WO2017139989A1 - Preparation method for graphene/titanium dioxide hollow sphere/sulphur composite material - Google Patents
Preparation method for graphene/titanium dioxide hollow sphere/sulphur composite material Download PDFInfo
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- WO2017139989A1 WO2017139989A1 PCT/CN2016/074184 CN2016074184W WO2017139989A1 WO 2017139989 A1 WO2017139989 A1 WO 2017139989A1 CN 2016074184 W CN2016074184 W CN 2016074184W WO 2017139989 A1 WO2017139989 A1 WO 2017139989A1
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- H01M4/02—Electrodes composed of, or comprising, active material
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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;
- the final product of the reaction, Li 2 S is also an electronic insulator, which is deposited on the sulfur electrode, and lithium
- the migration speed of ions in solid lithium sulfide is slow, which makes the electrochemical reaction kinetics slower.
- the technical problem to be solved by the present invention is to provide a graphene/titanium dioxide hollow sphere/sulfur composite material, which has a simple preparation method, and a conductive conductive graphene provides a conductive network, and the hollow structure of titanium dioxide is coated with a sulfur-based material to prevent discharge.
- the invention provides a preparation process of a graphene/titanium dioxide hollow sphere/sulfur composite material as follows:
- Graphene is added to an aqueous solution to be ultrasonically dispersed to form a suspension.
- Titanium sulphate and ammonium chloride are sequentially added to the above suspension and stirred uniformly, and then added to a hydrothermal kettle for hydrothermal reaction. After the reaction is completed, the mixture is naturally cooled, filtered, washed with water, washed with ethanol, and dried to obtain hollow titanium dioxide graphite. Aene composite.
- the concentration of the graphene suspension in the step (1) is 1-10 g / L, and the ultrasonic time is 20-60 minutes;
- the mass ratio of ammonium chloride: titanium sulfate: graphite oxide in the step (2) is 1:5-10:0.5-1, the temperature of the hydrothermal reaction is 160-200 ° C, and the reaction time is 3-10 hours.
- the invention has the following beneficial effects: (1) graphene has ultra-high electrical conductivity, and the graphene/titanium dioxide hollow sphere/sulfur composite material prepared by the method can effectively improve the electronic conductivity and ions of the lithium sulfur battery cathode material. Conductivity; (2) Graphene/titanium dioxide hollow sphere/sulfur composite material The titanium dioxide hollow sphere is coated with a sulfur-based material, which can inhibit the dissolution of the polysulfide of the discharge product and alleviate the volume expansion and improve its electrochemical performance.
- Figure 1 is an SEM image of a graphene/titanium dioxide hollow sphere/sulfur composite prepared in accordance with the present invention.
- Electrode preparation and performance test electrode material, acetylene black and PVDF were mixed in NMP at a mass ratio of 80:10:10, coated on aluminum foil as electrode film, lithium metal plate as counter electrode, CELGARD 2400 as separator, 1 mol /L LiTFSI/DOL-DME (volume ratio 1:1) is an electrolyte, 1mol/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
- 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 titanium oxide-coated lithium sulfide particles are uniformly distributed on the surface of the graphene, which is beneficial to improving the electrochemical performance of the material.
Abstract
Provided is a preparation method for a graphene/titanium dioxide hollow sphere/sulphur composite material, comprising the following steps: (1) adding graphene to an aqueous solution and implementing ultrasonic dispersion to form a suspension; (2) adding titanium sulphate and ammonium chloride to the suspension in turn and mixing uniformly, adding same to a hydrothermal kettle to implement a hydrothermal reaction, and after completion of the reaction, cooling naturally, filtering, washing with water, washing with ethanol, and drying to obtain a hollow titanium dioxide graphene composite material; and (3) adding the hollow titanium dioxide graphene composite material and elemental sulphur to carbon disulphide, implementing ultrasonic dispersion to form a suspension, and then evaporating the solvent to obtain a graphene/titanium dioxide hollow sphere/sulphur composite material. The titanium dioxide hollow spheres in the graphene/titanium dioxide hollow sphere/sulphur composite material are covered with a sulphur base material, and can inhibit the dissolution of polysulphides from the discharge product and mitigate volume expansion, improving electrochemical performance.
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 The migration speed of ions in solid lithium sulfide is slow, which makes the electrochemical reaction kinetics slower. (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 Li 2 . 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石墨烯/二氧化钛空心球/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，空心结构的二氧化钛包覆着硫基材料，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。The technical problem to be solved by the present invention is to provide a graphene/titanium dioxide hollow sphere/sulfur composite material, which has a simple preparation method, and a conductive conductive graphene provides a conductive network, and the hollow structure of titanium dioxide is coated with a sulfur-based material to prevent discharge. The dissolution of the product polysulfide and ease volume expansion, improve the electrical energy of the material
Chemical properties.
问题的解决方案Problem solution
本发明提供一种石墨烯/二氧化钛空心球/硫复合材料的制备工艺流程如下：The invention provides a preparation process of a graphene/titanium dioxide hollow sphere/sulfur composite material as follows:
(1)将石墨烯加入到水溶液中超声分散，形成悬浮液。(1) Graphene is added to an aqueous solution to be ultrasonically dispersed to form a suspension.
(2)将硫酸钛、氯化铵依次加入到上述悬浮液中搅拌均匀，然后加入水热釜中进行水热反应，反应完全后自然冷却、过滤、水洗、乙醇洗、干燥后得到空心二氧化钛石墨烯复合材料。(2) Titanium sulphate and ammonium chloride are sequentially added to the above suspension and stirred uniformly, and then added to a hydrothermal kettle for hydrothermal reaction. After the reaction is completed, the mixture is naturally cooled, filtered, washed with water, washed with ethanol, and dried to obtain hollow titanium dioxide graphite. Aene composite.
(3)将得到的空心二氧化钛石墨烯复合材料和硫单质加入到二硫化碳中，超声分散，形成悬浮液，然后蒸干溶剂，得到复合材料。(3) The obtained hollow titanium dioxide graphene composite material and sulfur element are added to carbon disulfide, ultrasonically dispersed to form a suspension, and then the solvent is evaporated to obtain a composite material.
步骤(1)中石墨烯悬浮液的浓度为1-10g/L，超声时间为20-60分钟；The concentration of the graphene suspension in the step (1) is 1-10 g / L, and the ultrasonic time is 20-60 minutes;
步骤(2)中氯化铵∶硫酸钛∶氧化石墨的质量比为：1∶5-10∶0.5-1，水热反应的温度为160-200℃，反应时间为3-10小时。The mass ratio of ammonium chloride: titanium sulfate: graphite oxide in the step (2) is 1:5-10:0.5-1, the temperature of the hydrothermal reaction is 160-200 ° C, and the reaction time is 3-10 hours.
步骤(3)空心二氧化钛石墨烯复合材料、硫单质质量比为1∶2-10，超声分散时间为0.5-5小时；蒸干溶剂的温度为40-60℃。Step (3) Hollow titanium dioxide graphene composite material, sulfur mass ratio is 1:2-10, ultrasonic dispersion time is 0.5-5 hours; evaporation dry solvent temperature is 40-60 °C.
发明的有益效果Advantageous effects of the invention
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/二氧化钛空心球/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/二氧化钛空心球/硫复合材料中二氧化钛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。The invention has the following beneficial effects: (1) graphene has ultra-high electrical conductivity, and the graphene/titanium dioxide hollow sphere/sulfur composite material prepared by the method can effectively improve the electronic conductivity and ions of the lithium sulfur battery cathode material. Conductivity; (2) Graphene/titanium dioxide hollow sphere/sulfur composite material The titanium dioxide hollow sphere is coated with a sulfur-based material, which can inhibit the dissolution of the polysulfide of the discharge product and alleviate the volume expansion and improve its electrochemical performance.
对附图的简要说明Brief description of the drawing
图1是本发明制备的石墨烯/二氧化钛空心球/硫复合材料的SEM图。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an SEM image of a graphene/titanium dioxide hollow sphere/sulfur composite prepared in accordance with 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500mg石墨烯加入到500mL水溶液中超声20分钟，形成1g/L悬浮液。(1) 500 mg of graphene was added to 500 mL of an aqueous solution for 20 minutes to form a 1 g/L suspension.
(2)将5g硫酸钛、1g氯化铵依次加入到上述悬浮液中搅拌均匀，然后加入水热釜中进行水热反应，160℃水热反应10小时，反应完全后自然冷却、过滤、水洗、乙醇洗、干燥后得到空心二氧化钛石墨烯复合材料。(2) 5 g of titanium sulphate and 1 g of ammonium chloride were sequentially added to the above suspension and stirred uniformly, and then added to a hydrothermal kettle for hydrothermal reaction, hydrothermal reaction at 160 ° C for 10 hours, after the reaction was completely cooled, filtered, washed with water. After washing with ethanol and drying, a hollow titanium dioxide graphene composite material is obtained.
(3)将100mg空心二氧化钛石墨烯复合材料和20mg硫单质加入到二硫化碳中，超声分散0.5小时，形成悬浮液，然后40℃蒸干溶剂，得到复合材料。(3) 100 mg of hollow titanium dioxide graphene composite material and 20 mg of sulfur elemental substance were added to carbon disulfide, ultrasonically dispersed for 0.5 hour to form a suspension, and then the solvent was evaporated to dryness at 40 ° C to obtain a composite material.
实施例2Example 2
(1)将500mg石墨烯加入到50mL水溶液中超声60分钟，形成10g/L悬浮液。(1) 500 mg of graphene was added to a 50 mL aqueous solution for 60 minutes to form a 10 g/L suspension.
(2)将5g硫酸钛、500mg氯化铵依次加入到上述悬浮液中搅拌均匀，然后加入水热釜中进行水热反应，200℃水热反应3小时，反应完全后自然冷却、过滤、水洗、乙醇洗、干燥后得到空心二氧化钛石墨烯复合材料。(2) 5 g of titanium sulphate and 500 mg of ammonium chloride were sequentially added to the above suspension and stirred uniformly, then added to a hydrothermal kettle for hydrothermal reaction, and hydrothermally reacted at 200 ° C for 3 hours. After the reaction was completed, it was naturally cooled, filtered, and washed. After washing with ethanol and drying, a hollow titanium dioxide graphene composite material is obtained.
(3)将100mg空心二氧化钛石墨烯复合材料和1g硫单质加入到二硫化碳中，超声分散5小时，形成悬浮液，然后60℃蒸干溶剂，得到复合材料。(3) 100 mg of a hollow titanium dioxide graphene composite material and 1 g of sulfur elemental substance 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.
实施例3Example 3
(1)将5mg石墨烯加入到200mL水溶液中超声30分钟，形成2.5g/L悬浮液。(1) 5 mg of graphene was added to a 200 mL aqueous solution for 30 minutes to form a 2.5 g/L suspension.
(2)将5g硫酸钛、625mg氯化铵依次加入到上述悬浮液中搅拌均匀，然后加入水热釜中进行水热反应，170℃水热反应8小时，反应完全后自然冷却、过滤、水洗、乙醇洗、干燥后得到空心二氧化钛石墨烯复合材料。(2) 5 g of titanium sulfate and 625 mg of ammonium chloride were sequentially added to the above suspension and stirred uniformly, and then added to a hydrothermal kettle for hydrothermal reaction, and hydrothermal reaction was carried out at 170 ° C for 8 hours. After the reaction was completed, it was naturally cooled, filtered, and washed. After washing with ethanol and drying, a hollow titanium dioxide graphene composite material is obtained.
(3)将100mg空心二氧化钛石墨烯复合材料和500mg硫单质加入到二硫化碳中，超声分散1小时，形成悬浮液，然后50℃蒸干溶剂，得到复合材料。(3) 100 mg of a hollow titanium dioxide graphene composite material and 500 mg of sulfur elemental substance were added to carbon disulfide, 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.
实施例4Example 4
(1)将300mg石墨烯加入到100mL水溶液中超声40分钟，形成3g/L悬浮液。(1) 300 mg of graphene was added to a 100 mL aqueous solution for 40 minutes to form a 3 g/L suspension.
(2)将3g硫酸钛、500mg氯化铵依次加入到上述悬浮液中搅拌均匀，然后加
入水热釜中进行水热反应，180℃水热反应6小时，反应完全后自然冷却、过滤、水洗、乙醇洗、干燥后得到空心二氧化钛石墨烯复合材料。(2) adding 3 g of titanium sulfate and 500 mg of ammonium chloride to the above suspension in this order, stirring uniformly, and then adding
The hydrothermal reaction was carried out in a hot water kettle, and hydrothermal reaction was carried out at 180 ° C for 6 hours. After the reaction was completed, it was naturally cooled, filtered, washed with water, washed with ethanol, and dried to obtain a hollow titanium dioxide graphene composite material.
(3)将100mg空心二氧化钛石墨烯复合材料和800mg硫单质加入到二硫化碳中，超声分散2小时，形成悬浮液，然后45℃蒸干溶剂，得到复合材料。(3) 100 mg of hollow titanium dioxide graphene composite material and 800 mg of sulfur elemental substance were added to carbon disulfide, ultrasonically dispersed for 2 hours to form a suspension, and then the solvent was evaporated to dryness at 45 ° C to obtain a composite material.
实施例5Example 5
(1)将200mg石墨烯加入到50mL水溶液中超声50分钟，形成4g/L悬浮液。(1) 200 mg of graphene was added to a 50 mL aqueous solution for 50 minutes to form a 4 g/L suspension.
(2)将2g硫酸钛、200mg氯化铵依次加入到上述悬浮液中搅拌均匀，然后加入水热釜中进行水热反应，190℃水热反应4小时，反应完全后自然冷却、过滤、水洗、乙醇洗、干燥后得到空心二氧化钛石墨烯复合材料。(2) 2g of titanium sulfate and 200mg of ammonium chloride were sequentially added to the above suspension and stirred uniformly, then added to the hydrothermal kettle for hydrothermal reaction, hydrothermal reaction at 190 ° C for 4 hours, after the reaction was completed, naturally cooled, filtered, washed After washing with ethanol and drying, a hollow titanium dioxide graphene composite material is obtained.
(3)将100mg空心二氧化钛石墨烯复合材料和400mg硫单质加入到二硫化碳中，超声分散3小时，形成悬浮液，然后55℃蒸干溶剂，得到复合材料。(3) 100 mg of hollow titanium dioxide graphene composite material and 400 mg of sulfur elemental substance were added to carbon disulfide, 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.
电极的制备及性能测试；将电极材料、乙炔黑和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 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; electrode material, acetylene black and PVDF were mixed in NMP at a mass ratio of 80:10:10, coated on aluminum foil as electrode film, lithium metal plate as counter electrode, CELGARD 2400 as separator, 1 mol /L LiTFSI/DOL-DME (volume ratio 1:1) is an electrolyte, 1mol/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]
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钛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 from the figure that the titanium oxide-coated lithium sulfide particles are uniformly distributed on the surface of the graphene, which is beneficial to improving the electrochemical performance of the material.
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)
- 一种石墨烯/二氧化钛空心球/硫复合材料的制备方法，其特征在于，包括以下几个步骤：A method for preparing a graphene/titanium dioxide hollow sphere/sulfur composite material, comprising the following steps:步骤(1)将石墨烯加入到水溶液中超声分散，形成悬浮液；Step (1) adding graphene to an aqueous solution to ultrasonically disperse to form a suspension;步骤(2)将硫酸钛、氯化铵依次加入到上述悬浮液中搅拌均匀，然后加入水热釜中进行水热反应，反应完全后自然冷却、过滤、水洗、乙醇洗、干燥后得到空心二氧化钛石墨烯复合材料；Step (2) adding titanium sulfate and ammonium chloride to the above suspension in sequence and stirring uniformly, and then adding to the hydrothermal kettle for hydrothermal reaction, after the reaction is completely cooled, filtered, washed with water, washed with ethanol, dried to obtain hollow titanium dioxide. Graphene composite material;步骤(3)将得到的空心二氧化钛石墨烯复合材料和硫单质加入到二硫化碳中，超声分散，形成悬浮液，然后蒸干溶剂，得到石墨烯/二氧化钛空心球/硫复合材料。Step (3) The obtained hollow titanium dioxide graphene composite material and sulfur element are added to carbon disulfide, ultrasonically dispersed to form a suspension, and then the solvent is evaporated to obtain a graphene/titanium dioxide hollow sphere/sulfur composite material.
- 如权利要求1所述的方法，其特征在于，所述步骤(1)中石墨烯悬浮液的浓度为1-10g/L，超声时间为20-60分钟。The method according to claim 1, wherein the concentration of the graphene suspension in the step (1) is 1-10 g/L, and the ultrasonic time is 20-60 minutes.
- 如权利要求1所述的方法，其特征在于，所述步骤(2)中氯化铵、硫酸钛与氧化石墨的质量比为：1∶5-10∶0.5-1，水热反应的温度为160-200℃，反应时间为3-10小时。The method according to claim 1, wherein the mass ratio of ammonium chloride, titanium sulfate and graphite oxide in the step (2) is 1:5-10:0.5-1, and the temperature of the hydrothermal reaction is 160-200 ° C, the reaction time is 3-10 hours.
- 如权利要求1所述的方法，其特征在于，所述步骤(3)空心二氧化钛石墨烯复合材料、硫单质质量比为1∶2-10，超声分散时间为0.5-5小时；蒸干溶剂的温度为40-60℃。 The method according to claim 1, wherein the step (3) hollow titanium dioxide graphene composite material has a sulfur mass ratio of 1:2-10, an ultrasonic dispersion time of 0.5-5 hours, and an evaporation of the solvent. The temperature is 40-60 ° C.
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