Engineering the interface between separators and cathodes to suppress polysulfide shuttling in lithium-sulfur batteries
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摘要: 锂硫电池由于具有较高的理论比容量和能量密度而受到广泛的关注。然而,多硫化物的穿梭效应极大地阻碍了其实际应用,许多研究表明,电池隔膜界面工程是解决多硫穿梭问题的有效策略之一。隔膜界面工程的主要功能可分为物理阻隔、化学吸附和催化作用。在这个界面工程过程中,炭材料因其导电率高、比表面积大、孔容大而备受关注,而炭材料的非极性难以紧密结合多硫化物;使用高极性的材料能够对多硫化物起到很好的化学结合作用,可有效吸附多硫化物。因此,人们常采用高极性材料与炭材料复合,或者在炭材料设计过程中掺杂异原子或引入官能团。此外,具有多硫催化转化作用的材料对于有效抑制多硫穿梭也十分重要。本文重点介绍了隔膜界面工程的具体实施策略及其主要功能,并对锂硫电池商用化中所面临的问题和挑战进行了总结。最后,结合目前电池性能改善的各种措施,对锂硫电池实用化的光明前景进行了展望。Abstract: Lithium-sulfur batteries have attracted extensive attention because of their high theoretical specific energy storage capacity and energy density. However, the shuttling of polysulfides greatly hinders their practical use. Many studies show that engineering the interface between separators and cathodes is an effective strategy to solve this problem. Ways to inhibit the shuttling can be divided into physical blocking, chemical adsorption, and catalysis. Among the interfacial materials, carbon materials have attracted enormous attention due to their high electrical conductivity, large specific area, and high pore volume. However, their non-polarity makes it impossible for them to bind polysulfides tightly and heteroatoms/functional groups are incorporated in them or highly polar materials are composited with them in the design of the interfacial materials. In addition, the catalytic effect of the carbon in the polysulfide conversion is believed to be very important in effectively suppressing the shuttling. This review focuses on the detailed strategies and functions of interfacial engineering in addressing the problems and challenges in the use of lithium sulfur batteries. Finally, practical applications of lithium sulfur batteries are proposed, based on a combination of various measures including interfacial engineering.
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Key words:
- Carbon materials /
- Interfacial engineering /
- Polar materials /
- Polysulfides /
- Lithium-sulfur batteries
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Figure 1. Theoretical energy density of different rechargeable battery systems based on the active materials[7]. Reprinted with permission.
Figure 3. (a) Schematic of (left) Li–S battery with traditional configuration and (right) with the MWCNT interlayer inserted between the cathode and commercial separator[30]. (b) Schematic of the Li-S batteries with the CFs@PP separator[58]. (c) Schematic illustration of the MMMS for regulating Li deposition and blocking polysulfide shuttle in Li–S batteries[59]. (d) Schematic configuration of the Li–S cells with (up) pristine separator and (down) meso C-coated separator[51]. Reproduced with permission.
Figure 4. (a) Schematic cell configuration of the Li–S battery with N–P–PC/G-modified separator[72]. (b) Schematic of a Li–S battery with electrode configuration. The paler yellow color represents the reduced shuttle effect[73]. (c) Schematic illustrationin of a combined strategy of integrating SPEEK into the cathode and inserting a SWCNT/rGO interlayer between the cathode and the separator[74]. (d) VGCF/PPY composite[75]. Reproduced with permission.
Figure 5. (a) Schematic of the fabrication of a porous VN/G composite and the cell assembly with corresponding optical images of the material obtained. Scale bar, 500 nm[91]. (b) Schematic diagrams of Li-S battery with (left) the pristine Celgard and (right) LBL-separator[92]. (c) Schematic representation of Li-S battery using the TiO/MWCNT-coated separator[94]. (d) Schematic of Li-S battery employing the SMO modified separators[95]. Reproduced with permission.
Figure 6. (a) Schematic configuration of Li-S batteries with PP separator; PG @ PP; and PG-Fe3O4 @ PP interlayer[53]. (b) Comparison of the LiPS migration and lithium-ion transport between pristine (left) and VN modified separators (right)[96]. (c) Schematic illustration of Li-S batteries with PP separator (left) and BTS/PP separator (right)[97]. (d) Schematic illustration of 3-D structure of CSUST-1[98]. Reproduced with permission.
Figure 7. (a) Schematic diagram of electrode structure with the functional G/M@CNT interlayer[104]. (b) Schematic illustration of the preparation procedure of Co9S8-Celgard[105]. (c) Schematic for Li–S batteries with different separators: with a routine separator (left) and with an NbN/NG modified separator (right)[106]. (d) Conceptual diagram to produce functionalized NGN (pyrolic, pyridinic, graphitic) N and -SO3- through NH3 treatment of OHGN and Nafion mixing (up), and N-NGN coated Celgard PP separator and their mechanism to chemically bind the PS through multifunctional effects (down)[107]. (e) Schematic illustration of the synthesis route of Ni/SiO2[60]. Reproduced with permission.
Table 1. Comparison of some previously reported literatures involving the separator interfacial engineering in the Li-S batteries (1 C=1675 mA g−1).
Materials Morphology Areal
density
(mg cm−2)Sulfur loading
(mg cm−2) &contentPreparation
methodRate capability
(mA h g−1)Cycling
performance
(mA h g−1)
(Cycles, Rate)Gravimetric
energy
densities
(wh kg−1)Ref. Carbon MWCNT Nanotubes 0.4 N.A. & 70% Vacuum filtration 1446 (0.1C), 855 (0.5C),
804 (1C)804(100, 1C) − [1] Mesoporous carbon 0.5 3.5 & 70% Blade coating 1359 (0.1C), 1281 (0.2C),
1216 (0.5C), 1060 (1C),
881 (2C), 443 (5C)723(500, 0.5C)683(500, 1C) 3.24 [2] Microporous carbon paper Particle - N.A. & 70% Vacuum filtration 1367 (0.1C), 1000 (1C),
846 (2C)850(100, 1C) − [3] Carbon-based material SWCNT/rGO Nanotubes & sheet 0.1 (Li2S)1.0 & 60% Vacuum filtration 773 (0.5A g−1), 660 (1A g−1),
440 (10A g−1)362(200, 1A g−1) − [4] N, P-doped porous carbon/RGO Homogeneous reticular 0.3 1.5 & 70% Blade coating 1416 (0.2C), 1168 (0.5C),
1009 (1C), 857 (2C),
639 (5C)733(500, 0.5C)661(500, 1C) 2.76 [5] Mesoporous Ni/SiO2 hollow sphere/RGO Particle/hollow spheres 0.24 1.2 & 80% Vacuum filtration 1456 (0.1C), 1080 (0.2C),
882 (0.5C), 826 (1C),
782 (2C)782(300, 2C) 1.25 [6] Polymers CTF@PDDA/PEDOT: PSS Lamellar 0.028 2 & 60% LBL 1038.4 (0.1C), 899.2 (0.2C),
795.7 (0.5C), 640.2 (1C),
191 (2C)577(1000, 1C) 1.78 [7] N-doped mesoporous carbon Sphere-like mesoporous 0.5 3.95 & 70% Blade coating 1364 (0.1C), 1062 (0.2C),
914 (0.5C), 838 (1C),
689 (2C)566(500, 0.5C) 1.51 [8] Metal oxides MnO2 Particle 0.02 1.2 & 70% LBL 733 (0.5C), 633 (1C),
494 (2C)494(500, 0.5C) 0.76 [9] TiO/MWCNT Particle/ Nanotubes 0.7 1.6 & 60% Blade coating 1354.3 (0.2C), 1247.2 (0.5C),
1073.3 (1C),893 (2C),
715.2 (3C)385.3(2000, 2C) 1.99 [10] MnO2/GO/
CNTVein-membrane 0.104 2.37 & 80% CVD 1259 (0.2C), 1055 (0.5C),
960 (1C), 829 (5C),
747 (10C)293(2500, 1C) 1.842 [11] PG-Fe3O4 Particle 0.478 0.9 & 60% Vacuum filtration 1423 (0.1C), 887 (0.3C),
789 (0.5C), 673 (1C) ,
589 (2C)356(2000, 1C) 0.95 [12] MnO-KB Particle 0.15 2 & 75% Blade coating 1200 (0.1C), 950 (2C), 901(200, 1C) 1.1 [13] Metal nitrides VN nanobelts Fiber 1.52 1.6 & 70% Vacuum filtration 1280 (0.1C), 1043 (0.5C),
895 (1C), 760 (2C)369(800, 1C) 1.14 [14] Doping Bi2Te2.7Se0.3 Particle 0.03 4 & 70% Magnetron sputtering 1284 (0.1C), 1061 (0.2C),
932 (0.5C), 847 (1C),
756 (2C)560(300, 2C) 3.17 [15] Sb2Se3−x Particle 0.5 1.8 & 70% Blade coating 1387 (0.1C), 1249 (0.2C),
787 (8C)874(500, 1C) 1.74 [16] -
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