CN109546209B - 一种全固态聚合物电解质及可充电氯离子电池 - Google Patents
一种全固态聚合物电解质及可充电氯离子电池 Download PDFInfo
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- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 11
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 9
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- 150000001450 anions Chemical class 0.000 claims description 4
- 229910052791 calcium Inorganic materials 0.000 claims description 4
- 239000011575 calcium Substances 0.000 claims description 4
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 4
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- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
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- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
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- XITGHTRVSNMXOD-UHFFFAOYSA-N [Nb].ClOCl Chemical compound [Nb].ClOCl XITGHTRVSNMXOD-UHFFFAOYSA-N 0.000 claims description 2
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- 239000000956 alloy Substances 0.000 claims description 2
- 229910052454 barium strontium titanate Inorganic materials 0.000 claims description 2
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 2
- 229910002113 barium titanate Inorganic materials 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 229940073609 bismuth oxychloride Drugs 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- CNRRZWMERIANGJ-UHFFFAOYSA-N chloro hypochlorite;molybdenum Chemical compound [Mo].ClOCl CNRRZWMERIANGJ-UHFFFAOYSA-N 0.000 claims description 2
- ZHXZNKNQUHUIGN-UHFFFAOYSA-N chloro hypochlorite;vanadium Chemical compound [V].ClOCl ZHXZNKNQUHUIGN-UHFFFAOYSA-N 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- NKZSPGSOXYXWQA-UHFFFAOYSA-N dioxido(oxo)titanium;lead(2+) Chemical compound [Pb+2].[O-][Ti]([O-])=O NKZSPGSOXYXWQA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
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- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 2
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- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 2
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- IAZSXUOKBPGUMV-UHFFFAOYSA-N 1-butyl-3-methyl-1,2-dihydroimidazol-1-ium;chloride Chemical compound [Cl-].CCCC[NH+]1CN(C)C=C1 IAZSXUOKBPGUMV-UHFFFAOYSA-N 0.000 description 1
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Abstract
本发明涉及一种全固态聚合物电解质及可充电氯离子电池，以可传导氯离子的全固态聚合物材料为电解质，该电解质的组成包括聚合物基体、活性氯盐及固态增塑剂，通过溶液浇注法及随后的干燥处理制得；本发明所制备的固态聚合物电解质不含液态物质，同时具有很好的氯离子传导能力和较宽的电化学窗口，将其和正负极材料组合，构建全固态可充电氯离子电池体系，可以解决金属氯化物正极材料以及镁负极材料在液态电解液中经充放电循环而产生的脱溶及副反应问题，从而有效提高氯离子电池的电化学性能。
Description
技术领域
本发明属于能源领域，涉及一种全固态聚合物电解质及可充电氯离子电池，具体是制备一种基于氯离子传导的全固态聚合物电解质，用于构建一种全固态可充电氯离子电池。
背景技术
随着能源的日益短缺和环境的污染，对环保型和高能量密度的可充电电池进行了广泛的研究。其中，基于阴离子传导的电化学储能体系也得到了研究。可充电氯离子电池具有资源丰富、环境友好等优点，其理论上的能量密度可达2500Wh/L。但是，以金属氯化物/金属作为电极体系，当电解质采用有机液态电解液时，一方面，金属氯化物因为路易斯酸碱反应在液态电解液里会产生脱溶问题，另一方面，具有高储量的镁负极材料的放电产物也会溶于液态电解液中，而且液态电解液中的另一种阴离子和镁负极会发生副反应。因此，开发基于氯离子传导的全固态电解质是解决上述问题的手段之一。而基于氯离子传导的电解质研究较少。Derrington等人在期刊Journal of Solid State Chemistry的15卷题为“IonicConductivity of Some Alkaline Earth Halides”和Imanaka等人在期刊AngewandteChemie International Edition的41卷题为“Water-Insoluble Lanthanum Oxychloride-Based Solid Electrolytes with Ultra-High Chloride Ion Conductivity”中报道的无机金属氯化物或氯氧化物如BaCl2、SrCl2、LaCl3和LaOCl在500K的高温下的电导率仅为10- 6S/cm。Murin等人在期刊Russian Journal of Electrochemistry的45卷题为“SolidElectrolytes with Predominant Chloride Conductivity”中报道的立方结构的CsSnCl3的室温电导率可达10-4S/cm，但因为其半导体性质，不能够作为电解质材料。Huang等人在期刊Macromolecular Materials Engineering的165卷题为“Polymerization ofDiallyldimethylammonium Chloride in Inverse Emulsion,II.Molecular Weight andElectrical Conductivity of the Polymer”中报道了聚合物电解质，但该电解质采用的增塑剂为液态的聚乙烯醇，不是全固态聚合物电解质。Gschwind等人在期刊Chemistryopen的5卷题为“Facile Preparation of Chloride-Conducting Membranes:First SepTowards a Room-Temperature Solid-State Chloride-Ion Battery”报道了类似的准固态聚合物电解质，同样是采用了液态的增塑剂，而且所构建的电池体系仅有放电性能，为不可充电电池。
发明内容
本发明的目的是为了解决液态电解液中存在的脱溶和副反应等问题，而提供一种基于氯离子传导的全固态聚合物电解质，本发明的另一目的是提供上述全固态聚合物电解质的制备方法，并构建一种全固态可充电氯离子电池。
本发明的技术方案为：一种全固态聚合物电解质，其特征在于该电解质的组分为聚合物基体、活性氯盐及固态增塑剂，其中聚合物基体的质量分数为10％～70％；活性氯盐的质量分数为10％～50％；固态增塑剂的质量分数为3％～70％。
优选所述的聚合物基体为聚环氧乙烷、聚环氧丙烷、聚甲基丙烯酸甲酯、聚苯乙烯、聚乙烯基吡咯烷酮、聚丙烯腈、聚乙烯醇、聚乙烯醇缩丁醛、聚碳酸酯或聚碳酸丙烯酯。所述的聚合物基体的平均分子量为10～60万。
优选所述的活性氯盐的阴离子为氯离子；阳离子为四烷基铵根离子、二烷基咪唑离子、二烷基哌啶离子、二烷基吡咯烷离子或烷基吡啶离子。
优选所述的固态增塑剂，为丁二腈、二氧化钛、二氧化硅、三氧化二铝、钛酸钡、钛酸锶钡或钛酸铅。
本发明还提供了一种制备上述的全固态聚合物电解质的方法，其具体步骤为：将聚合物基体、活性氯盐和固态增塑剂按比例加入腈类或醇类的低沸点有机溶剂中，经搅拌后，浇注在基板上，挥发溶剂，随后在30-60℃温度下真空干燥24-96h，进一步除去残留溶剂，制得全固态聚合物电解质。
优选低沸点有机溶剂为腈类或醇类的低沸点有机溶剂，更优选乙腈或甲醇。
优选所述的搅拌时间为24-72h；所述的基板为聚四氟乙烯或玻璃平板；所述的挥发溶剂为在氮气气氛及常压条件下挥发溶剂3-8h。
本发明还提供了一种利用上述的全固态聚合物电解质构建的全固态可充电氯离子电池，其特征在于将全固态聚合物电解质与正极材料、负极材料组装；其中正极材料为金属氯化物、金属氯氧化物或氯掺杂的导电聚合物材料，负极材料为金属锂、镁或钙，或其中一种与过渡金属的合金，或其中一种与碳的复合材料，或其中一种合金与碳的复合材料。
优选上述的金属氯化物为氯化钒、氯化铬、氯化锰、氯化铁、氯化钴、氯化镍、氯化铜、氯化锡或氯化铋；所述的金属氯氧化物为氯氧化铁、氯氧化铋、氯氧化锑、氯氧化钒、氯氧化铌或氯氧化钼；所述的氯掺杂的导电聚合物材料中的导电聚合物为聚吡咯、聚苯胺或聚噻吩。
本发明制备一种基于氯离子传导的全固态聚合物电解质，该聚合物电解质的成分包含聚合物基体、活性氯盐及固态增塑剂，和正极材料及负极材料组装为全电池。将制得的全固态聚合物电解质和正负极组装为扣式或软包的全固态可充电氯离子电池。并通过充放电测试、循环伏安测试、X射线衍射、差热分析、热重分析、红外光谱、X射线光电子能谱、扫描电镜、透射电镜等方法证明了该电池的可行性和基于氯离子传输的电池原理。该新型全固态电池体系可解决氯离子电池采用液态电解液时所存在的脱溶和副反应，从而有望实现高能量密度金属氯化物正极和高储量的镁负极的应用。
有益效果：
本发明提供的一种全固态聚合物电解质及其制备方法，具体应用表现为构建了全固态可充电氯离子电池。该新型全固态电池体系可解决氯离子电池采用液态电解液时所存在的脱溶和副反应，从而有望实现高能量密度金属氯化物正极和高储量的镁负极的应用。
附图说明
图1为实施例1中制得的全固态聚合物电解质膜的光学照片和断面的扫描电镜图，其中a,b为光学照片，c为断面的扫描电镜图；
图2为实施例1中制得的全固态聚合物电解质的阿雷尼乌斯图；
图3为实施例1中制得的全固态聚合物电解质的线性扫描伏安图；
图4为实施例1中采用全固态聚合物电解质的氯离子电池的充放电曲线图。
具体实施方式
实施例1：
材料制备：将平均分子量为30万的聚环氧乙烷与三丁基甲基氯化铵和丁二腈三者以质量比为20％：20％：60％置于20mL的试剂瓶中，加入3mL无水乙腈，在磁力搅拌器上以450rpm的转速搅拌48h，然后置于聚四氟乙烯板，用具有一定厚度的刮刀在板上将溶液轻轻刮平，在氮气气氛及常压下挥发6h并在50℃真空干燥箱真空干燥48h，即可得到控制在一定均匀厚度的膜，后冲切成19mm的圆片待用。
光学照片分析(图1a，b)：制得的全固态聚合物电解质膜的机械性能良好，可弯曲)，为半透明膜；电镜照片(图1c)分析表明，膜的厚度约为80μm。
电化学性能测试：将制得的全固态聚合物电解质膜装于阻塞型电池。正负极为不锈钢，在电化学工作站上用交流阻抗法进行测试，将得到聚合物电解质的本体电阻Rb，通过公式计算出不同温度下的离子电导率，以Logσ-1000/T作图，得到离子电导率与温度关系图，可以看出温度越高，离子电导率越大(图2)。
电化学窗口测试：将制得的全固态聚合物电解质装于扣式电池，正负极为不锈钢电极，在电化学工作站上用线性扫描伏安法进行测试，测试温度为313K，扫描速度为5mV/s，测得结果显示膜的氧化电位为2.11V，还原电位为-2.09V，电化学窗口为4.20V，所制备的全固态聚合物电解质的电化学窗口较宽(图3)。
恒流充放电测试：将制得的全固态聚合物电解质装于扣式电池，正极为氯氧化铁正极，负极为金属锂片，在电化学工作站上进行测试，测试温度为313K，测得结果显示首次放电容量可达到87mAh/g，第三次放电比容量可以达到98mAh/g(图4)。
实施例2：
材料制备与电化学性能测试：将平均分子量为15万的聚环氧乙烷、1-甲基-4-丁基哌啶氯盐和纳米二氧化钛以质量比为65％：32％：3％的比例置于20mL的试剂瓶中，加入5mL无水乙腈溶解，在磁力搅拌器上以450rpm的转速搅拌72h，然后置于聚四氟乙烯板，用具有一定厚度的刮刀在板上轻轻刮平，在通风橱挥发3h并在40℃下真空干燥72h，即可得到控制在一定均匀厚度的膜，将全固态聚合物电解质薄膜冲切成19mm圆片后转移至惰性气氛的手套箱中放置待用。采用聚吡咯为正极、金属锂为负极组装全固态可充电氯离子电池，以10mA/g的电流密度在313K下进行循环测试，首次放电比容量可以达到50mAh/g，第三次放电比容量可达70mAh/g。
实施例3：
材料制备与电化学性能测试：将平均分子量为30万的聚环氧丙烷和1-甲基-4丁基吡咯烷氯盐、氧化铝以质量比为70％：15％：15％的比例置于20mL的试剂瓶中，加入5mL甲醇溶解，在磁力搅拌器上以450rpm的转速搅拌72h，然后置于聚四氟乙烯板，用具有一定厚度的刮刀在板上轻轻刮平，在氮气气氛及常压下挥发3-6h并在60℃真空干燥24h，即可得到控制在一定均匀厚度的膜，将制得的全固态聚合物电解质薄膜冲切成19mm圆片后转移至惰性气氛的手套箱中放置待用。采用氯氧化铁为正极、金属镁/碳复合材料为负极组装全固态氯离子电池，以10mA/g的电流密度在313K下进行循环测试，首次放电比容量可以达到55mAh/g。
实施例4：
材料制备与电化学性能测试：将分子量为20万的聚偏氟乙烯、1-丁基-3-甲基咪唑氯盐、纳米二氧化硅以质量比为40％：40％：20％的比例置于20mL的试剂瓶中，加入5mL甲醇，在磁力搅拌器上以450rpm的转速搅拌72h，然后置于聚四氟乙烯板，用具有一定厚度的刮刀在板上轻轻刮平，在氮气气氛及常压下挥发8h并在30℃真空干燥96h，即可得到控制在一定均匀厚度的膜，后冲切成19mm的圆片，采用氯氧化铁为正极、金属镁/碳为负极组装全固态氯离子电池，以10mA/g的电流密度在313K下进行循环测试，首次放电比容量可以达到80mAh/g。
实施例5：
材料制备与电化学性能测试：将平均分子量为60万的聚乙烯基吡咯烷酮、三丁基甲基氯化铵、丁二腈以质量比为20％：10％：70％的比例置于20mL的试剂瓶中，加入3mL无水乙腈溶解，在磁力搅拌器上以450rpm的转速搅拌48h，然后置于聚四氟乙烯板，用具有一定厚度的刮刀在板上轻轻刮平，在在氮气气氛及常压下挥发5h并在50℃下真空干燥48h，即可得到控制在一定均匀厚度的膜，将制得的全固态聚合物电解质薄膜冲切成19mm圆片后转移至惰性气氛的手套箱中放置待用。采用氯化铜为正极、金属锂为负极组装全固态可充电氯离子电池，以10mA/g的电流密度在313K下进行循环测试，首次放电比容量可以达到200mAh/g。
Claims (6)
1.一种全固态聚合物电解质，其特征在于该电解质的组分为聚合物基体、活性氯盐及固态增塑剂，其中聚合物基体的质量分数为10％～70％；活性氯盐的质量分数为10％～50％；固态增塑剂的质量分数为3％～70％；其中所述的聚合物基体为聚环氧乙烷、聚环氧丙烷、聚甲基丙烯酸甲酯、聚苯乙烯、聚乙烯基吡咯烷酮、聚丙烯腈、聚乙烯醇、聚乙烯醇缩丁醛、聚碳酸酯或聚碳酸丙烯酯；所述的活性氯盐的阴离子为氯离子；阳离子为四烷基铵根离子、二烷基咪唑离子、二烷基哌啶离子、二烷基吡咯烷离子或烷基吡啶离子；所述的固态增塑剂，为丁二腈、二氧化钛、二氧化硅、三氧化二铝、钛酸钡、钛酸锶钡或钛酸铅。
2.根据权利要求1所述的全固态聚合物电解质，其特征在于所述的聚合物基体的平均分子量为10～60万。
3.一种制备如权利要求1所述的全固态聚合物电解质的方法，其具体步骤为：将聚合物基体、活性氯盐和固态增塑剂按比例加入低沸点有机溶剂中，经搅拌后，浇注在基板上，挥发溶剂，随后在30-60℃温度下真空干燥24-96h，制得全固态聚合物电解质。
4.根据权利要求3所述的方法，其特征在于搅拌时间为24-72h；所述的基板为聚四氟乙烯或玻璃平板；所述的挥发溶剂为在氮气气氛及常压条件下挥发溶剂3-8h。
5.一种利用如权利要求1所述的全固态聚合物电解质构建的全固态可充电氯离子电池，其特征在于将全固态聚合物电解质与正极材料、负极材料组装；其中正极材料为金属氯化物、金属氯氧化物或氯掺杂的导电聚合物材料，负极材料为金属锂、镁或钙，或其中一种与过渡金属的合金，或其中一种与碳的复合材料，或其中一种合金与碳的复合材料。
6.根据权利要求5所述的全固态可充电氯离子电池，其特征在于所述的金属氯化物为氯化钒、氯化铬、氯化锰、氯化铁、氯化钴、氯化镍、氯化铜、氯化锡或氯化铋；所述的金属氯氧化物为氯氧化铁、氯氧化铋、氯氧化锑、氯氧化钒、氯氧化铌或氯氧化钼；所述的氯掺杂的导电聚合物材料中的导电聚合物为聚吡咯、聚苯胺或聚噻吩。
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