，其特征在于，所述步骤（4) 中，马弗炉的升温速率为 l-5°C/min，煅烧温度为 500-550°C，反应吋间 3-7小时；醋酸溶液为 5-10%，搅拌反应吋间 0.5-5小时。 [Claim 7] The method according to claim 1, wherein in the step (4), the muffle furnace The heating rate is l-5 ° C / min, the calcination temperature is 500-550 ° C, the reaction time is 3-7 hours; the acetic acid solution is 5-10%, and the reaction reaction is stirred for 0.5-5 hours.

[权利要求 8] 如权利要求 1所述的方法，其特征在于，所述步骤（5) 空心二氧化销[Claim 8] The method according to claim 1, wherein the step (5) hollow dioxide pin

、硫单质、石墨烯的质量比为 15-30:60-80: The mass ratio of sulfur elemental to graphene is 15-30:60-80:

5-10；超声分散时间为 0.5-5小时；蒸干溶剂的温度为 40-60°C。 5-10; The ultrasonic dispersion time is 0.5-5 hours; the temperature of the evaporated solvent is 40-60 °C.