WO2018184237A1 - Ti3c2tx/nafion/celgard composite separator - Google Patents
Ti3c2tx/nafion/celgard composite separator Download PDFInfo
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- WO2018184237A1 WO2018184237A1 PCT/CN2017/079805 CN2017079805W WO2018184237A1 WO 2018184237 A1 WO2018184237 A1 WO 2018184237A1 CN 2017079805 W CN2017079805 W CN 2017079805W WO 2018184237 A1 WO2018184237 A1 WO 2018184237A1
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- nafion
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/52—Removing gases inside the secondary cell, e.g. by absorption
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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 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 /Nafion/Celgard composite separator, including a commercial Celgard separator and a Ti 3 C 2 T x /Nafion layer on the surface thereof, the Ti 3 C 2 T x /Nafion layer having a thickness of 1 to 10 ⁇ m, in the Ti 3 C 2 T x /Nafion layer Ti 3 C 2 T x
- the mass ratio to Nafion is 0.05-0.5: 1.
- the present invention provides a Ti 3 C 2 T x /Nafion/Celgard composite separator prepared 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;
- Ti 3 C 2 T x powder was ultrasonically dispersed in a Nafion solution to form a suspension, and the suspension was applied to a Celgard separator, and vacuum dried to obtain a Ti 3 C 2 T / Nafion/Celgard composite diaphragm.
- 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 fraction of the Nafion solution in the step (2) is 5%, the ultrasonic volume is 1-5 hours, and the Ti 3 C 2 T x powder is added in an amount of 0.25-2.5% of the mass of the Nafion solution.
- Ti T on 3 C 2 T x Ti 3 C 2 T x / Nafion layer is -F group or a -OH group, with a group Nafion membrane -F They are all highly polar groups, which can form strong chemisorption of polysulfides formed during charge and discharge, can effectively prevent polysulfide from passing through the separator to the negative electrode, reduce the occurrence of shuttle effect, and improve the lithium-sulfur battery. life.
- FIG. 1 is a schematic view showing the structure of a Ti 3 C 2 T x /Nafion/Celgard composite separator of the present invention.
- FIG. 2 is a flow chart for preparing a Ti 3 C 2 T x /Nafion/Celgard composite separator of the present invention.
- FIG 3 is a cycle life diagram of a Ti 3 C 2 T x /Nafion/Celgard composite separator of the present invention.
- Embodiment 1 [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;
- 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.
- Embodiment 5 [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 cliff;
- the comparative example uses a Celgard separator as a lithium-sulfur battery separator, and other conditions are the same as described above.
- Example 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 73% of the initial capacity after 400 charge and discharge, and the comparative example is assembled into a lithium-sulfur battery by Celgard diaphragm, 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/Nafion/Celgard composite separator, comprising: a Celgard separator; and a Ti3C2Tx/ Nafion layer formed on a surface thereof. The Ti3C2Tx/Nafion layer has a thickness of 1-10μm. In the Ti3C2Tx/Nafion layer, a mass ratio of Ti3C2Tx to Nafion is 0.05-0.5:1. For the Ti3C2Tx in the Ti3C2Tx/Nafion layer, T represents an -F group or an -OH group, which along with an -F group of a Nafion film 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 2T x/Nafion/Celgard复合隔膜 技术领域 Title of Invention: A Ti 3 C 2 T x /Nafion/Celgard Composite Membrane 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。 [0001] The present invention relates to the field of lithium sulfur batteries, and in particular to 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 /Nafion/Celgard复合隔膜， 包括
商用 Celgard隔膜和其表面的 Ti 3C 2T x/Nafion层组成， 所述的 Ti 3C 2T x/Nafion层 的厚度为 1〜10μηι， 所述的 Ti 3C 2T x/Nafion层中 Ti 3C 2T x [0004] The technical problem to be solved by the present invention is to provide a Ti 3 C 2 T /Nafion/Celgard composite separator, including a commercial Celgard separator and a Ti 3 C 2 T x /Nafion layer on the surface thereof, the Ti 3 C 2 T x /Nafion layer having a thickness of 1 to 10 μm, in the Ti 3 C 2 T x /Nafion layer Ti 3 C 2 T x
与 Nafion的质量比为 0.05-0.5: 1。 The mass ratio to Nafion is 0.05-0.5: 1.
[0005] 本发明提供一种 Ti 3C 2T x/Nafion/Celgard复合隔膜的制备方法如下： [0005] The present invention provides a Ti 3 C 2 T x /Nafion/Celgard composite separator prepared 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 Ti 3C 2T x粉体加入 Nafion溶液中超声分散， 形成的悬浮液， 再将悬浮液 涂覆到 Celgard隔膜上， 真空干燥后得到一种 Ti 3C 2T /Nafion/Celgard复合隔膜。 [0007] (2) Ti 3 C 2 T x powder was ultrasonically dispersed in a Nafion solution to form a suspension, and the suspension was applied to a Celgard separator, and vacuum dried to obtain a Ti 3 C 2 T / Nafion/Celgard composite diaphragm.
[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 Nafion溶液的质量分数为 5%， 超声吋间为 1-5小吋， Ti 3C 2T x粉体 的加入量为 Nafion溶液的质量 0.25-2.5%。 [0009] The mass fraction of the Nafion solution in the step (2) is 5%, the ultrasonic volume is 1-5 hours, and the Ti 3 C 2 T x powder is added in an amount of 0.25-2.5% of the mass of the Nafion solution.
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 x/Nafion层中的 Ti 3C 2T x上的 T为 -F基团或 -OH基团， 与 Nafion膜上的 -F基团均为强极性基团， 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 T on 3 C 2 T x Ti 3 C 2 T x / Nafion layer is -F group or a -OH group, with a group Nafion membrane -F They are all highly polar groups, which can form strong chemisorption of polysulfides formed during charge and discharge, can effectively prevent polysulfide from passing through the separator to the negative electrode, reduce the occurrence of shuttle effect, and improve the lithium-sulfur battery. life.
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 x/Nafion/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 x /Nafion/Celgard composite separator of the present invention.
[0012] 图 2是本发明的 Ti 3C 2T x/Nafion/Celgard复合隔膜制备流程图。 2 is a flow chart for preparing a Ti 3 C 2 T x /Nafion/Celgard composite separator of the present invention.
[0013] 图 3是本发明的 Ti 3C 2T x/Nafion/Celgard复合隔膜的循环寿命图。 3 is a cycle life diagram of a Ti 3 C 2 T x /Nafion/Celgard composite separator of the present invention.
[0014] 其中， 1为 Ti 3C 2T x/Nafion层， 2为 Celgard隔膜。 Wherein 1 is a Ti 3 C 2 T x /Nafion layer, and 2 is a Celgard separator.
本发明的实施方式 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
[0017] (1) 将 Ti 3AlC 2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 Ti 3C 2T 崖； [0016] Embodiment 1 [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 0.025gTi 3C 2T χ粉体加入到 10g质量分数为 5%的 Nafion溶液中超声分散 ， 超声吋间为 1小吋， 形成的悬浮液， 再将悬浮液涂覆到 Celgard隔膜上， 真空干 燥后得到 Ti 3C 2T x/Nafion/Celgard复合隔膜。 [0018] (2) 0.025 g of Ti 3 C 2 T χ powder was added to 10 g of a 5% by mass Nafion solution, ultrasonically dispersed, 1 吋 between the ultrasonic turns, a suspension formed, and then the suspension was coated. On a Celgard separator, vacuum dried to obtain a Ti 3 C 2 T x /Nafion/Celgard composite separator.
[0019] 实施例 2 [0019] Example 2
[0020] (1) 将 Ti 3AlC 2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 Ti 3C 2T 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 0.25gTi 3C 2T χ粉体加入到 10g质量分数为 5%的 Nafion溶液中超声分散， 超声吋间为 5小吋， 形成的悬浮液， 再将悬浮液涂覆到 Celgard隔膜上， 真空干燥 后得到 Ti 3C 2T x/Nafion/Celgard复合隔膜。 [0021] (2) 0.25 g of Ti 3 C 2 T χ powder was added to 10 g of a 5% by mass Nafion solution, ultrasonically dispersed, 5 吋 between the ultrasonic turns, a suspension formed, and then the suspension was coated. On a Celgard separator, vacuum dried to obtain a Ti 3 C 2 T x /Nafion/Celgard composite separator.
[0022] 实施例 3 Embodiment 3
[0023] (1) 将 Ti 3AlC 2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 Ti 3C 2T 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 0.05gTi 3C 2T χ粉体加入到 10g质量分数为 5%的 Nafion溶液中超声分散， 超声吋间为 2小吋， 形成的悬浮液， 再将悬浮液涂覆到 Celgard隔膜上， 真空干燥 后得到 Ti 3C 2T x/Nafion/Celgard复合隔膜。 [0024] (2) 0.05 g of Ti 3 C 2 T χ powder was added to 10 g of a 5% by mass Nafion solution, ultrasonically dispersed, 2 hours of ultrasonic turbidity, a suspension formed, and then the suspension was coated. On a Celgard separator, vacuum dried to obtain a Ti 3 C 2 T x /Nafion/Celgard composite separator.
[0025] 实施例 4 [0025] Example 4
[0026] (1) 将 Ti 3AlC 2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 Ti 3C 2T 晨； [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 morning;
[0027] (2) 将 O.lgTi 3C 2T χ粉体加入到 10g质量分数为 5%的 Nafion溶液中超声分散， 超声吋间为 3小吋， 形成的悬浮液， 再将悬浮液涂覆到 Celgard隔膜上， 真空干燥 后得到 Ti 3C 2T x/Nafion/Celgard复合隔膜。 [0027] (2) O.lgTi 3 C 2 T χ powder was added to 10 g of a 5% by mass Nafion solution, ultrasonically dispersed, 3吋 between the ultrasonic turns, the resulting suspension, and then the suspension was coated It was coated on a Celgard separator and vacuum dried to obtain a Ti 3 C 2 T x /Nafion/Celgard composite separator.
[0028] 实施例 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 崖； Embodiment 5 [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 cliff;
[0030] (2) 将 0.2gTi 3C 2T χ粉体加入到 10g质量分数为 5%的 Nafion溶液中超声分散， 超声吋间为 4小吋， 形成的悬浮液， 再将悬浮液涂覆到 Celgard隔膜上， 真空干燥 后得到 Ti 3C 2T x/Nafion/Celgard复合隔膜。 [0030] (2) 0.2 g of Ti 3 C 2 T χ powder was added to 10 g of a 5% by mass Nafion solution, ultrasonically dispersed, 4 hours of ultrasonic turbidity, a suspension formed, and then the suspension was coated. On a Celgard separator, vacuum dried to obtain a Ti 3 C 2 T x /Nafion/Celgard composite separator.
[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] 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 73%， 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 73% of the initial capacity after 400 charge and discharge, and the comparative example is assembled into a lithium-sulfur battery by Celgard diaphragm, 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.
[0034] 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。
[0034] 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 x/Nafion/Celgard复合隔膜， 包括 Celgard隔膜和其表面的 [Claim 1] A Ti 3 C 2 T x /Nafion/Celgard composite separator comprising a Celgard separator and a surface thereof
Ti 3C 2T x/Nafion层组成， 所述的 Ti 3C 2T x/Nafion层的厚度为 1〜10μηιTi 3 C 2 T x /Nafion layer composition, the thickness of the Ti 3 C 2 T x /Nafion layer is 1~10μηι
， 所述的 Ti 3C 2T x/Nafion层中 Ti 3C 2T x Said Ti 3 C 2 T x / Nafion layer Ti 3 C 2 T x
与 Nafion的质量比为 0.05-0.5: 1。 The mass ratio to Nafion is 0.05-0.5: 1.
[权利要求 2] —种制备如权利要求 1所述的 Ti 3C 2T /Nafion/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 /Nafion/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 3C 2Τ χ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 Τ χ powder;
步骤 （2) ： 将 Ti 3C 2T x¾体加入 Nafion溶液中超声分散， 形成的悬浮 液， 再将悬浮液涂覆到 Celgard隔膜上， 真空干燥后得到 Ti 3C 2T x Step (2): Ti 3 C 2 T x 3⁄4 body is added to the Nafion solution to be ultrasonically dispersed, and the resulting suspension is applied to the Celgard separator and vacuum dried to obtain Ti 3 C 2 T x .
/Nafion/Celgard复合隔膜。 /Nafion/Celgard composite diaphragm.
[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， 步骤 （2) 中 Nafion溶液的质 量分数为 5%， 超声吋间为 1-5小吋。 [Claim 4] The method according to claim 2, wherein the mass fraction of the Nafion solution in the step (2) is 5%, and the ultrasonic volume 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， Ti 3C 2T x [Claim 5] The method according to claim 2, wherein Ti 3 C 2 T x
粉体的加入量为 Nafion溶液的质量 0.25-2.5%。
The powder is added in an amount of 0.25-2.5% by mass of the Nafion solution.
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| PCT/CN2017/079805 WO2018184237A1 (en) | 2017-04-08 | 2017-04-08 | Ti3c2tx/nafion/celgard composite separator |
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| PCT/CN2017/079805 WO2018184237A1 (en) | 2017-04-08 | 2017-04-08 | Ti3c2tx/nafion/celgard composite separator |
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| CN115207567A (en) * | 2022-05-18 | 2022-10-18 | 上海交通大学 | Difunctional modified diaphragm for lithium-sulfur battery and preparation method thereof |
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| CN107017376A (en) * | 2017-04-08 | 2017-08-04 | 深圳市佩成科技有限责任公司 | A kind of Ti3C2Tx/Nafion/Celgard composite diaphragms |
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| CN104592541A (en) * | 2015-01-20 | 2015-05-06 | 浙江大学 | Microporous polybenzimidazole membrane and lithium-sulfur battery with modified polybenzimidazole as membrane |
| CN107017376A (en) * | 2017-04-08 | 2017-08-04 | 深圳市佩成科技有限责任公司 | A kind of Ti3C2Tx/Nafion/Celgard composite diaphragms |
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| CN115207567A (en) * | 2022-05-18 | 2022-10-18 | 上海交通大学 | Difunctional modified diaphragm for lithium-sulfur battery and preparation method thereof |
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