WO2018184235A1 - Ti3c2tx/graphene oxide/celgard composite separator - Google Patents
Ti3c2tx/graphene oxide/celgard composite separator Download PDFInfo
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- WO2018184235A1 WO2018184235A1 PCT/CN2017/079803 CN2017079803W WO2018184235A1 WO 2018184235 A1 WO2018184235 A1 WO 2018184235A1 CN 2017079803 W CN2017079803 W CN 2017079803W WO 2018184235 A1 WO2018184235 A1 WO 2018184235A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/403—Manufacturing processes of separators, membranes or diaphragms
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Definitions
- the present invention relates to the field of lithium-sulfur batteries, and in particular, to a method for preparing a lithium-sulfur battery separator.
- a lithium-sulfur battery is a battery system in which lithium metal is used as a negative electrode and elemental sulfur is a positive electrode.
- Lithium-sulfur batteries have two discharge platforms (approximately 2.4 V and 2.1 V), but their electrochemical reaction mechanisms are complex. Lithium-sulfur batteries have the advantages of high specific energy (2600 Wh/kg), high specific capacity (1675 mAh/g), and low cost, and are considered to be promising new generation batteries.
- the highly polylithium polysulfide Li 2 S n (8 >n>4) generated during the electrode reaction is easily soluble in the electrolyte, forming a concentration difference between the positive and negative electrodes, under the action of the concentration gradient
- the highly polylithium polysulfide is reduced by lithium metal to 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.
- the technical problem to be solved by the present invention is to provide a Ti 3 C 2 T ⁇ / graphene oxide / Celgard composite separator, Including commercial Celgard membrane and the surface of the Ti 3 C 2 T ⁇ / graphene oxide layers, the thickness of the Ti 3 C 2 TJ the graphene oxide layer is 1 ⁇ 10 ⁇ , said Ti 3 C 2 T ⁇ / The mass ratio of Ti 3 C 2 ⁇ ⁇ to graphene oxide in the graphene oxide layer was 1: 0.2-1.
- the present invention provides a Ti 3 C 2 T ⁇ / graphene oxide / Celgard composite membrane preparation method is as follows:
- Ti 3 AlC ⁇ 3 ⁇ 4 porcelain powder is etched in hydrofluoric acid, and the solution is added to deionized water for centrifugation after etching, and then the precipitate is dried to obtain a stacked sheet of Ti 3 C. 2 T x powder;
- the concentration of hydrofluoric acid in step (1) is 20 ⁇ 3 ⁇ 4-50 ⁇ 3 ⁇ 4, and the corroded turns are 4-24 hours;
- the mass ratio of the graphite oxide and the Ti 3 C 2 T x powder in the step (2) is 1: 0.2-1, and the ultrasonic ratio is 1-5 hours.
- the concentration of the graphite oxide and Ti 3 C 2 T x powder suspension is 0.1-lmg/mL, and the Celgard membrane is directly contacted with the suspension on the filter paper.
- Ti 3 C 2 T ⁇ / graphene oxide / Celgard ⁇ composite membrane on the Ti 3 C 2 T graphene oxide layer of Ti 3 C 2 T ⁇ group is -F Or -OH groups, and oxygen on the surface of graphene oxide are strong polar groups, which can form strong chemisorption of polysulfides formed during charge and discharge, and can effectively prevent polysulfides from passing through the separator to the negative electrode. , reduce the occurrence of the shuttle effect and improve the life of the lithium-sulfur battery.
- FIG. 1 is a schematic view showing the structure of a Ti 3 C 2 T ⁇ / graphene oxide/Celgard composite separator of the present invention.
- FIG. 2 is a flow chart for preparing a Ti 3 C 2 T ⁇ / graphene oxide/Celgard composite separator of the present invention.
- FIG 3 is a cycle life diagram of a Ti 3 C 2 T ⁇ / graphene oxide/Celgard composite separator of the present invention.
- Ti 3 AlC 2 ceramic powder is placed in a hydrofluoric acid having a mass concentration of 20% for 24 hours, and the solution is added to deionized water for centrifugation after etching, and then the precipitate is dried to obtain a stack.
- Ti 3 AlC 2 ceramic powder is placed in a hydrofluoric acid having a mass concentration of 50% for 4 hours, and after etching, the solution is added to deionized water for centrifugation, and then the precipitate is dried to obtain a stack. Layered Ti 3 C 2 T morning;
- Ti 3 AlC 2 ceramic powder is placed in hydrofluoric acid with a concentration of 30% for 20h, after etching, the solution is added to deionized water for centrifugation, and then the precipitate is dried to obtain a stack.
- Ti 3 AlC 2 ceramic powder is placed in hydrofluoric acid with a concentration of 35% for 13h, after etching, the solution is added to deionized water for centrifugation, and then the precipitate is dried to obtain a stack. Layered Ti 3 C 2 T morning;
- the comparative example uses a Celgard separator as a lithium-sulfur battery separator, and other conditions are the same as described above.
- FIG. 3 is a cycle life diagram of a composite separator prepared in Example 1 of the present invention assembled into a lithium sulfur battery. It can be seen from the figure that the composite separator prepared by the present invention retains the capacity of more than 70% of the initial capacity after 400 times of charge and discharge, and the comparative example is assembled into a lithium-sulfur battery by using a Celgard separator, and the capacity is entered into the initial capacity after 200 cycles. 40%, indicating that the composite diaphragm can effectively suppress the shuttle effect and improve the life of the sulfur battery.
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Abstract
Provided is a Ti3C2Tx/graphene oxide/Celgard composite separator, comprising: a Celgard separator; and a Ti3C2Tx/graphene oxide layer formed on a surface thereof. The Ti3C2Tx/graphene oxide layer has a thickness of 1-10μm. In the Ti3C2Tx/graphene oxide layer, a mass ratio of Ti3C2Tx to graphene oxide is 1:0.2-1. For the Ti3C2Tx in the Ti3C2Tx/graphene oxide layer, T represents an -F group or an -OH group, which along with oxygen on a surface of the graphene oxide are groups with strong polarity exhibiting high chemical adsorption with respect to polysulfide formed in a charging/discharging process, thereby effectively preventing polysulfide from penetrating the separator to reach a negative electrode, reducing shuttle effect, and increasing service life of a lithium-sulfur battery.
Description
发明名称：一种 Ti 3C 2Τ χ/氧化石墨烯 /Celgard复合隔膜 Title: A Ti 3 C 2 Τ χ / Graphene Oxide / Celgard Composite Membrane
技术领域 Technical field
[0001] 本发明涉及锂硫电池领域， 特别涉及一种锂硫电池隔膜的制备方法。 [0001] The present invention relates to the field of lithium-sulfur batteries, and in particular, to a method for preparing a lithium-sulfur battery separator.
背景技术 Background technique
[0002] 锂硫电池是以金属锂为负极， 单质硫为正极的电池体系。 锂硫电池的具有两个 放电平台 （约为 2.4 V和 2.1 V) ， 但其电化学反应机理比较复杂。 锂硫电池具有 比能量高 （2600 Wh/kg) 、 比容量高 （1675 mAh/g) 、 成本低等优点， 被认为 是很有发展前景的新一代电池。 [0002] A lithium-sulfur battery is a battery system in which lithium metal is used as a negative electrode and elemental sulfur is a positive electrode. Lithium-sulfur batteries have two discharge platforms (approximately 2.4 V and 2.1 V), but their electrochemical reaction mechanisms are complex. Lithium-sulfur batteries have the advantages of high specific energy (2600 Wh/kg), high specific capacity (1675 mAh/g), and low cost, and are considered to be promising new generation batteries.
技术问题 technical problem
[0003] 但是目前其存在着活性物质利用率低、 循环寿命低和安全性差等问题， 这严重 制约着锂硫电池的发展。 造成上述问题的主要原因有以下几个方面： （1) 单质 硫是电子和离子绝缘体， 室温电导率低 （5x10 ^s^m ) ， 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 Li 28和 Li 2S 2沉积在锂负极表面， 更进一步 恶化了锂硫电池的性能； （3) 反应最终产物 Li 2S同样是电子绝缘体， 会沉积在 硫电极上， 而锂离子在固态硫化锂中迁移速度慢， 使电化学反应动力学速度变 慢； （4) 硫和最终产物 Li 2S的密度不同， 当硫被锂化后体积膨胀大约 79%， 易 导致 28的粉化， 引起锂硫电池的安全问题。 上述不足制约着锂硫电池的发展 ， 这也是目前锂硫电池研究需要解决的重点问题。 [0003] However, at present, there are problems such as low utilization rate of active materials, low cycle life and poor safety, which seriously restricts the development of lithium-sulfur batteries. The main causes of the above problems are as follows: (1) Elemental sulfur is an electron and ion insulator, and the room temperature conductivity is low (5x10 ^s^m). Since there is no ionic sulfur, it is difficult to activate as a positive electrode material; (2) The highly polylithium polysulfide Li 2 S n (8 >n>4) generated during the electrode reaction is easily soluble in the electrolyte, forming a concentration difference between the positive and negative electrodes, under the action of the concentration gradient Upon migration to the negative electrode, the highly polylithium polysulfide is reduced by lithium metal to oligomeric lithium polysulfide. As the above reaction proceeds, the oligomeric lithium polysulfide aggregates at the negative electrode, eventually forming a concentration difference between the two electrodes, and then migrating to the positive electrode to be oxidized to a highly polylithium polysulfide. This phenomenon is known as the shuttle effect, which reduces the utilization of sulfur active substances. The same insoluble Li 2 8 and Li 2 S 2 are deposited on the surface of the lithium negative electrode, which further deteriorates the performance of the lithium sulfur battery; (3) The final product of the reaction, Li 2 S, is also an electronic insulator, which is deposited on the sulfur electrode. Lithium ions migrate slowly in solid lithium sulfide, which slows the electrochemical reaction kinetics. (4) The density of sulfur and the final product Li 2 S is different. When the sulfur is lithiated, the volume expands by about 79%, which easily leads to 2 The powdering of 8 causes safety problems of lithium-sulfur batteries. The above-mentioned shortcomings restrict the development of lithium-sulfur batteries, which is also the key issue that needs to be solved in the research of lithium-sulfur batteries.
问题的解决方案 Problem solution
技术解决方案 Technical solution
[0004] 本发明要解决的技术问题是提供一种 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜，
包括商用 Celgard隔膜和其表面的 Ti 3C 2T χ/氧化石墨烯层组成， 所述的 Ti 3C 2T J 氧化石墨烯层的厚度为 1〜10μηι， 所述的 Ti 3C 2T χ/氧化石墨烯层中 Ti 3C 2Τ χ与氧 化石墨烯的质量比为 1 : 0.2-1。 [0004] The technical problem to be solved by the present invention is to provide a Ti 3 C 2 T χ / graphene oxide / Celgard composite separator, Including commercial Celgard membrane and the surface of the Ti 3 C 2 T χ / graphene oxide layers, the thickness of the Ti 3 C 2 TJ the graphene oxide layer is 1~10μηι, said Ti 3 C 2 T χ / The mass ratio of Ti 3 C 2 Τ χ to graphene oxide in the graphene oxide layer was 1: 0.2-1.
[0005] 本发明提供一种 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜的制备方法如下： [0005] The present invention provides a Ti 3 C 2 T χ / graphene oxide / Celgard composite membrane preparation method is as follows:
[0006] (1) 将 Ti 3AlC ^¾瓷粉末放入氢氟酸中腐蚀， 腐蚀后溶液加入去离子水进行 离心处理， 然后将沉淀物烘干， 得到堆垛的层片状 Ti 3C 2T x粉体； [0006] (1) Ti 3 AlC ^ 3⁄4 porcelain powder is etched in hydrofluoric acid, and the solution is added to deionized water for centrifugation after etching, and then the precipitate is dried to obtain a stacked sheet of Ti 3 C. 2 T x powder;
[0007] (2) 将氧化石墨和 Ti 3C 2T x粉体加入到水中超声分散， 形成的悬浮液， 再将 悬浮液加入到垫有 Celgard隔膜和滤纸的抽滤瓶中抽滤， 烘干后撕去滤纸及得到 T i 3C 2T χ/氧化石墨烯 /Celgard复合隔膜。 [0007] (2) The graphite oxide and the Ti 3 C 2 T x powder are added to the ultrasonic dispersion to form a suspension, and the suspension is added to a suction filter bottle with a Celgard separator and a filter paper, and filtered. After drying, the filter paper was peeled off and a T i 3 C 2 T χ / graphene oxide/Celgard composite separator was obtained.
[0008] 步骤 （1) 中氢氟酸的浓度为 20<¾-50<¾， 腐蚀的吋间为 4-24小吋； [0008] The concentration of hydrofluoric acid in step (1) is 20<3⁄4-50<3⁄4, and the corroded turns are 4-24 hours;
[0009] 步骤 （2) 中氧化石墨和 Ti 3C 2T x粉体的质量比为 1 : 0.2-1， 超声吋间为 1-5小吋[0009] The mass ratio of the graphite oxide and the Ti 3 C 2 T x powder in the step (2) is 1: 0.2-1, and the ultrasonic ratio is 1-5 hours.
， 氧化石墨和 Ti 3C 2T x粉体悬浮液的浓度为 0.1-lmg/mL， 抽滤吋 Celgard隔膜在 滤纸的上面与悬浮液直接接触。 The concentration of the graphite oxide and Ti 3 C 2 T x powder suspension is 0.1-lmg/mL, and the Celgard membrane is directly contacted with the suspension on the filter paper.
发明的有益效果 Advantageous effects of the invention
有益效果 Beneficial effect
[0010] 本发明具有如下有益效果： Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜中 Ti 3C 2T 氧化石墨烯层中的 Ti 3C 2T χ上的 Τ为 -F基团或 -OH基团， 与氧化石墨烯表面的氧 均为强极性基团， 能对充放电过程中形成的多硫化物形成强烈的化学吸附， 能 有效的阻止多硫化物穿过隔膜到达负极， 减少飞梭效应的发生， 提高锂硫电池 的寿命。 [0010] The present invention has the following advantages: Ti 3 C 2 T χ / graphene oxide / Celgard Τ composite membrane on the Ti 3 C 2 T graphene oxide layer of Ti 3 C 2 T χ group is -F Or -OH groups, and oxygen on the surface of graphene oxide are strong polar groups, which can form strong chemisorption of polysulfides formed during charge and discharge, and can effectively prevent polysulfides from passing through the separator to the negative electrode. , reduce the occurrence of the shuttle effect and improve the life of the lithium-sulfur battery.
对附图的简要说明 Brief description of the drawing
附图说明 DRAWINGS
[0011] 图 1是本发明的 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜结构示意图。 1 is a schematic view showing the structure of a Ti 3 C 2 T χ / graphene oxide/Celgard composite separator of the present invention.
[0012] 图 2是本发明的 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜制备流程图。 2 is a flow chart for preparing a Ti 3 C 2 T χ / graphene oxide/Celgard composite separator of the present invention.
[0013] 图 3是本发明的 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜的循环寿命图。 3 is a cycle life diagram of a Ti 3 C 2 T χ / graphene oxide/Celgard composite separator of the present invention.
[0014] 其中， 1为 Ti 3C 2T x/氧化石墨烯层， 2为 Celgard隔膜。
本发明的实施方式 Wherein 1 is a Ti 3 C 2 T x / graphene oxide layer, and 2 is a Celgard separator. Embodiments of the invention
[0015] 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： [0015] The preferred embodiments of the present invention are further described in detail below with reference to the accompanying drawings:
[0016] 实施例 1 Embodiment 1
[0017] (1) 将 Ti3AlC2陶瓷粉末放入质量浓度为 20%的氢氟酸中腐蚀 24h， 腐蚀后溶 液加入去离子水进行离心处理， 然后将沉淀物烘干， 得到堆垛的层片状 Ti3C2T 崖； [0017] (1) Ti 3 AlC 2 ceramic powder is placed in a hydrofluoric acid having a mass concentration of 20% for 24 hours, and the solution is added to deionized water for centrifugation after etching, and then the precipitate is dried to obtain a stack. Layered Ti 3 C 2 T cliff;
[0018] (2) 将 10g氧化石墨和 2gTi3C2Tx粉体加入到水中超声分散， 超声吋间为 1小 吋， 形成浓度为 O.lmg/mL悬浮液， 再将悬浮液加入到垫有 Celgard隔膜和滤纸的 抽滤瓶中抽滤， 烘干后撕去滤纸及得到 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜。 [0018] (2) 10g of graphite oxide and 2g of Ti 3 C 2 T x powder was added to the water to ultrasonic dispersion, 1 吋 between the ultrasonic turns, forming a concentration of O.lmg / mL suspension, and then the suspension was added The filter was filtered through a filter bottle with a Celgard separator and filter paper. After drying, the filter paper was removed and a Ti 3 C 2 T χ / graphene oxide/Celgard composite separator was obtained.
[0019] 实施例 2 [0019] Example 2
[0020] (1) 将 Ti3AlC2陶瓷粉末放入质量浓度为 50%的氢氟酸中腐蚀 4h， 腐蚀后溶 液加入去离子水进行离心处理， 然后将沉淀物烘干， 得到堆垛的层片状 Ti3C2T 晨； [0020] (1) Ti 3 AlC 2 ceramic powder is placed in a hydrofluoric acid having a mass concentration of 50% for 4 hours, and after etching, the solution is added to deionized water for centrifugation, and then the precipitate is dried to obtain a stack. Layered Ti 3 C 2 T morning;
[0021] (2) 将 10g氧化石墨和 10gTi3C2Tx粉体加入到水中超声分散， 超声吋间为 5小 吋， 形成浓度为 lmg/mL悬浮液， 再将悬浮液加入到垫有 Celgard隔膜和滤纸的抽 滤瓶中抽滤， 烘干后撕去滤纸及得到 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜。 [0021] (2) 10 g of graphite oxide and 10 g of Ti 3 C 2 T x powder were added to water for ultrasonic dispersion, and the ultrasonic time was 5 hours, forming a suspension of 1 mg/mL, and then the suspension was added to the pad. The Celgard separator and the filter paper were suction filtered, dried, and then the filter paper was removed to obtain a Ti 3 C 2 T χ / graphene oxide/Celgard composite separator.
[0022] 实施例 3 Embodiment 3
[0023] (1) 将 Ti3AlC2陶瓷粉末放入质量浓度为 30%的氢氟酸中腐蚀 20h， 腐蚀后溶 液加入去离子水进行离心处理， 然后将沉淀物烘干， 得到堆垛的层片状 Ti3C2T 崖； [0023] (1) Ti 3 AlC 2 ceramic powder is placed in hydrofluoric acid with a concentration of 30% for 20h, after etching, the solution is added to deionized water for centrifugation, and then the precipitate is dried to obtain a stack. Layered Ti 3 C 2 T cliff;
[0024] (2) 将 10g氧化石墨和 6gTi3C2Tx粉体加入到水中超声分散， 超声吋间为 3小 吋， 形成浓度为 0.5mg/mL悬浮液， 再将悬浮液加入到垫有 Celgard隔膜和滤纸的 抽滤瓶中抽滤， 烘干后撕去滤纸及得到 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜。 [0024] (2) 10 g of graphite oxide and 6 g of Ti 3 C 2 T x powder were added to water for ultrasonic dispersion, and the ultrasonic volume was 3 hours to form a suspension having a concentration of 0.5 mg/mL, and then the suspension was added to the pad. The filter was filtered in a suction flask with a Celgard separator and filter paper. After drying, the filter paper was removed and a Ti 3 C 2 T χ / graphene oxide/Celgard composite separator was obtained.
[0025] 实施例 4 [0025] Example 4
[0026] (1) 将 Ti3AlC2陶瓷粉末放入质量浓度为 40%的氢氟酸中腐蚀 15h， 腐蚀后溶 液加入去离子水进行离心处理， 然后将沉淀物烘干， 得到堆垛的层片状 Ti3C2T 崖； [0026] (1) The Ti 3 AlC 2 ceramic powder is placed in a hydrofluoric acid having a mass concentration of 40% for 15 hours. After the etching, the solution is added to deionized water for centrifugation, and then the precipitate is dried to obtain a stack. Layered Ti 3 C 2 T cliff;
[0027] (2) 将 10g氧化石墨和 4gTi3C2Tx粉体加入到水中超声分散， 超声吋间为 2小
吋， 形成浓度为 0.3mg/mL悬浮液， 再将悬浮液加入到垫有 Celgard隔膜和滤纸的 抽滤瓶中抽滤， 烘干后撕去滤纸及得到 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜。 [0027] (2) 10 g of graphite oxide and 4 g of Ti 3 C 2 T x powder were added to water for ultrasonic dispersion, and the ultrasonic inter-twist was 2 small 吋, a concentration of 0.3 mg / mL suspension is formed, and the suspension is added to a suction filter bottle with a Celgard separator and filter paper, and filtered, dried, and then the filter paper is removed and Ti 3 C 2 T χ / graphene oxide is obtained. /Celgard composite diaphragm.
[0028] 实施例 5 [0028] Example 5
[0029] (1) 将 Ti 3AlC 2陶瓷粉末放入质量浓度为 35%的氢氟酸中腐蚀 13h， 腐蚀后溶 液加入去离子水进行离心处理， 然后将沉淀物烘干， 得到堆垛的层片状 Ti 3C 2T 晨； [0029] (1) Ti 3 AlC 2 ceramic powder is placed in hydrofluoric acid with a concentration of 35% for 13h, after etching, the solution is added to deionized water for centrifugation, and then the precipitate is dried to obtain a stack. Layered Ti 3 C 2 T morning;
[0030] (2) 将 10g氧化石墨和 8gTi 3C 2T x粉体加入到水中超声分散， 超声吋间为 4小 吋， 形成浓度为 0.7mg/mL悬浮液， 再将悬浮液加入到垫有 Celgard隔膜和滤纸的 抽滤瓶中抽滤， 烘干后撕去滤纸及得到 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜。 [0030] (2) 10 g of graphite oxide and 8 g of Ti 3 C 2 T x powder were added to water for ultrasonic dispersion, and the ultrasonic volume was 4 hours to form a suspension having a concentration of 0.7 mg/mL, and then the suspension was added to the pad. The filter was filtered in a suction flask with a Celgard separator and filter paper. After drying, the filter paper was removed and a Ti 3 C 2 T χ / graphene oxide/Celgard composite separator was obtained.
[0031] 锂硫电池的制备及性能测试； 将硫单质材料、 乙炔黑和 PVDF按质量比 70: 20 ： 10在 NMP中混合， 涂覆在铝箔上为电极膜， 金属锂片为对电极， 实施例 1制备 的复合隔膜做为隔膜， 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电池测试系统 进行恒流充放电测试。 充放电电压范围为 1-3V， 电流密度为 0.5C。 [0031] Preparation and performance test of lithium-sulfur battery; sulfur elemental material, acetylene black and PVDF are mixed in NMP at a mass ratio of 70:20:10, coated on an aluminum foil as an electrode film, and a lithium metal plate as a counter electrode. The composite membrane prepared in Example 1 was used as a separator, and 1 mol/L of LiTFSI/DOL-DME (volume ratio of 1:1) was used as an electrolyte, and 1 mol/L of LiN03 was used as an additive, and a button cell was assembled in a St-filled glove box. , using the Land battery test system for constant current charge and discharge testing. The charge and discharge voltage ranges from 1-3V and the current density is 0.5C.
[0032] 对比例采用 Celgard隔膜为锂硫电池隔膜， 其他的条件与上述相同。 [0032] The comparative example uses a Celgard separator as a lithium-sulfur battery separator, and other conditions are the same as described above.
[0033] [0033]
[0034] 图 3是本发明实施例 1制备的复合隔膜组装成锂硫电池的循环寿命图。 从图中可 以看出本发明制备的复合隔膜进行 400次充放电后容量仍保有初始容量的 70%以 上， 而对比例采用 Celgard隔膜组装成锂硫电池， 进行 200次循环后容量进为初始 容量的 40%， 说明该复合隔膜能有效抑制飞梭效应， 提高硫电池的寿命。 3 is a cycle life diagram of a composite separator prepared in Example 1 of the present invention assembled into a lithium sulfur battery. It can be seen from the figure that the composite separator prepared by the present invention retains the capacity of more than 70% of the initial capacity after 400 times of charge and discharge, and the comparative example is assembled into a lithium-sulfur battery by using a Celgard separator, and the capacity is entered into the initial capacity after 200 cycles. 40%, indicating that the composite diaphragm can effectively suppress the shuttle effect and improve the life of the sulfur battery.
[0035] 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 conjunction with the specific preferred embodiments. 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.
Claims
[权利要求 1] 一种 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜， 包括 Celgard隔膜和其表 面的 Ti 3C 2Τ χ/氧化石墨烯层组成， 所述的 Ti 3C 2Τ χ/氧化石墨烯层的 厚度为 1〜10μηι， 所述的 Ti 3C 2T χ/氧化石墨烯层中 Ti 3C 2T 与氧化石 墨烯的质量比为 1 : 0.2-1。 One kind of Ti 3 C 2 T χ / graphene oxide / Celgard composite membrane [claim 1], comprising Celgard membrane and the surface of the Ti 3 C 2 Τ χ / graphene oxide layers, the Ti 3 C 2 Τ The thickness of the χ /graphene oxide layer is 1 to 10 μm, and the mass ratio of Ti 3 C 2 T to graphene oxide in the Ti 3 C 2 T χ / graphene oxide layer is 1: 0.2-1.
[权利要求 2] —种如权利要求 1所述的 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜的制备 方法， 其特征在于， 包括以下几个步骤： [Claim 2] A method for preparing a Ti 3 C 2 T χ / graphene oxide/Celgard composite separator according to claim 1, comprising the following steps:
步骤 （1) 将 Ti 3AlC ^¾瓷粉末放入氢氟酸中腐蚀， 腐蚀后溶液加入 去离子水进行离心处理， 然后将沉淀物烘干， 得到堆垛的层片状 Ti 3 C 2T X粉体； Step (1) Ti 3 AlC ^ 3⁄4 porcelain powder is etched in hydrofluoric acid, and the solution is added to deionized water for centrifugation after etching, and then the precipitate is dried to obtain a stacked sheet of Ti 3 C 2 T. X powder;
步骤 （2) 将氧化石墨和 Ti 3C 2T x粉体加入到水中超声分散， 形成的 悬浮液， 再将悬浮液加入到垫有 Celgard隔膜和滤纸的抽滤瓶中抽滤Step (2) Adding graphite oxide and Ti 3 C 2 T x powder to ultrasonic dispersion, forming a suspension, and then adding the suspension to a suction filter bottle with Celgard separator and filter paper for suction filtration
， 烘干后撕去滤纸及得到 Ti 3C 2T χ/氧化石墨烯 /Celgard复合隔膜。 After drying, the filter paper was peeled off and a Ti 3 C 2 T χ / graphene oxide/Celgard composite separator was obtained.
[权利要求 3] 如权利要求 2所述的方法， 其特征在于， 所述步骤 （1) 中氢氟酸的浓 度为 20<¾-50<¾， 腐蚀的吋间为 4-24小吋。 [Claim 3] The method according to claim 2, wherein the concentration of hydrofluoric acid in the step (1) is 20 < 3⁄4 - 50 < 3⁄4, and the corrugated turns are 4-24 hours.
[权利要求 4] 如权利要求 2所述的方法， 其特征在于， 所述步骤 （2) 中氧化石墨和 [Claim 4] The method according to claim 2, wherein in the step (2), graphite oxide and
11 ^ 21\粉体的质量比为1： 0.2-1， 超声吋间为 1-5小吋。 The mass ratio of 11 ^ 2 1 \ powder is 1: 0.2-1, and the ultrasonic ratio is 1-5 hours.
[权利要求 5] 如权利要求 2所述的方法， 其特征在于， 所述步骤 （2) 中氧化石墨和 [Claim 5] The method according to claim 2, wherein in the step (2), graphite oxide and
Ti 3C 2T χ粉体悬浮液的浓度为 0.1- lmg/mL， 抽滤吋 Celgard隔膜在滤纸 的上面与悬浮液直接接触。
The concentration of the Ti 3 C 2 T χ powder suspension was 0.1-lmg/mL, and the Celgard membrane was directly contacted with the suspension on the filter paper.
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