WO2017139939A1 - Method for preparing graphene/polyaniline/sulfur composite positive electrode material - Google Patents

Method for preparing graphene/polyaniline/sulfur composite positive electrode material Download PDF

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WO2017139939A1
WO2017139939A1 PCT/CN2016/074003 CN2016074003W WO2017139939A1 WO 2017139939 A1 WO2017139939 A1 WO 2017139939A1 CN 2016074003 W CN2016074003 W CN 2016074003W WO 2017139939 A1 WO2017139939 A1 WO 2017139939A1
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sulfur
graphene
stirred
composite material
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肖丽芳
钟玲珑
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肖丽芳
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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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
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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  • the invention belongs to the field of nano material synthesis, and relates to a preparation method of a lithium sulfur battery cathode material, in particular to a method for preparing a graphene/polyaniline/sulfur composite cathode material.
  • 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 ionic insulator, and the room temperature conductivity is low (5 ⁇ 10 -3 OS ⁇ cm -1 ). Since there is no ionic sulfur, it acts as a positive electrode.
  • 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. The gradient 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 invention provides a graphene/polyaniline/sulfur composite material, the preparation method is simple, the conductive conductive graphene provides a conductive network, and the sulfur particles are coated to limit the movement of the polysulfide, and the outer layer is aggregated.
  • the aniline coated sulfur nanographene not only improves the conductivity of sulfur, but also prevents the dissolution of the polysulfide of the discharge product and relieves the volume expansion.
  • the composite material is used as the positive electrode of the lithium-sulfur battery, and has the characteristics of high capacity and stable cycle performance. .
  • the mass ratio of sodium sulfide to elemental sulfur is 1:1 to 1:5
  • the mass fraction of Triton X-100 is 1%
  • the ratio of sodium sulfide to Triton X-100 solution is 1- 50g: 1ml.
  • the mass ratio of the amount of the graphite oxide to the sodium sulfide is 1:5-50.
  • the ratio of the amount of the graphite oxide to the potassium iodide solution is 1 mg: 1-5 ml; and the volume ratio of the dilute hydrochloric acid to the potassium iodide solution is 1:5-10.
  • the mass ratio of the aniline to the sodium sulfide is 1:10-50; the mass ratio of the initiator to the aniline is 1:0.5-5.
  • the initiator is one of ammonium persulfate, potassium dichromate and ferric chloride.
  • the mass fraction of concentrated hydrochloric acid is 30%, and in the step (3), the mass fraction of dilute hydrochloric acid is 10%.
  • the invention has the following beneficial effects: (1)
  • the graphene/polyaniline/sulfur composite material prepared by the method prepared by the method has a three-layer structure, the inner layer of sulfur particles, and the intermediate layer is a curved graphene coating layer, The layer is a polyaniline coating; (2) both graphene and polyaniline have ultra-high electrical conductivity, and the graphene/polyaniline/sulfur composite prepared by the method can effectively improve the electron of the cathode material of the lithium-sulfur battery. Conductivity and ionic conductivity; (3)
  • the sulfur in the graphene/polyaniline/sulfur composite is coated with flexible graphene and polyaniline, which can inhibit the dissolution of the polysulfide of the discharge product and alleviate the volume expansion.
  • Figure 1 is an SEM image of a graphene/polyaniline/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, 1 mol/L LiNO 3 is an additive, assembled into a button-type battery in a filled glove box, and a constant current charge and discharge is performed using a Land battery test system. test.
  • the charging and discharging voltage range is 1-3V
  • the current density is 0.01C
  • performance results are shown in Table 1;
  • the SEM image of the graphene/polyaniline/sulfur composite shows that the graphene is bent and wrapped on the surface of the nano-sulfur particles instead of the usual lamellar structure, while the polyaniline is also coated on the graphite.
  • the outer layer of the olefin can effectively prevent the expansion of sulfur and the shuttle of polysulfide to affect the capacity.

Abstract

Provided in the present invention is a method for preparing a graphene/polyaniline/sulfur composite positive electrode material, which comprises the following steps: (1) grinding sodium sulfide and elemental sulfur in an agate mortar, then dissolving the mixture in distilled water to obtain an orange-colored solution, adding TritonX-100 into the solution, and adding concentrated hydrochloric acid to form a yellow-colored suspension; (2) adding graphite oxide to distilled water and performing ultrasonic treatment, and adding the obtained graphene oxide solution to the yellow-colored suspension to obtain a sulfur graphene oxide composite material; (3) adding the obtained sulfur graphene oxide composite material to a potassium iodide solution, and then adding diluted hydrochloric acid to obtain a sulfur graphene composite material; (4) adding the obtained sulfur graphene composite material to water and then stirring, adding aniline and then stirring, and adding an initiator to obtain the graphene/polyaniline/sulfur composite material. The graphene/polyaniline/sulfur composite material of the present invention may inhibit the dissolution of a polysulfide discharging product, while easing the volumetric expansion thereof.

Description

一种石墨烯/聚苯胺/硫复合正极材料的制备方法Method for preparing graphene/polyaniline/sulfur composite cathode material 技术领域Technical field
本发明属于纳米材料合成领域，涉及一种锂硫电池正极材料的制备方法，尤其涉及一种石墨烯/聚苯胺/硫复合正极材料的制备方法。The invention belongs to the field of nano material synthesis, and relates to a preparation method of a lithium sulfur battery cathode material, in particular to a method for preparing a graphene/polyaniline/sulfur composite cathode material.
背景技术Background technique
锂硫电池是以金属锂为负极，单质硫为正极的电池体系。锂硫电池的具有两个放电平台(约为2.4V和2.1V)，但其电化学反应机理比较复杂。锂硫电池具有比能量高(2600Wh/kg)、比容量高(1675mAh/g)、成本低等优点，被认为是很有发展前景的新一代电池。但是目前其存在着活性物质利用率低、循环寿命低和安全性差等问题，这严重制约着锂硫电池的发展。造成上述问题的主要原因有以下几个方面：(1)单质硫是电子和离子绝缘体，室温电导率低(5×10-3OS·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 ionic insulator, and the room temperature conductivity is low (5 × 10 -3 OS · cm -1 ). Since there is no ionic sulfur, it acts as a positive electrode. (1) 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. The gradient migrates to the negative electrode, and the high poly lithium polysulfide is reduced by the lithium metal to the oligomeric lithium polysulfide. As the above reaction proceeds, the oligomeric lithium polysulfide aggregates at the negative electrode, eventually forming a concentration difference between the two electrodes, and then migrating to the positive electrode to be oxidized to a highly polylithium polysulfide. This phenomenon is known as the shuttle effect, which reduces the utilization of sulfur active substances. At the same time, insoluble Li 2 S and Li 2 S 2 are deposited on the surface of the lithium negative electrode, which further deteriorates the performance of the lithium-sulfur battery; (3) the final product of the reaction, Li 2 S, is also an electronic insulator, which is deposited on the sulfur electrode, and lithium slow ion mobility in the solid state lithium sulfide, the slow electrochemical reaction kinetics; different density (4) sulfur and Li 2 S final product when sulfur is expanded to about 79% of the volume of lithium, Li 2 easily lead The powdering of S causes safety problems in lithium-sulfur batteries. The above-mentioned shortcomings restrict the development of lithium-sulfur batteries, which is also the key issue that needs to be solved in the research of lithium-sulfur batteries.
技术问题technical problem
本发明提供一种石墨烯/聚苯胺/硫复合材料，该制备方法简单，导电性良好的石墨烯提供导电网络，同时对硫颗粒进行包覆限制多硫化物的移动，外层的聚 苯胺包覆硫纳米石墨烯，不但改善硫的导电性，而且能够阻止放电产物多硫化物的溶解并缓解体积膨胀，以该复合材料作为锂硫电池的正极，具有容量高、循环性能稳定的特点。The invention provides a graphene/polyaniline/sulfur composite material, the preparation method is simple, the conductive conductive graphene provides a conductive network, and the sulfur particles are coated to limit the movement of the polysulfide, and the outer layer is aggregated. The aniline coated sulfur nanographene not only improves the conductivity of sulfur, but also prevents the dissolution of the polysulfide of the discharge product and relieves the volume expansion. The composite material is used as the positive electrode of the lithium-sulfur battery, and has the characteristics of high capacity and stable cycle performance. .
问题的解决方案Problem solution
技术解决方案Technical solution
具体方案如下：一种石墨烯/聚苯胺/硫复合正极材料的制备方法，包括以下几个步骤：The specific scheme is as follows: a preparation method of a graphene/polyaniline/sulfur composite cathode material, comprising the following steps:
(1)硫化钠和单质硫按比例在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水中，得到橙色溶液，将Triton X-100加入上述溶液，一边搅拌一边加入浓盐酸，逐渐形成黄色悬浮液；(1) Sodium sulfide and elemental sulfur are ground in an agate mortar in proportion, and then the mixture is dissolved in distilled water to obtain an orange solution. Triton X-100 is added to the above solution, and concentrated hydrochloric acid is added while stirring to gradually form a yellow suspension. ;
(2)将氧化石墨加入蒸馏水中超声，得到氧化石墨烯溶液，取氧化石墨烯溶液加入上述黄色悬浮液，水浴中搅拌，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料；(2) Adding graphite oxide to distilled water to obtain a graphene oxide solution, adding the graphene oxide solution to the above yellow suspension, stirring in a water bath, and obtaining a suspension which is centrifuged, washed with water, and freeze-dried to obtain dark gray sulfur oxide graphite. Alkene composite material;
(3)将得到的硫氧化石墨烯复合材料加入碘化钾溶液，然后加入稀盐酸，密封，并移至黑暗环境下反应，离心，水洗，乙醇洗，得到硫石墨烯复合材料；(3) adding the obtained sulfur oxide graphene composite material to a potassium iodide solution, then adding dilute hydrochloric acid, sealing, and moving to a dark environment for reaction, centrifugation, water washing, and ethanol washing to obtain a sulfur graphene composite material;
(4)将得到的硫石墨烯复合材料加入水中搅拌，再加入苯胺搅拌，然后加入引发剂，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) The obtained sulfur graphene composite material is stirred in water, stirred with aniline, and then added with an initiator, stirred, stood, filtered, and vacuum dried to obtain a graphene/polyaniline/sulfur composite material.
优选的，所述步骤(1)中硫化钠和单质硫质量比为1∶1-1∶5，Triton X-100的质量分数为1％，硫化钠与Triton X-100溶液的比例为1-50g∶1ml。Preferably, in the step (1), the mass ratio of sodium sulfide to elemental sulfur is 1:1 to 1:5, the mass fraction of Triton X-100 is 1%, and the ratio of sodium sulfide to Triton X-100 solution is 1- 50g: 1ml.
优选的，所述步骤(2)中，氧化石墨的量与硫化钠的质量比例为1∶5-50。Preferably, in the step (2), the mass ratio of the amount of the graphite oxide to the sodium sulfide is 1:5-50.
优选的，所述步骤(3)中，氧化石墨的量与碘化钾溶液的比例为1mg∶1-5ml；稀盐酸与碘化钾溶液的体积比例为1∶5-10。Preferably, in the step (3), the ratio of the amount of the graphite oxide to the potassium iodide solution is 1 mg: 1-5 ml; and the volume ratio of the dilute hydrochloric acid to the potassium iodide solution is 1:5-10.
优选的，所述步骤(4)中，苯胺与硫化钠的质量比例为1∶10-50；引发剂与苯胺的质量比为1∶0.5-5。Preferably, in the step (4), the mass ratio of the aniline to the sodium sulfide is 1:10-50; the mass ratio of the initiator to the aniline is 1:0.5-5.
优选的，所述引发剂采用过硫酸铵、重铬酸钾和氯化铁中的一种。Preferably, the initiator is one of ammonium persulfate, potassium dichromate and ferric chloride.
优选的，所述步骤(1)中，浓盐酸的质量分数为30％，所述步骤(3)中，稀盐酸的质量分数为10％。Preferably, in the step (1), the mass fraction of concentrated hydrochloric acid is 30%, and in the step (3), the mass fraction of dilute hydrochloric acid is 10%.
发明的有益效果 Advantageous effects of the invention
有益效果Beneficial effect
本发明具有如下有益效果：(1)该方法制备的该方法制备出的石墨烯/聚苯胺/硫复合材料具有三层结构，内层的硫颗粒，中间层是弯曲石墨烯包覆层，外层是聚苯胺包覆层；(2)石墨烯和聚苯胺都具有超高的电导率，通过该方法制备出的石墨烯/聚苯胺/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；(3)石墨烯/聚苯胺/硫复合材料中硫被具有柔韧性的石墨烯和聚苯胺包覆着，能抑制放电产物多硫化物的溶解以及缓解体积膨胀。The invention has the following beneficial effects: (1) The graphene/polyaniline/sulfur composite material prepared by the method prepared by the method has a three-layer structure, the inner layer of sulfur particles, and the intermediate layer is a curved graphene coating layer, The layer is a polyaniline coating; (2) both graphene and polyaniline have ultra-high electrical conductivity, and the graphene/polyaniline/sulfur composite prepared by the method can effectively improve the electron of the cathode material of the lithium-sulfur battery. Conductivity and ionic conductivity; (3) The sulfur in the graphene/polyaniline/sulfur composite is coated with flexible graphene and polyaniline, which can inhibit the dissolution of the polysulfide of the discharge product and alleviate the volume expansion.
对附图的简要说明Brief description of the drawing
附图说明DRAWINGS
图1是本发明制备的石墨烯/聚苯胺/硫复合材料的SEM图。BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an SEM image of a graphene/polyaniline/sulfur composite prepared in accordance with the present invention.
发明实施例Invention embodiment
本发明的实施方式Embodiments of the invention
下面结合附图，对本发明的较优的实施例作进一步的详细说明：The preferred embodiments of the present invention are further described in detail below with reference to the accompanying drawings:
实施例1Example 1
(1)10g硫化钠和50g单质硫在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水中，得到橙色溶液，将10ml质量分数1％的triton X-100加入上述溶液，并搅拌3小时，然后不断加入质量分数为30％的浓盐酸，搅拌3h，逐渐形成黄色悬浮液。(1) 10 g of sodium sulfide and 50 g of elemental sulfur were ground in an agate mortar, and then the mixture was dissolved in distilled water to obtain an orange solution, and 10 ml of a 1% by mass of triton X-100 was added to the above solution, and stirred for 3 hours, and then Concentrated hydrochloric acid with a mass fraction of 30% was continuously added and stirred for 3 hours to gradually form a yellow suspension.
(2)将2g氧化石墨加入蒸馏水中超声30min，形成1g/L的氧化石墨烯溶液，将氧化石墨烯溶液加入上述黄色悬浮液，在70℃水浴中搅拌1h，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料。(2) 2 g of graphite oxide was added to distilled water for 30 min to form a 1 g/L graphene oxide solution, and the graphene oxide solution was added to the above yellow suspension, and stirred in a water bath at 70 ° C for 1 h, and the obtained suspension was centrifuged and washed with water. After lyophilization, a dark gray sulfur oxide graphene composite material was obtained.
(3)将得到的硫氧化石墨烯复合材料加入2L浓度为2mol/L碘化钾溶液，然后再快速加入0.4L质量分数为10％的盐酸，密封，并移至黑暗环境下反应1h，离心，水洗，乙醇洗，得到硫石墨烯复合材料。(3) Add the obtained sulfur oxide graphene composite material to 2L of 2mol/L potassium iodide solution, then quickly add 0.4L of 10% hydrochloric acid, seal, and move to dark environment for 1h, centrifuge, wash. , washing with ethanol to obtain a sulfur graphene composite material.
(4)将得到的硫石墨烯复合材料加入水中搅拌10分钟，加入1g苯胺搅拌1h，然后加入0.5g引发剂过硫酸铵，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。 (4) The obtained sulphur graphene composite material was stirred in water for 10 minutes, 1 g of aniline was added and stirred for 1 hour, then 0.5 g of initiator ammonium persulfate was added, stirred, allowed to stand, filtered, and vacuum dried to obtain graphene/polyaniline. / sulfur composite material.
实施例2Example 2
(1)50g硫化钠和50g单质硫在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水中，得到橙色溶液，将1ml质量分数1％的triton X-100加入上述溶液，并搅拌3h，然后不断加入质量分数为30％的浓盐酸，搅拌3h，逐渐形成黄色悬浮液。(1) 50 g of sodium sulfide and 50 g of elemental sulfur were ground in an agate mortar, and then the mixture was dissolved in distilled water to obtain an orange solution, and 1 ml of a 1% by mass of triton X-100 was added to the above solution, and stirred for 3 hours, and then continuously Concentrated hydrochloric acid having a mass fraction of 30% was added and stirred for 3 hours to gradually form a yellow suspension.
(2)将1g氧化石墨加入蒸馏水中超声30min，形成1g/L的氧化石墨烯溶液，将氧化石墨烯溶液加入上述黄色悬浮液，在70℃水浴中搅拌1h，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料。(2) 1 g of graphite oxide was added to distilled water for 30 min to form a 1 g/L graphene oxide solution, and the graphene oxide solution was added to the above yellow suspension, and stirred in a water bath at 70 ° C for 1 h, and the obtained suspension was centrifuged and washed with water. After lyophilization, a dark gray sulfur oxide graphene composite material was obtained.
(3)将得到的硫氧化石墨烯复合材料加入5L浓度为2mol/L碘化钾溶液，然后再快速加入0.5L质量分数为10％的盐酸，密封，并移至黑暗环境下反应1h，离心，水洗，乙醇洗，得到硫石墨烯复合材料。(3) Add the obtained sulfur oxide graphene composite material to 5L of 2mol/L potassium iodide solution, then quickly add 0.5L of 10% hydrochloric acid, seal, and transfer to dark environment for 1h, centrifuge, wash. , washing with ethanol to obtain a sulfur graphene composite material.
(4)将得到的硫石墨烯复合材料加入水中搅拌10分钟，加入1g苯胺搅拌5h，然后加入5g引发剂重铬酸钾，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) The obtained sulfur graphene composite material was added to water and stirred for 10 minutes, and 1 g of aniline was added and stirred for 5 hours, then 5 g of initiator potassium dichromate was added, stirred, allowed to stand, filtered, and vacuum dried to obtain graphene/polyaniline. / sulfur composite material.
实施例3Example 3
(1)10g硫化钠和20g单质硫在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水中，得到橙色溶液，将1ml质量分数1％的triton X-100加入上述溶液，并搅拌3h，然后不断加入质量分数为30％的浓盐酸，搅拌3h，逐渐形成黄色悬浮液。(1) 10 g of sodium sulfide and 20 g of elemental sulfur were ground in an agate mortar, and then the mixture was dissolved in distilled water to obtain an orange solution, and 1 ml of a 1% by mass of triton X-100 was added to the above solution, and stirred for 3 hours, and then continuously Concentrated hydrochloric acid having a mass fraction of 30% was added and stirred for 3 hours to gradually form a yellow suspension.
(2)将1g氧化石墨加入蒸馏水中超声30min，形成1g/L的氧化石墨烯溶液，将氧化石墨烯溶液加入上述黄色悬浮液，在70℃水浴中搅拌1h，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料。(2) 1 g of graphite oxide was added to distilled water for 30 min to form a 1 g/L graphene oxide solution, and the graphene oxide solution was added to the above yellow suspension, and stirred in a water bath at 70 ° C for 1 h, and the obtained suspension was centrifuged and washed with water. After lyophilization, a dark gray sulfur oxide graphene composite material was obtained.
(3)将得到的硫氧化石墨烯复合材料加入2L浓度为2mol/L碘化钾溶液，然后再快速加入0.3L质量分数为10％的盐酸，密封，并移至黑暗环境下反应1h，离心，水洗，乙醇洗，得到硫石墨烯复合材料。(3) Add the obtained sulfur oxide graphene composite material to 2L of 2mol/L potassium iodide solution, then quickly add 0.3L of 10% hydrochloric acid, seal, and move to dark environment for 1h, centrifuge, wash. , washing with ethanol to obtain a sulfur graphene composite material.
(4)将得到的硫石墨烯复合材料加入水中搅拌10分钟，加入0.5g苯胺搅拌2h，然后加入0.5g引发剂氯化铁，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) The obtained sulphur graphene composite material was stirred in water for 10 minutes, 0.5 g of aniline was added and stirred for 2 hours, then 0.5 g of initiator ferric chloride was added, stirred, allowed to stand, filtered, and vacuum dried to obtain graphene/poly. Aniline/sulfur composite.
实施例4Example 4
(1)10g硫化钠和30g单质硫在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水 中，得到橙色溶液，将0.5ml质量分数1％的triton X-100加入上述溶液，并搅拌3h，然后不断加入质量分数为30％的浓盐酸，搅拌3h，逐渐形成黄色悬浮液。(1) 10 g of sodium sulfide and 30 g of elemental sulfur are ground in an agate mortar, and then the mixture is dissolved in distilled water. In the orange solution, 0.5 ml of a 1% triton X-100 was added to the above solution and stirred for 3 hours, then concentrated hydrochloric acid having a mass fraction of 30% was continuously added, and stirred for 3 hours to gradually form a yellow suspension.
(2)将0.5g氧化石墨加入蒸馏水中超声30min，形成1g/L的氧化石墨烯溶液，将氧化石墨烯溶液加入上述黄色悬浮液，在70℃水浴中搅拌1h，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料。(2) 0.5 g of graphite oxide was added to distilled water for 30 min to form a 1 g/L graphene oxide solution, and the graphene oxide solution was added to the above yellow suspension, and stirred in a water bath at 70 ° C for 1 h, and the obtained suspension was centrifuged and washed. After lyophilization, a dark gray sulfur oxide graphene composite material is obtained.
(3)将得到的硫氧化石墨烯复合材料加入1.5L浓度为2mol/L碘化钾溶液，然后再快速加入0.2L质量分数为10％的盐酸，密封，并移至黑暗环境下反应1h，离心，水洗，乙醇洗，得到硫石墨烯复合材料。(3) Add the obtained sulfur oxide graphene composite material to 1.5 L of a 2 mol/L potassium iodide solution, and then quickly add 0.2 L of 10% hydrochloric acid, seal, and transfer to a dark environment for 1 h, and centrifuge. Washed with water and washed with ethanol to obtain a sulfur graphene composite material.
(4)将得到的硫石墨烯复合材料加入水中搅拌10分钟，加入0.35g苯胺搅拌2h，然后加入0.7g引发剂过硫酸铵，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) The obtained sulfur graphene composite material was stirred in water for 10 minutes, 0.35 g of aniline was added and stirred for 2 hours, then 0.7 g of initiator ammonium persulfate was added, stirred, allowed to stand, filtered, and vacuum dried to obtain graphene/poly. Aniline/sulfur composite.
实施例5Example 5
(1)10g硫化钠和40g单质硫在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水中，得到橙色溶液，将0.25ml质量分数1％的triton X-100加入上述溶液，并搅，3h，然后不断加入质量分数为30％的浓盐酸，搅拌3h，逐渐形成黄色悬浮液。(1) 10 g of sodium sulfide and 40 g of elemental sulfur were ground in an agate mortar, and then the mixture was dissolved in distilled water to obtain an orange solution, and 0.25 ml of a 1% by mass of triton X-100 was added to the above solution, and stirred for 3 hours. Then, concentrated hydrochloric acid having a mass fraction of 30% was continuously added, and the mixture was stirred for 3 hours to gradually form a yellow suspension.
(2)将0.25g氧化石墨加入蒸馏水中超声30min，形成1g/L的氧化石墨烯溶液，将氧化石墨烯溶液加入上述黄色悬浮液，在70℃水浴中搅拌1h，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料。(2) 0.25 g of graphite oxide was added to distilled water for 30 min to form a 1 g/L graphene oxide solution, and the graphene oxide solution was added to the above yellow suspension, and stirred in a water bath at 70 ° C for 1 h, and the obtained suspension was centrifuged and washed. After lyophilization, a dark gray sulfur oxide graphene composite material is obtained.
(3)将得到的硫氧化石墨烯复合材料加入1L浓度为2mol/L碘化钾溶液，然后再快速加入0.12质量分数为10％L的盐酸，密封，并移至黑暗环境下反应1h，离心，水洗，乙醇洗，得到硫石墨烯复合材料。(3) Add the obtained sulfur oxide graphene composite material to 1 L of a 2 mol/L potassium iodide solution, then quickly add 0.12 mass fraction of 10% L hydrochloric acid, seal, and transfer to a dark environment for 1 h, centrifuge, and wash. , washing with ethanol to obtain a sulfur graphene composite material.
(4)将得到的硫石墨烯复合材料加入水中搅拌10分钟，加入0.25g苯胺搅拌4h，然后加入0.75g引发剂过硫酸铵，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) The obtained sulphur graphene composite material was stirred in water for 10 minutes, 0.25 g of aniline was added and stirred for 4 hours, then 0.75 g of initiator ammonium persulfate was added, stirred, allowed to stand, filtered, and vacuum dried to obtain graphene/poly Aniline/sulfur composite.
实施例6Example 6
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0.01C，性能结果如表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, 1 mol/L LiNO 3 is an additive, assembled into a button-type battery in a filled glove box, and a constant current charge and discharge is performed using a Land battery test system. test. The charging and discharging voltage range is 1-3V, the current density is 0.01C, and the performance results are shown in Table 1;
表1Table 1
[Table 1][Table 1]
Figure PCTCN2016074003-appb-000001
Figure PCTCN2016074003-appb-000001
如图1所示，石墨烯/聚苯胺/硫复合材料的SEM图可以看出石墨烯发生了弯曲，包裹在纳米硫粒子表面，而不是通常的片层结构，同时聚苯胺也包覆在石墨烯外层，能有效的防止硫发生膨胀及多硫化物的穿梭而影响容量。As shown in Figure 1, the SEM image of the graphene/polyaniline/sulfur composite shows that the graphene is bent and wrapped on the surface of the nano-sulfur particles instead of the usual lamellar structure, while the polyaniline is also coated on the graphite. The outer layer of the olefin can effectively prevent the expansion of sulfur and the shuttle of polysulfide to affect the capacity.
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 (1)

  1. 一种石墨烯/聚苯胺/硫复合正极材料的制备方法Method for preparing graphene/polyaniline/sulfur composite cathode material
    技术领域Technical field
    本发明属于纳米碳材料合成领域，涉及一种锂硫电池正极材料的制备方法，尤其涉及一种石墨烯/聚苯胺/硫复合正极材料的制备方法。The invention belongs to the field of nano carbon material synthesis, and relates to a preparation method of a lithium sulfur battery cathode material, in particular to a method for preparing a graphene/polyaniline/sulfur composite cathode material.
    背景技术Background technique
    锂硫电池是以金属锂为负极，单质硫为正极的电池体系。锂硫电池的具有两个放电平台(约为2.4V和2.1V)，但其电化学反应机理比较复杂。锂硫电池具有比能量高(2600Wh/kg)、比容量高(1675mAh/g)、成本低等优点，被认为是很有发展前景的新一代电池。但是目前其存在着活性物质利用率低、循环寿命低和安全性差等问题，这严重制约着锂硫电池的发展。造成上述问题的主要原因有以下几个方面：(1)单质硫是电子和离子绝缘体，室温电导率低(5×10-30S·cm-1)，由于没有离子态的硫存在，因而作为正极材料活化困难；(2)在电极反应过程中产生的高聚态多硫化锂Li2Sn(8＞n≥4)易溶于电解液中，在正负极之间形成浓度差，在浓度梯度的作用下迁移到负极，高聚态多硫化锂被金属锂还原成低聚态多硫化锂。随着以上反应的进行，低聚态多硫化锂在负极聚集，最终在两电极之间形成浓度差，又迁移到正极被氧化成高聚态多硫化锂。这种现象被称为飞梭效应，降低了硫活性物质的利用率。同时不溶性的Li2S和Li2S2沉积在锂负极表面，更进一步恶化了锂硫电池的性能；(3)反应最终产物Li2S同样是电子绝缘体，会沉积在硫电极上，而锂离子在固态硫化锂中迁移速度慢，使电化学反应动力学速度变慢；(4)硫和最终产物Li2S的密度不同，当硫被锂化后体积膨胀大约79％，易导致Li2S的粉化，引起锂硫电池的安全问题。上述不足制约着锂硫电池的 发展，这也是目前锂硫电池研究需要解决的重点问题。The lithium-sulfur battery is a battery system in which lithium metal is used as a negative electrode and elemental sulfur is used as a positive electrode. Lithium-sulfur batteries have two discharge platforms (about 2.4V and 2.1V), but their electrochemical reaction mechanism is complicated. Lithium-sulfur batteries have the advantages of high specific energy (2600Wh/kg), high specific capacity (1675mAh/g), low cost, etc., and are considered to be promising new generation batteries. However, at present, there are problems such as low utilization rate of active materials, low cycle life and poor safety, which seriously restricts the development of lithium-sulfur batteries. The main causes of the above problems are as follows: (1) Elemental sulfur is an electron and ion insulator, and the room temperature conductivity is low (5 × 10 -30 S·cm -1 ). Since there is no ionic sulfur, it is used as The activation of the positive electrode material is difficult; (2) the high polylithium polysulfide Li 2 S n (8>n≥4) generated during the electrode reaction is easily dissolved in the electrolyte, forming a concentration difference between the positive and negative electrodes. Under the action of the concentration gradient, it migrates to the negative electrode, and the high poly lithium polysulfide is reduced by the lithium metal to the oligomeric lithium polysulfide. As the above reaction proceeds, the oligomeric lithium polysulfide aggregates at the negative electrode, eventually forming a concentration difference between the two electrodes, and then migrating to the positive electrode to be oxidized to a highly polylithium polysulfide. This phenomenon is known as the shuttle effect, which reduces the utilization of sulfur active substances. At the same time, insoluble Li 2 S and Li 2 S 2 are deposited on the surface of the lithium negative electrode, which further deteriorates the performance of the lithium-sulfur battery; (3) the final product of the reaction, Li 2 S, is also an electronic insulator, which is deposited on the sulfur electrode, and lithium 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.
    技术问题technical problem
    本发明提供一种石墨烯/聚苯胺/硫复合材料，该制备方法简单，导电性良好的石墨烯提供导电网络，同时对硫颗粒进行包覆限制多硫化物的移动，外层的聚苯胺包覆硫纳米石墨烯，不但改善硫的导电性，而且能够阻止放电产物多硫化物的溶解并缓解体积膨胀，以该复合材料作为锂硫电池的正极，具有容量高、循环性能稳定的特点。The invention provides a graphene/polyaniline/sulfur composite material, the preparation method is simple, the conductive conductive graphene provides a conductive network, and the sulfur particles are coated to limit the movement of the polysulfide, and the outer polyaniline package The sulfur-coated nanographene not only improves the conductivity of sulfur, but also prevents the dissolution of the polysulfide of the discharge product and relieves the volume expansion. The composite material is used as the positive electrode of the lithium-sulfur battery, and has the characteristics of high capacity and stable cycle performance.
    技术解决方案Technical solution
    具体方案如下：一种石墨烯/聚苯胺/硫复合正极材料的制备方法，包括以下几个步骤：The specific scheme is as follows: a preparation method of a graphene/polyaniline/sulfur composite cathode material, comprising the following steps:
    (1)硫化钠和单质硫按比例在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水中，得到橙色溶液，将Triton X-100加入上述溶液，一边搅拌一边加入浓盐酸，逐渐形成黄色悬浮液；(1) Sodium sulfide and elemental sulfur are ground in an agate mortar in proportion, and then the mixture is dissolved in distilled water to obtain an orange solution. Triton X-100 is added to the above solution, and concentrated hydrochloric acid is added while stirring to gradually form a yellow suspension. ;
    (2)将氧化石墨加入蒸馏水中超声，得到氧化石墨烯溶液，取氧化石墨烯溶液加入上述黄色悬浮液，水浴中搅拌，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料；(2) Adding graphite oxide to distilled water to obtain a graphene oxide solution, adding the graphene oxide solution to the above yellow suspension, stirring in a water bath, and obtaining a suspension which is centrifuged, washed with water, and freeze-dried to obtain dark gray sulfur oxide graphite. Alkene composite material;
    (3)将得到的硫氧化石墨烯复合材料加入碘化钾溶液，然后加入稀盐酸，密封，并移至黑暗环境下反应，离心，水洗，乙醇洗，得到硫石墨烯复合材料；(3) adding the obtained sulfur oxide graphene composite material to a potassium iodide solution, then adding dilute hydrochloric acid, sealing, and moving to a dark environment for reaction, centrifugation, water washing, and ethanol washing to obtain a sulfur graphene composite material;
    (4)将得到的硫石墨烯复合材料加入水中搅拌，再加入苯胺搅拌，然后加入引发剂，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) The obtained sulfur graphene composite material is stirred in water, stirred with aniline, and then added with an initiator, stirred, stood, filtered, and vacuum dried to obtain a graphene/polyaniline/sulfur composite material.
    优选的，所述步骤(1)中硫化钠和单质硫质量比为1∶1-1∶5，Triton X-100的质量分数为1％，硫化钠与Triton X-100溶液的比例为1-50g∶1ml。Preferably, in the step (1), the mass ratio of sodium sulfide to elemental sulfur is 1:1 to 1:5, the mass fraction of Triton X-100 is 1%, and the ratio of sodium sulfide to Triton X-100 solution is 1- 50g: 1ml.
    优选的，所述步骤(2)中，氧化石墨的量与硫化钠的质量 比例为1∶5-50。Preferably, in the step (2), the amount of graphite oxide and the quality of sodium sulfide The ratio is 1:5-50.
    优选的，所述步骤(3)中，氧化石墨的量与碘化钾溶液的比例为1mg∶1-5ml；稀盐酸与碘化钾溶液的体积比例为1∶5-10。Preferably, in the step (3), the ratio of the amount of the graphite oxide to the potassium iodide solution is 1 mg: 1-5 ml; and the volume ratio of the dilute hydrochloric acid to the potassium iodide solution is 1:5-10.
    优选的，所述步骤(4)中，苯胺与硫化钠的质量比例为1∶10-50；引发剂与苯胺的质量比为1∶0.5-5。Preferably, in the step (4), the mass ratio of the aniline to the sodium sulfide is 1:10-50; the mass ratio of the initiator to the aniline is 1:0.5-5.
    优选的，所述引发剂采用过硫酸铵、重铬酸钾和氯化铁中的一种。Preferably, the initiator is one of ammonium persulfate, potassium dichromate and ferric chloride.
    优选的，所述步骤(1)中，浓盐酸的质量分数为30％，所述步骤(3)中，稀盐酸的质量分数为10％。Preferably, in the step (1), the mass fraction of concentrated hydrochloric acid is 30%, and in the step (3), the mass fraction of dilute hydrochloric acid is 10%.
    有益效果Beneficial effect
    本发明具有如下有益效果：(1)该方法制备的该方法制备出的石墨烯/聚苯胺/硫复合材料具有三层结构，内层的硫颗粒，中间层是弯曲石墨烯包覆层，外层是聚苯胺包覆层；(2)石墨烯和聚苯胺都具有超高的电导率，通过该方法制备出的石墨烯/聚苯胺/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；(3)石墨烯/聚苯胺/硫复合材料中硫被具有柔韧性的石墨烯和聚苯胺包覆着，能抑制放电产物多硫化物的溶解以及缓解体积膨胀。The invention has the following beneficial effects: (1) The graphene/polyaniline/sulfur composite material prepared by the method prepared by the method has a three-layer structure, the inner layer of sulfur particles, and the intermediate layer is a curved graphene coating layer, The layer is a polyaniline coating; (2) both graphene and polyaniline have ultra-high electrical conductivity, and the graphene/polyaniline/sulfur composite prepared by the method can effectively improve the electron of the cathode material of the lithium-sulfur battery. Conductivity and ionic conductivity; (3) The sulfur in the graphene/polyaniline/sulfur composite is coated with flexible graphene and polyaniline, which can inhibit the dissolution of the polysulfide of the discharge product and alleviate the volume expansion.
    附图说明DRAWINGS
    图1是实施例1制备的石墨烯/聚苯胺/硫复合材料的SEM图。1 is an SEM image of a graphene/polyaniline/sulfur composite prepared in Example 1.
    本发明的实施方式Embodiments of the invention
    下面结合附图，对本发明的较优的实施例作进一步的详细The preferred embodiment of the present invention will be further described in detail below with reference to the accompanying drawings.
    说明：Description:
    实施例1Example 1
    (1)10g硫化钠和50g单质硫在玛瑙研钵中研磨，然后将混 合物溶解于蒸馏水中，得到橙色溶液，将10ml质量分数1％的triton X-100加入上述溶液，并搅拌3小时，然后不断加入质量分数为30％的浓盐酸，搅拌3h，逐渐形成黄色悬浮液。(1) 10g of sodium sulfide and 50g of elemental sulfur are ground in an agate mortar and then mixed The compound was dissolved in distilled water to obtain an orange solution. 10 ml of 1% triton X-100 was added to the above solution and stirred for 3 hours, then concentrated hydrochloric acid with a mass fraction of 30% was continuously added, and stirred for 3 hours to gradually form a yellow suspension. liquid.
    (2)将2g氧化石墨加入蒸馏水中超声30min，形成1g/L的氧化石墨烯溶液，将氧化石墨烯溶液加入上述黄色悬浮液，在70℃水浴中搅拌1h，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料。(2) 2 g of graphite oxide was added to distilled water for 30 min to form a 1 g/L graphene oxide solution, and the graphene oxide solution was added to the above yellow suspension, and stirred in a water bath at 70 ° C for 1 h, and the obtained suspension was centrifuged and washed with water. After lyophilization, a dark gray sulfur oxide graphene composite material was obtained.
    (3)将得到的硫氧化石墨烯复合材料加入2L浓度为2mol/L碘化钾溶液，然后再快速加入0.4L质量分数为10％的盐酸，密封，并移至黑暗环境下反应1h，离心，水洗，乙醇洗，得到硫石墨烯复合材料。(3) Add the obtained sulfur oxide graphene composite material to 2L of 2mol/L potassium iodide solution, then quickly add 0.4L of 10% hydrochloric acid, seal, and move to dark environment for 1h, centrifuge, wash. , washing with ethanol to obtain a sulfur graphene composite material.
    (4)将得到的硫石墨烯复合材料加入水中搅拌10分钟，加入1g苯胺搅拌1h，然后加入0.5g引发剂过硫酸铵，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) The obtained sulphur graphene composite material was stirred in water for 10 minutes, 1 g of aniline was added and stirred for 1 hour, then 0.5 g of initiator ammonium persulfate was added, stirred, allowed to stand, filtered, and vacuum dried to obtain graphene/polyaniline. / sulfur composite material.
    实施例2Example 2
    (1)50g硫化钠和50g单质硫在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水中，得到橙色溶液，将1ml质量分数1％的triton X-100加入上述溶液，并搅拌3h，然后不断加入质量分数为30％的浓盐酸，搅拌3h，逐渐形成黄色悬浮液。(1) 50 g of sodium sulfide and 50 g of elemental sulfur were ground in an agate mortar, and then the mixture was dissolved in distilled water to obtain an orange solution, and 1 ml of a 1% by mass of triton X-100 was added to the above solution, and stirred for 3 hours, and then continuously Concentrated hydrochloric acid having a mass fraction of 30% was added and stirred for 3 hours to gradually form a yellow suspension.
    (2)将1g氧化石墨加入蒸馏水中超声30min，形成1g/L的氧化石墨烯溶液，将氧化石墨烯溶液加入上述黄色悬浮液，在70℃水浴中搅拌1h，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料。(2) 1 g of graphite oxide was added to distilled water for 30 min to form a 1 g/L graphene oxide solution, and the graphene oxide solution was added to the above yellow suspension, and stirred in a water bath at 70 ° C for 1 h, and the obtained suspension was centrifuged and washed with water. After lyophilization, a dark gray sulfur oxide graphene composite material was obtained.
    (3)将得到的硫氧化石墨烯复合材料加入5L浓度为2mol/L碘化钾溶液，然后再快速加入0.5L质量分数为10％的盐酸，密封，并移至黑暗环境下反应1h，离心，水洗，乙醇洗，得到硫石墨烯复合材料。(3) Add the obtained sulfur oxide graphene composite material to 5L of 2mol/L potassium iodide solution, then quickly add 0.5L of 10% hydrochloric acid, seal, and transfer to dark environment for 1h, centrifuge, wash. , washing with ethanol to obtain a sulfur graphene composite material.
    (4)将得到的硫石墨烯复合材料加入水中搅拌10分钟，加 入1g苯胺搅拌5h，然后加入5g引发剂重铬酸钾，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) Add the obtained sulphur graphene composite material to water and stir for 10 minutes. 1 g of aniline was stirred for 5 h, then 5 g of initiator potassium dichromate was added, stirred, allowed to stand, filtered, and vacuum dried to obtain a graphene/polyaniline/sulfur composite.
    实施例3Example 3
    (1)10g硫化钠和20g单质硫在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水中，得到橙色溶液，将1ml质量分数1％的triton X-100加入上述溶液，并搅拌3h，然后不断加入质量分数为30％的浓盐酸，搅拌3h，逐渐形成黄色悬浮液。(1) 10 g of sodium sulfide and 20 g of elemental sulfur were ground in an agate mortar, and then the mixture was dissolved in distilled water to obtain an orange solution, and 1 ml of a 1% by mass of triton X-100 was added to the above solution, and stirred for 3 hours, and then continuously Concentrated hydrochloric acid having a mass fraction of 30% was added and stirred for 3 hours to gradually form a yellow suspension.
    (2)将1g氧化石墨加入蒸馏水中超声30min，形成1g/L的氧化石墨烯溶液，将氧化石墨烯溶液加入上述黄色悬浮液，在70℃水浴中搅拌1h，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料。(2) 1 g of graphite oxide was added to distilled water for 30 min to form a 1 g/L graphene oxide solution, and the graphene oxide solution was added to the above yellow suspension, and stirred in a water bath at 70 ° C for 1 h, and the obtained suspension was centrifuged and washed with water. After lyophilization, a dark gray sulfur oxide graphene composite material was obtained.
    (3)将得到的硫氧化石墨烯复合材料加入2L浓度为2mol/L碘化钾溶液，然后再快速加入0.3L质量分数为10％的盐酸，密封，并移至黑暗环境下反应1h，离心，水洗，乙醇洗，得到硫石墨烯复合材料。(3) Add the obtained sulfur oxide graphene composite material to 2L of 2mol/L potassium iodide solution, then quickly add 0.3L of 10% hydrochloric acid, seal, and move to dark environment for 1h, centrifuge, wash. , washing with ethanol to obtain a sulfur graphene composite material.
    (4)将得到的硫石墨烯复合材料加入水中搅拌10分钟，加入0.5g苯胺搅拌2h，然后加入0.5g引发剂氯化铁，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) The obtained sulphur graphene composite material was stirred in water for 10 minutes, 0.5 g of aniline was added and stirred for 2 hours, then 0.5 g of initiator ferric chloride was added, stirred, allowed to stand, filtered, and vacuum dried to obtain graphene/poly. Aniline/sulfur composite.
    实施例4Example 4
    (1)10g硫化钠和30g单质硫在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水中，得到橙色溶液，将0.5ml质量分数1％的triton X-100加入上述溶液，并搅拌3h，然后不断加入质量分数为30％的浓盐酸，搅拌3h，逐渐形成黄色悬浮液。(1) 10 g of sodium sulfide and 30 g of elemental sulfur were ground in an agate mortar, and then the mixture was dissolved in distilled water to obtain an orange solution, and 0.5 ml of a 1% by mass of triton X-100 was added to the above solution, and stirred for 3 hours, and then Concentrated hydrochloric acid with a mass fraction of 30% was continuously added and stirred for 3 hours to gradually form a yellow suspension.
    (2)将0.5g氧化石墨加入蒸馏水中超声30min，形成1g/L的氧化石墨烯溶液，将氧化石墨烯溶液加入上述黄色悬浮液，在70℃水浴中搅拌1h，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料。 (2) 0.5 g of graphite oxide was added to distilled water for 30 min to form a 1 g/L graphene oxide solution, and the graphene oxide solution was added to the above yellow suspension, and stirred in a water bath at 70 ° C for 1 h, and the obtained suspension was centrifuged and washed. After lyophilization, a dark gray sulfur oxide graphene composite material is obtained.
    (3)将得到的硫氧化石墨烯复合材料加入1.5L浓度为2mol/L碘化钾溶液，然后再快速加入0.2L质量分数为10％的盐酸，密封，并移至黑暗环境下反应1h，离心，水洗，乙醇洗，得到硫石墨烯复合材料。(3) Add the obtained sulfur oxide graphene composite material to 1.5 L of a 2 mol/L potassium iodide solution, and then quickly add 0.2 L of 10% hydrochloric acid, seal, and transfer to a dark environment for 1 h, and centrifuge. Washed with water and washed with ethanol to obtain a sulfur graphene composite material.
    (4)将得到的硫石墨烯复合材料加入水中搅拌10分钟，加入0.35g苯胺搅拌2h，然后加入0.7g引发剂过硫酸铵，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) The obtained sulfur graphene composite material was stirred in water for 10 minutes, 0.35 g of aniline was added and stirred for 2 hours, then 0.7 g of initiator ammonium persulfate was added, stirred, allowed to stand, filtered, and vacuum dried to obtain graphene/poly. Aniline/sulfur composite.
    实施例5Example 5
    (1)10g硫化钠和40g单质硫在玛瑙研钵中研磨，然后将混合物溶解于蒸馏水中，得到橙色溶液，将0.25m1质量分数1％的triton X-100加入上述溶液，并搅，3h，然后不断加入质量分数为30％的浓盐酸，搅拌3h，逐渐形成黄色悬浮液。(1) 10 g of sodium sulfide and 40 g of elemental sulfur were ground in an agate mortar, and then the mixture was dissolved in distilled water to obtain an orange solution, and 0.25 ml of a 1% triton X-100 was added to the above solution and stirred for 3 hours. Then, concentrated hydrochloric acid having a mass fraction of 30% was continuously added, and the mixture was stirred for 3 hours to gradually form a yellow suspension.
    (2)将0.25g氧化石墨加入蒸馏水中超声30min，形成1g/L的氧化石墨烯溶液，将氧化石墨烯溶液加入上述黄色悬浮液，在70℃水浴中搅拌1h，得到的悬浮液离心、水洗，冷冻干燥后得到深灰色的硫氧化石墨烯复合材料。(2) 0.25 g of graphite oxide was added to distilled water for 30 min to form a 1 g/L graphene oxide solution, and the graphene oxide solution was added to the above yellow suspension, and stirred in a water bath at 70 ° C for 1 h, and the obtained suspension was centrifuged and washed. After lyophilization, a dark gray sulfur oxide graphene composite material is obtained.
    (3)将得到的硫氧化石墨烯复合材料加入1L浓度为2mol/L碘化钾溶液，然后再快速加入0.12质量分数为10％L的盐酸，密封，并移至黑暗环境下反应1h，离心，水洗，乙醇洗，得到硫石墨烯复合材料。(3) Add the obtained sulfur oxide graphene composite material to 1 L of a 2 mol/L potassium iodide solution, then quickly add 0.12 mass fraction of 10% L hydrochloric acid, seal, and transfer to a dark environment for 1 h, centrifuge, and wash. , washing with ethanol to obtain a sulfur graphene composite material.
    (4)将得到的硫石墨烯复合材料加入水中搅拌10分钟，加入0.25g苯胺搅拌4h，然后加入0.75g引发剂过硫酸铵，搅拌、静置、过滤、真空烘干，获得石墨烯/聚苯胺/硫复合材料。(4) The obtained sulphur graphene composite material was stirred in water for 10 minutes, 0.25 g of aniline was added and stirred for 4 hours, then 0.75 g of initiator ammonium persulfate was added, stirred, allowed to stand, filtered, and vacuum dried to obtain graphene/poly Aniline/sulfur composite.
    实施例6Example 6
    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，CELGARD2400为隔膜，1mol/L的LiTFSI/DOL-DME(体积比1∶1)为电解液，1 mol/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0.01C，性能结果如表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, CELGARD2400 as separator, 1 mol/ L LiTFSI/DOL-DME (volume ratio 1:1) is an electrolyte, 1 mol/L LiNO 3 is an additive, assembled into a button-type battery in a filled glove box, and a constant current charge and discharge is performed using a Land battery test system. test. The charging and discharging voltage range is 1-3V, the current density is 0.01C, and the performance results are shown in Table 1;
    表1Table 1
    [Table 1][Table 1]
    Figure PCTCN2016074003-appb-100001
    Figure PCTCN2016074003-appb-100001
    如图1所示，石墨烯/聚苯胺/硫复合材料的SEM图可以看出石墨烯发生了弯曲，包裹在纳米硫粒子表面，而不是通常的片层结构，同时聚苯胺也包覆在石墨烯外层，能有效的防止硫发生膨胀及多硫化物的穿梭而影响容量。As shown in Figure 1, the SEM image of the graphene/polyaniline/sulfur composite shows that the graphene is bent and wrapped on the surface of the nano-sulfur particles instead of the usual lamellar structure, while the polyaniline is also coated on the graphite. The outer layer of the olefin can effectively prevent the expansion of sulfur and the shuttle of polysulfide to affect the capacity.
    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.
PCT/CN2016/074003 2016-02-18 2016-02-18 Method for preparing graphene/polyaniline/sulfur composite positive electrode material WO2017139939A1 (en)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110422835A (en) * 2019-07-22 2019-11-08 通化师范学院 A kind of preparation method of the carbon material surface grafting fire proofing for the difunctional diaphragm of Li-S battery
CN112436114A (en) * 2020-11-16 2021-03-02 扬州大学 Three-dimensional graphene/carbon nanotube/phosphotungstic acid/sulfur composite material, preparation method and application thereof
CN113008958A (en) * 2021-02-10 2021-06-22 陕西省石油化工研究设计院 Method for detecting nitrite by electrochemistry
CN114744174A (en) * 2022-04-14 2022-07-12 桂林理工大学 Sulfur/copper hydroxide/graphene oxide composite material for lithium-sulfur battery anode and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102769126A (en) * 2012-07-18 2012-11-07 上海大学 Method for preparing nano-sulfur / graphene oxide composite electrode material
CN103682274A (en) * 2013-12-19 2014-03-26 浙江师范大学 Graphene/polyaniline/sulfur composite material and preparation method thereof
CN104600268A (en) * 2015-01-16 2015-05-06 中国计量学院 Method for preparing polyaniline/sulfur/graphene composite material
CN204315664U (en) * 2014-11-10 2015-05-06 南京中储新能源有限公司 A kind of aluminium-sulfur battery Graphene/organic sulfur/polyaniline composite material positive pole

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102769126A (en) * 2012-07-18 2012-11-07 上海大学 Method for preparing nano-sulfur / graphene oxide composite electrode material
CN103682274A (en) * 2013-12-19 2014-03-26 浙江师范大学 Graphene/polyaniline/sulfur composite material and preparation method thereof
CN204315664U (en) * 2014-11-10 2015-05-06 南京中储新能源有限公司 A kind of aluminium-sulfur battery Graphene/organic sulfur/polyaniline composite material positive pole
CN104600268A (en) * 2015-01-16 2015-05-06 中国计量学院 Method for preparing polyaniline/sulfur/graphene composite material

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110422835A (en) * 2019-07-22 2019-11-08 通化师范学院 A kind of preparation method of the carbon material surface grafting fire proofing for the difunctional diaphragm of Li-S battery
CN112436114A (en) * 2020-11-16 2021-03-02 扬州大学 Three-dimensional graphene/carbon nanotube/phosphotungstic acid/sulfur composite material, preparation method and application thereof
CN113008958A (en) * 2021-02-10 2021-06-22 陕西省石油化工研究设计院 Method for detecting nitrite by electrochemistry
CN114744174A (en) * 2022-04-14 2022-07-12 桂林理工大学 Sulfur/copper hydroxide/graphene oxide composite material for lithium-sulfur battery anode and preparation method thereof
CN114744174B (en) * 2022-04-14 2023-10-27 桂林理工大学 Positive electrode composite material of lithium-sulfur battery and preparation method thereof

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