Conductive Polymers on the Cathode Side of Lithium-Sulfur Batteries
DOI:
https://doi.org/10.70088/e3hrez86Keywords:
Lithium-sulfur battery, Polymer, Cathode, SeparatorAbstract
Lithium--sulfur batteries are regarded as highly promising next-generation energy storage devices due to their outstanding theoretical specific capacity (1675 mAh/g), high energy density (2600 Wh/kg), abundant raw material sources, environmental compatibility, and low cost. Nevertheless, their practical implementation remains hindered by rapid capacity fading and limited cycle life. Conductive polymers can not only enhance overall electrode conductivity but also provide physical or chemical barriers that suppress the shuttle effect of lithium polysulfides, thus alleviating capacity decay and improving electrochemical performance. This review focuses on the use of polypyrrole, polythiophene, polyaniline, and polyacrylonitrile in lithium--sulfur batteries. Representative advances in recent years are highlighted, and the future role of polymers in advancing the practical application of lithium--sulfur batteries is envisioned.References
A. M. Armand and J.-M. Tarascon, “Building better batteries,” Nature, vol. 451, no. 7179, pp. 652–657, 2008.
H. Cha, J. Kim, Y. Lee et al., “Issues and challenges facing flexible lithium-ion batteries for practical application,” Small, vol. 14, no. 43, pp. 1702989–1703006, 2018.
J. Hassoun, S. Panero, P. Reale et al., “A new, safe, high-rate and high-energy polymer lithium-ion battery,” Advanced Materials, vol. 21, no. 47, pp. 4807–4810, 2009.
S. Gao, Y. Su, L. Bao et al., “High-performance LiFePO₄/C electrode with polytetrafluoroethylene as an aqueous-based binder,” Journal of Power Sources, vol. 298, pp. 292–298, 2015.
F. Wu, W. Li, L. Chen et al., “Polyacrylonitrile-polyvinylidene fluoride as high-performance composite binder for layered Li-rich oxides,” Journal of Power Sources, vol. 359, pp. 226–233, 2017.
J. Xu, S. Dou, H. Liu et al., “Cathode materials for next generation lithium ion batteries,” Nano Energy, vol. 2, no. 4, pp. 439–442, 2013.
P. G. Bruce, S. A. Freunberger, L. J. Hardwick et al., “Li-O₂ and Li-S batteries with high energy storage,” Nature Materials, vol. 11, no. 1, pp. 19–29, 2011.
C. Huang, J. Xiao, Y. Shao et al., “Manipulating surface reactions in lithium-sulphur batteries using hybrid anode structures,” Nature Communications, vol. 5, p. 3015, 2014.
M. K. Song, E. J. Cairns, and Y. Zhang, “Lithium/sulfur batteries with high specific energy: old challenges and new opportunities,” Nanoscale, vol. 5, no. 6, pp. 2186–2204, 2013.
F. Wu, S. Zhao, L. Chen et al., “Metal-organic frameworks composites threaded on the CNT knitted separator for suppressing the shuttle effect of lithium sulfur batteries,” Energy Storage Materials, vol. 14, pp. 383–391, 2018.
D. H. and J. U., “Electric dry cells and storage batteries,” U.S. Patent US3043896, 1962.
F. Wu, J. Li, Y. Tian et al., “3D coral-like nitrogen-sulfur co-doped carbon-sulfur composite for high performance lithium-sulfur batteries,” Scientific Reports, vol. 5, p. 13340, 2015.
A. Y. Coran, “Vulcanization: conventional and dynamic,” Rubber Chemistry and Technology, vol. 68, no. 3, pp. 351–375, 1995.
R. L. Fan, Y. Zhang, and C. Huang, “Simulation and verification for sulfur accelerated vulcanization of gum natural rubber compound,” Rubber Chemistry and Technology, vol. 75, no. 2, pp. 287–297, 2002.
G. Milani, E. Leroy, and F. Milani et al., “Mechanistic modeling of reversion phenomenon in sulphur cured natural rubber vulcanization kinetics,” Polymer Testing, vol. 32, no. 6, pp. 1052–1063, 2013.
M. Barghamadi, A. Kapoor, and C. Wen, “A review on Li-S batteries as a high efficiency rechargeable lithium battery,” Journal of the Electrochemical Society, vol. 160, no. 8, pp. A1256–A1263, 2013.
M. J. Lacey, F. Jeschull, and K. Edström et al., “Functional, water-soluble binders for improved capacity and stability of lithium--sulfur batteries,” Journal of Power Sources, vol. 264, pp. 8–14, 2014.
A. Rosenman, E. Markevich, G. Salitra et al., “Review on Li-sulfur battery systems: an integral perspective,” Advanced Energy Materials, vol. 5, no. 16, p. 1500212, 2015.
M. Wang, G. Liu, H. Wang et al., “Anchor and activate sulfide with LiTi₂(PO₄)₂.₈₈F₀.₁₂ nano spheres for lithium sulfur battery application,” Journal of Materials Chemistry A, vol. 6, no. 17, pp. 7639–7648, 2018.
Z. Wei Seh, W. Li, J. J. Cha et al., “Sulphur-TiO₂ yolk-shell nanoarchitecture with internal void space for long-cycle lithium-sulphur batteries,” Nature Communications, vol. 4, p. 1331, 2013.
W. Dou, Y. Huang, X. Sun et al., “Conductive polymers in the application of lithium-sulfur batteries,” Development & Application Materials, 2017.
L. Ma, K. E. Hendrickson, S. Wei et al., “Nanomaterials: science and applications in the lithium--sulfur battery,” Nano Today, vol. 10, no. 3, pp. 315–338, 2015.
Y. Shang, C. Wang, and B. Liu et al., “Preparation and properties of manganese dioxide coated carbon nanotubes-sulfur composite cathode material,” Energy Storage Science & Technology, 2017.
G. Xu, Q.-b. Yan, A. Kushima et al., “Conductive graphene oxide-polyacrylic acid (GOPAA) binder for lithium-sulfur battery,” Nano Energy, vol. 31, pp. 568–574, 2017.
A. F. Hofmann, D. N. Fronczek, and W. G. Bessler, “Mechanistic modeling of polysulfide shuttle and capacity loss in lithium-sulfur batteries,” Journal of Power Sources, vol. 259, pp. 300–310, 2014.
W. Hua, Z. Yang, H. Nie et al., “Polysulfide-scission reagents for the suppression of the shuttle effect in lithium-sulfur batteries,” ACS Nano, vol. 11, no. 2, pp. 2209–2218, 2017.
L. Kong, X. Chen, B. Q. Li et al., “A bifunctional perovskite promoter for polysulfide regulation toward stable lithium-sulfur batteries,” Advanced Materials, vol. 30, no. 2, 2018.
J. Liu, L. Yuan, K. Yuan et al., “SnO₂ as a high-efficiency polysulfide trap in lithium-sulfur batteries,” Nanoscale, vol. 8, no. 28, pp. 13638–13645, 2016.
X. Yu, Z. Bi, F. Zhao et al., “Polysulfide-shuttle control in lithium-sulfur batteries with a chemically/electrochemically compatible NaSICON-Type solid electrolyte,” Advanced Energy Materials, vol. 6, no. 24, p. 1601392, 2016.
S. Chen, B. Sun, X. Xie et al., “Multi-chambered micro/mesoporous carbon nanocubes as new polysulfides reserviors for lithium--sulfur batteries with long cycle life,” Nano Energy, vol. 16, pp. 268–280, 2015.
D. Li, F. Han, S. Wang et al., “High sulfur loading cathodes fabricated using peapodlike, large pore volume mesoporous carbon for lithium-sulfur battery,” ACS Applied Materials & Interfaces, vol. 5, no. 6, pp. 2208–2213, 2013.
L. Wang, Y. Zhao, M. L. Thomas et al., “In situ synthesis of bipyramidal sulfur with 3d carbon nanotube framework for lithium-sulfur batteries,” Advanced Functional Materials, vol. 24, no. 15, pp. 2248–2252, 2014.
S. Zhao, C. Li, and W. Wang et al., “A novel porous nanocomposite of sulfur/carbon obtained from fish scales for lithium--sulfur batteries,” Journal of Materials Chemistry A, vol. 1, no. 10, p. 3334, 2013.
S. Jiang, Y. Lu, and Y. Lu, “Nafion/titanium dioxide-coated lithium anode for stable lithium--sulfur batteries,” Chemistry—An Asian Journal, vol. 13, no. 10, pp. 1379–1385, 2018.
J. Chen, D. Wu, E. Walter et al., “Molecular-confinement of polysulfides within mesoscale electrodes for the practical application of lithium sulfur batteries,” Nano Energy, vol. 13, pp. 267–274, 2015.
X. B. Cheng, H. J. Peng, J. Q. Huang et al., “Dendrite-free nanostructured anode: entrapment of lithium in a 3D fibrous matrix for ultra-stable lithium-sulfur batteries,” Small, vol. 10, no. 21, pp. 4257–4263, 2014.
H. Zhong, C. Wang, Z. Xu et al., “A novel quasi-solid state electrolyte with highly effective polysulfide diffusion inhibition for lithium-sulfur batteries,” Scientific Reports, vol. 6, p. 25484, 2016.
L. Liang, C. Gao, and G. Chen et al., “Large-area, stretchable, super flexible and mechanically stable thermoelectric films of polymer/carbon nanotube composites,” Journal of Materials Chemistry C, vol. 4, no. 3, pp. 526–532, 2016.
H. Ma, H.-L. Yip, F. Huang et al., “Interface engineering for organic electronics,” Advanced Functional Materials, vol. 20, no. 9, pp. 1371–1388, 2010.
L. Maiolo, A. Pecora, F. Maita et al., “Flexible sensing systems based on polysilicon thin film transistors technology,” Sensors and Actuators B: Chemical, vol. 179, pp. 114–124, 2013.
S. A. Sun, Y. W. Fei, Y. P. Xiao et al., “Preparation of flexible polymer-cement mortar,” Advanced Materials Research, vol. 299–300, pp. 708–711, 2011.
P. Xin, B. Jin, H. Li et al., “Facile synthesis of sulfur-polypyrrole as cathodes for lithium-sulfur batteries,” ChemElectroChem, vol. 4, no. 1, pp. 115–121, 2017.
Y. Zhang, Z. Bakenov, and Y. Zhao et al., “One-step synthesis of branched sulfur/polypyrrole nanocomposite cathode for lithium rechargeable batteries,” Journal of Power Sources, vol. 208, pp. 1–8, 2012.
Y. Fu and A. Manthiram, “Core-shell structured sulfur-polypyrrole composite cathodes for lithium-sulfur batteries,” RSC Advances, vol. 2, no. 14, pp. 5927–5929, 2012.
G. Ma, Z. Wen, and J. Jin et al., “Enhanced performance of lithium sulfur battery with polypyrrole warped mesoporous carbon/sulfur composite,” Journal of Power Sources, vol. 254, pp. 353–359, 2014.
W. Yang, W. Yang, J. Feng et al., “A polypyrrole-coated acetylene black/sulfur composite cathode material for lithium--sulfur batteries,” Journal of Energy Chemistry, vol. 27, no. 3, pp. 813–819, 2018.
X. Liang, M. Zhang, M. R. Kaiser et al., “Split-half-tubular polypyrrole@sulfur@polypyrrole composite with a novel three-layer-3D structure as cathode for lithium/sulfur batteries,” Nano Energy, vol. 11, pp. 587–599, 2015.
L. Zhang, W. Zhu, Y. Zhang et al., “Proteomics analysis of mahonia bealei leaves with induction of alkaloids via combinatorial peptide ligand libraries,” Journal of Proteomics, vol. 110, pp. 59–71, 2014.
Y. Q. Wei, Y. Li, Z. Bakenova et al., “Synthesis and electrochemical performance of polypyrrole-coated sulfur/multi-walled carbon nanotube composite cathode materials for lithium/sulfur batteries,” Materials Science Forum, vol. 847, pp. 33–38, 2016.
C. Wang, W. Wan, and J.-T. Chen et al., “Dual core--shell structured sulfur cathode composite synthesized by a one-pot route for lithium sulfur batteries,” Journal of Materials Chemistry A, vol. 1, no. 5, pp. 1716–1723, 2013.
F. Yin, J. Ren, Y. Zhang et al., “A ppy/ZnO functional interlayer to enhance electrochemical performance of lithium/sulfur batteries,” Nanoscale Research Letters, vol. 13, no. 1, p. 307, 2018.
G. Ma, F. Huang, and Z. Wen et al., “Enhanced performance of lithium sulfur batteries with conductive polymer modified separators,” Journal of Materials Chemistry A, vol. 4, no. 43, pp. 16968–16974, 2016.
F. Li, M. R. Kaiser, J. Ma et al., “Free-standing sulfur-polypyrrole cathode in conjunction with polypyrrole-coated separator for flexible Li-S batteries,” Energy Storage Materials, vol. 13, pp. 312–322, 2018.
F. Wu, W. Li, and L. Guan et al., “A polypyrrole-supported carbon paper acting as a polysulfide trap for lithium--sulfur batteries,” RSC Advances, vol. 5, no. 114, pp. 94479–94485, 2015.
G. Ma, Z. Wen, and Q. Wang et al., “Enhanced performance of lithium sulfur battery with self-assembly polypyrrole nanotube film as the functional interlayer,” Journal of Power Sources, vol. 273, pp. 511–516, 2015.
F. Wu, J. Chen, and R. Chen et al., “Sulfur/polythiophene with a core/shell structure: Synthesis and electrochemical properties of the cathode for rechargeable lithium batteries,” The Journal of Physical Chemistry C, vol. 115, no. 13, pp. 6057–6063, 2011.
F. Wu, S. Wu, and R. Chen et al., “Sulfur--polythiophene composite cathode materials for rechargeable lithium batteries,” Electrochemical and Solid-State Letters, vol. 13, no. 4, p. A29, 2010.
B. Oschmann, J. Park, C. Kim et al., “Copolymerization of polythiophene and sulfur to improve the electrochemical performance in lithium--sulfur batteries,” Chemistry of Materials, vol. 27, no. 20, pp. 7011–7017, 2015.
P. Xiao, F. Bu, and G. Yang et al., “Integration of graphene, nano sulfur, and conducting polymer into compact, flexible lithium-sulfur battery cathodes with ultrahigh volumetric capacity and superior cycling stability for foldable devices,” Advanced Materials, vol. 29, no. 40, p. 1703324–1703331, 2017.
Y. Yang, G. Yu, and J. J. Cha et al., “Improving the Performance of Lithium–Sulfur Batteries by Conductive Polymer Coating,” ACS Nano, vol. 5, no. 11, pp. 9187–9193, 2011.
H. Chen, W. Dong, J. Ge et al., “Ultrafine sulfur nanoparticles in conducting polymer shell as cathode materials for high performance lithium/sulfur batteries,” Scientific Reports, vol. 3, p. 1910, 2013.
S.-c. Zhang, L. Zhang, and W.-k. Wang et al., “A novel cathode material based on polyaniline used for lithium/sulfur secondary battery,” Synthetic Metals, vol. 160, no. 17–18, pp. 2041–2044, 2010.
X. Li, M. Rao, and W. Li, “Sulfur encapsulated in porous carbon nanospheres and coated with conductive polyaniline as cathode of lithium--sulfur battery,” Journal of Solid State Electrochemistry, vol. 20, no. 1, pp. 153–161, 2015.
X. Li, M. Rao, and H. Lin et al., “Sulfur loaded in curved graphene and coated with conductive polyaniline: preparation and performance as a cathode for lithium--sulfur batteries,” Journal of Materials Chemistry A, vol. 3, no. 35, pp. 18098–18104, 2015.
Z.-W. Ding, D.-L. Zhao, R.-R. Yao et al., “Polyaniline@spherical ordered mesoporous carbon/sulfur nanocomposites for high-performance lithium-sulfur batteries,” International Journal of Hydrogen Energy, vol. 43, no. 22, pp. 10502–10510, 2018.
Y. Zou, J. Duan, Z. Qi et al., “Nonfilling polyaniline coating of sulfur/acetylene black for high-performance lithium sulfur batteries,” Journal of Electroanalytical Chemistry, vol. 811, pp. 46–52, 2018.
L. Shi, F. Zeng, X. Cheng et al., “Enhanced performance of lithium-sulfur batteries with high sulfur loading utilizing ion selective MWCNT/SPANI modified separator,” Chemical Engineering Journal, vol. 334, pp. 305–312, 2018.
L. Yin, H. Dou, and A. Wang et al., “A functional interlayer as a polysulfides blocking layer for high-performance lithium--sulfur batteries,” New Journal of Chemistry, vol. 42, no. 2, pp. 1431–1436, 2018.
H. Peng, X. Wang, and Y. Zhao et al., “Enhanced electrochemical performance of sulfur/polyacrylonitrile composite by carbon coating for lithium/sulfur batteries,” Journal of Nanoparticle Research, vol. 19, no. 10, p. 348, 2017.
K. K., R. S., and M. R. et al., “Sulfur/PAN/acetylene black composite prepared by a solution processing technique for lithium-sulfur batteries,” Journal of Applied Polymer Science, vol. 135, no. 34, p. 46598, 2018.
J. Wang, J. Yang, and J. Xie et al., “A novel conductive polymer-sulfur composite cathode material for rechargeable lithium batteries,” Advanced Materials, vol. 14, no. 13–14, pp. 963–965, 2002.
L. Yin, J. Wang, and J. Yang et al., “A novel pyrolyzed polyacrylonitrile-sulfur@MWCNT composite cathode material for high-rate rechargeable lithium/sulfur batteries,” Journal of Materials Chemistry, vol. 21, no. 19, pp. 6807–6810, 2011.
Z.-Q. Jin, Y.-G. Liu, and W.-K. Wang et al., “A new insight into the lithium storage mechanism of sulfurized polyacrylonitrile with no soluble intermediates,” Energy Storage Materials, vol. 14, pp. 272–278, 2018.
Y. Liu, W. Wang, and A. Wang et al., “Effect of vapor pressure on performance of sulfurized polyacrylonitrile cathodes for Li/S batteries,” RSC Advances, vol. 6, no. 108, pp. 106625–106630, 2016.
Y. Zhang, Y. Zhao, and Z. Bakenov et al., “Preparation of novel network nanostructured sulfur composite cathode with enhanced stable cycle performance,” Journal of Power Sources, vol. 270, pp. 326–331, 2014.
Y. Liu, X. Zhao, and G. S. Chauhan et al., “Nanostructured nitrogen-doped mesoporous carbon derived from polyacrylonitrile for advanced lithium sulfur batteries,” Applied Surface Science, vol. 380, pp. 151–158, 2016.
Y. Liu, A. K. Haridas, and K.-K. Cho et al., “Highly ordered mesoporous sulfurized polyacrylonitrile cathode material for high-rate lithium sulfur batteries,” The Journal of Physical Chemistry C, vol. 121, no. 47, pp. 26172–26179, 2017.
Y. Zhang, Y. Zhao, and A. Yermukhambetova et al., “Ternary sulfur/polyacrylonitrile/Mg₀.₆Ni₀.₄O composite cathodes for high performance lithium/sulfur batteries,” Journal of Materials Chemistry A, vol. 1, no. 2, pp. 295–301, 2013.
Y. Li, J. Zhu, and P. Zhu et al., “Glass fiber separator coated by porous carbon nanofiber derived from immiscible PAN/PMMA for high-performance lithium-sulfur batteries,” Journal of Membrane Science, vol. 552, pp. 31–42, 2018.
J. Zhu, C. Chen, and Y. Lu et al., “Highly porous polyacrylonitrile/graphene oxide membrane separator exhibiting excellent anti-self-discharge feature for high-performance lithium--sulfur batteries,” Carbon, vol. 101, pp. 272–280, 2016.
Q. Li, M. Liu, and X. Qin et al., “Cyclized-polyacrylonitrile modified carbon nanofiber interlayers enabling strong trapping of polysulfides in lithium--sulfur batteries,” Journal of Materials Chemistry A, vol. 4, no. 33, pp. 12973–12980, 2016.
Y. Deng, H. Xu, and Z. Bai et al., “Durable polydopamine-coated porous sulfur core--shell cathode for high performance lithium--sulfur batteries,” Journal of Power Sources, vol. 300, pp. 386–394, 2015.
X. Zhang, D. Xie, and Y. Zhong et al., “Performance enhancement of a sulfur/carbon cathode by polydopamine as an efficient shell for high-performance lithium-sulfur batteries,” Chemistry, vol. 23, no. 44, pp. 10610–10615, 2017.
S. Xiao, S. Liu, and J. Zhang et al., “Polyurethane-derived N-doped porous carbon with interconnected sheet-like structure as polysulfide reservoir for lithium--sulfur batteries,” Journal of Power Sources, vol. 293, pp. 119–126, 2015.
Z. Zhang, Z. Zhang, and J. Li et al., “Polydopamine-coated separator for high-performance lithium-sulfur batteries,” Journal of Solid State Electrochemistry, vol. 19, no. 6, pp. 1709–1715, 2015.
S. Song, L. Shi, and S. Lu et al., “A new polysulfide blocker - poly(acrylic acid) modified separator for improved performance of lithium-sulfur battery,” Journal of Membrane Science, vol. 563, pp. 277–283, 2018.
S. Tu, X. Chen, and X. Zhao et al., “A polysulfide-immobilizing polymer retards the shuttling of polysulfide intermediates in lithium-sulfur batteries,” Advanced Materials, p. 1804581–1804588, 2018, doi: 10.1002/adma.201804581.
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