Research progress of power/energy storage battery separator based on selective ion migration strategy
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摘要: 随着锂离子电池等新能源电池在动力/储能领域的不断发展，传统商业聚烯烃隔膜由于润湿性与离子选择性差、孔隙率低等缺点已不能满足高性能锂电池的发展需要。近年来学者针对提升隔膜离子导电性能方面做了大量研究，然而锂电池充放电过程中通常只有阳离子传输参与氧化还原反应，二元电解质中锂离子通常被溶剂分子包围形成较大的溶剂鞘导致阴离子的移动能力反而强于锂离子，电池内部低的阳离子传输效率导致电池出现浓差极化、锂枝晶等问题，限制电池在高倍率下的应用，因此设计抑制阴离子穿梭促进阳离子快速迁移的新型电池隔膜在提升电池综合性能方面具有优异的发展前景。本文从近期的研究热点出发，主要从基团功能化设计、路易斯酸的俘获效应、空间筛分等策略详细介绍基于提升阳离子迁移能力的新型隔膜在电池领域的发展，最后总结指出电池隔膜领域存在的挑战和未来的发展方向。Abstract: With the continuous development of lithium-ion batteries and other new energy batteries in the power/energy storage field, traditional commercial polyolefin separators can no longer meet the development needs of high-performance lithium batteries due to the disadvantages of poor wettability, ion selectivity, and low porosity. In recent years, scholars have done a lot of research on improving the ionic conductivity of separators. However, during the charging and discharging process of lithium batteries, only cations can transport to participate in the redox reaction. Lithium ions in binary electrolytes are usually surrounded by solvent molecules to form a larger solvent sheath, which causes the mobility of anions to be stronger than that of lithium ions. The low cation transmission efficiency inside the battery leads to problems such as concentration polarization and lithium dendrites in the battery, which limits the application of the battery at high rates. Therefore, the design of a new type of battery separator that inhibits the shuttle of anions and promotes the rapid migration of cations has excellent development prospects in improving the electrochemical performance of the battery. Starting from recent research hotspots, this article mainly introduces the development of new separators based on the improvement of cation migration ability in the battery field from the functional design of groups, the trapping effect of Lewis acid, and spatial screening. Finally, it concludes that the battery separator field exists challenges and future development directions.
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图 1 锂离子电池和锂硫电池隔膜的离子电导率和锂离子迁移数
Figure 1. Ion conductivity and lithium ion transference number for lithium ion battery and lithium sulfur battery separators
图 2 PAA纳米纤维隔膜的制备过程示意图[17](a)；0.2C倍率下电池的循环性能和库仑效率[17](b)；改性PVA功能隔膜的合成路线[21](c)；聚酰亚胺隔膜的碱性水解示意图[23](d)
Figure 2. Schematic illustration of the preparation process of the PAA nanofiber separator[17](a); Cycle performance and coulombic efficiencies of the batteries at 0.2C[17](b); Synthesis route of the modified PVA new functional separator[21](c); Schematic for alkaline hydrolysis of the polyimide separator[23](d)
图 3 PP隔膜功能化的示意图[24](a)；TA/PEI改性隔膜影响锂离子迁移示意图[25](b) ；电池在电流密度为0.2C至7C时的倍率能力[25](c)；N-Al2O3/PE复合隔膜对锂离子迁移的影响示意图[28]
Figure 3. (a) Schematic illustration showing the functionalization of PP separator[24](a); Schematic of TA/PEI modified separator influence on lithium ion migration[25](b); Rate capability of the cells at the current densities range from 0.2C to 7C[25](c); Schematic of N-Al2O3/PE composite separator influence on lithium ion migration[28](d)
图 4 SnO2官能化PP的合成示意图[34](a)；PP-MWCNTs /CeO2隔膜制备示意图[35](b)；双层隔板的制备示意图[37](c)；自组装过程示意图以及自组装前后的PE隔膜横截面示意图[40](d)；原始和PAA / ZrO2 LbL改性PE隔膜横截面图及在PE隔膜上构建PAA / ZrO2多层的逐层自组装过程[41](e)；13X沸石结构中的酸性位点[46](f)
Figure 4. (a)Schematic illustration of the synthesis of SnO2 functionalized PP[34](a); Schematic diagram for the preparation of PP-MWCNTs/CeO2 separators[35](b); Schematic illustration of preparation of bi-layer separators[39](c); Schematic illustrations for Self-assembly process and cross-sectional diagram of PE separator before and after self-assembly[40](d); Cross-sectional diagram of pristine and PAA/ZrO2 LbL-modified PE separators and layer-by-layer self assembly process for the construction of PAA/ZrO2 multilayers on PE separator[41](e); Acidic sites in the 13X zeolite structure[46](f)
图 5 过滤制备Ni3(HITP)2/PP隔膜的过程及其在Li-S电池中的组装[53](a)；Ni-MOF / MWCNT改性PE隔膜用于阻止多硫化锂迁移到Li-S电池锂阳极示意图[54](b)；功能性电纺MOF-PVA膜吸附阴离子并促进锂离子的运输示意图[57](c)；GF、MOF-GF复合隔膜和MOF-GF中离子传输行为的放大图[58](d)；Mn-BTC MOF涂层的Li-S电池循环前后的电化学阻抗谱[59](e)；亲水性微孔膜的快速离子传输和高离子分子选择性的工作原理[64](f)
Figure 5. Illustration of the preparation process of the Ni3(HITP)2-modified separator by filtration and its assembly into the Li−S battery[51](a); Schematic illustration of Ni-MOF/MWCNT-coated PE separator for blocking lithium polysulfide migration to the lithium anode in the lithium-sulfur cell[52](b); Schematics showing a functional electrospun MOF–PVA for adsorbing anions and facilitating the transport of lithium ions[55](c); Schematic illustrations of glass fiber; MOF-GF composite separator and an enlarged view showing ion transport behaviours in MOG[56](d); Electrochemical impedance spectra for the Li-S cell with Mn-BTC MOF -coated membrane before and after cycling[57](e); Working principle of hydrophilic microporous membranes for fast ion transport and high ionic and molecular selectivity[62](f)
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