Issue

Vol. 16 (2024)

Construction of a High-Performance Composite Solid Electrolyte Through In-Situ Polymerization within a Self-Supported Porous Garnet Framework

https://doi.org/10.1007/s40820-023-01294-0
An‑Giang Nguyen
Department of Materials Science and Engineering, Chonnam National University, 77 Yongbong‑ro, Buk‑gu, Gwangju 61186, South Korea
Min‑Ho Lee
Department of Materials Science and Engineering, Chonnam National University, 77 Yongbong‑ro, Buk‑gu, Gwangju 61186, South Korea
Jaekook Kim
Department of Materials Science and Engineering, Chonnam National University, 77 Yongbong‑ro, Buk‑gu, Gwangju 61186, South Korea
Chan‑Jin Park
Department of Materials Science and Engineering, Chonnam National University, 77 Yongbong‑ro, Buk‑gu, Gwangju 61186, South Korea

Corresponding Author: Chan‑Jin Park

parkcj@jnu.ac.kr

Nano-Micro Letters, Vol. 16 (2024), Article Number: 83

Abstract

Composite solid electrolytes (CSEs) have emerged as promising candidates for safe and high-energy–density solid-state lithium metal batteries (SSLMBs). However, concurrently achieving exceptional ionic conductivity and interface compatibility between the electrolyte and electrode presents a significant challenge in the development of high-performance CSEs for SSLMBs. To overcome these challenges, we present a method involving the in-situ polymerization of a monomer within a self-supported porous Li6.4La3Zr1.4Ta0.6O12 (LLZT) to produce the CSE. The synergy of the continuous conductive LLZT network, well-organized polymer, and their interface can enhance the ionic conductivity of the CSE at room temperature. Furthermore, the in-situ polymerization process can also construct the integration and compatibility of the solid electrolyte–solid electrode interface. The synthesized CSE exhibited a high ionic conductivity of 1.117 mS cm−1, a significant lithium transference number of 0.627, and exhibited electrochemical stability up to 5.06 V vs. Li/Li+ at 30 °C. Moreover, the Li|CSE|LiNi0.8Co0.1Mn0.1O2 cell delivered a discharge capacity of 105.1 mAh g−1 after 400 cycles at 0.5 C and 30 °C, corresponding to a capacity retention of 61%. This methodology could be extended to a variety of ceramic, polymer electrolytes, or battery systems, thereby offering a viable strategy to improve the electrochemical properties of CSEs for high-energy–density SSLMBs.


Highlights:
1 A scalable tape-casting method produces self-supported porous Li6.4La3Zr1.4Ta0.6O12.
2 Combining the in-situ polymerization approach, a composite solid electrolyte with superior electrochemical properties is fabricated.
3 Solid-state Li|CSE|LiNi0.8Co0.1Mn0.1O2 cells show remarkable cyclability and rate capability.
4 LiF-and B-rich interphase layers mitigate interfacial reactions, enhancing solid-state battery performance.

Keywords

Scalable tape-casting method Self-supported porous Li6.4La3Zr1.4Ta0.6O12 Composite solid electrolyte LiF-and B-rich interphase layers
Nguyen, An‑Giang, Min‑Ho Lee, Jaekook Kim, and Chan‑Jin Park. 2024. “Construction of a High-Performance Composite Solid Electrolyte Through In-Situ Polymerization Within a Self-Supported Porous Garnet Framework”. Nano-Micro Letters 16 (January):83. https://doi.org/10.1007/s40820-023-01294-0.
Download Citation
Endnote/Zotero/Mendeley (RIS)
BibTeX
References
  1. Y.L. Gao, Z.H. Pan, J.G. Sun, Z.L. Liu, J. Wang, High-energy batteries: beyond lithium-ion and their long road to commercialisation. Nano-Micro Lett. 14(1), 94 (2022). https://doi.org/10.1007/s40820-022-00844-2
  2. J.J. Xu, Critical review on cathode-electrolyte interphase toward high-voltage cathodes for Li-ion batteries. Nano-Micro Lett. 14(1), 166 (2022). https://doi.org/10.1007/s40820-022-00917-2
  3. J. Janek, W.G. Zeier, Challenges in speeding up solid-state battery development. Nat. Energy 8, 230–240 (2023). https://doi.org/10.1038/s41560-023-01208-9
  4. X. Zhang, Y.A. Yang, Z. Zhou, Towards practical lithium-metal anodes. Chem. Soc. Rev. 49(10), 3040–3071 (2020). https://doi.org/10.1039/c9cs00838a
  5. X.X. Zhu, L.G. Wang, Z.Y. Bai, J. Lu, T.P. Wu, Sulfide-based all-solid-state lithium-sulfur batteries: challenges and perspectives. Nano-Micro Lett. 15(1), 75 (2023). https://doi.org/10.1007/s40820-023-01053-1
  6. D.L. Vu, D. Kim, A.G. Nguyen, C.J. Park, Stabilizing interface of novel 3D-hierarchical porous carbon for high-performance lithium-sulfur batteries. Electrochim. Acta 418, 140369 (2022). https://doi.org/10.1016/j.electacta.2022.140369
  7. A.G. Nguyen, H.T.T. Le, R. Verma, D.L. Vu, C.J. Park, Boosting sodium-ion battery performance using an antimony nanop self-embedded in a 3D nitrogen-doped carbon framework anode. Chem. Eng. J. 429, 132359 (2022). https://doi.org/10.1016/j.cej.2021.132359
  8. R. Verma, A.G. Nguyen, P.N. Didwal, C.E. Moon, J. Kim et al., In-situ synthesis of antimony nanops encapsulated in nitrogen-doped porous carbon framework as high performance anode material for potassium-ion batteries. Chem. Eng. J. 446, 137302 (2022). https://doi.org/10.1016/j.cej.2022.137302
  9. A. Nazir, H.T.T. Le, A.G. Nguyen, J. Kim, C.J. Park, Conductive metal organic framework mediated Sb nanops as high-capacity anodes for rechargeable potassium-ion batteries. Chem. Eng. J. 450, 138408 (2022). https://doi.org/10.1016/j.cej.2022.138408
  10. A.G. Nguyen, R. Verma, P.N. Didwal, C.J. Park, Challenges and design strategies for alloy-based anode materials toward high-performance future-generation potassium-ion batteries. Energy Mater. 3, 300030 (2023). https://doi.org/10.20517/energymater.2023.11
  11. J.B. Gu, Z.T. Liang, J.W. Shi, Y. Yang, Electrochemo-mechanical stresses and their measurements in sulfide-based all-solid-state batteries: a review. Adv. Energy Mater. 13(2), 2203153 (2023). https://doi.org/10.1002/aenm.202203153
  12. S.J. Tan, W.P. Wang, Y.F. Tian, S. Xin, Y.G. Guo, Advanced electrolytes enabling safe and stable rechargeable li-metal batteries: progress and prospects. Adv. Funct. Mater. 31(45), 2105253 (2021). https://doi.org/10.1002/adfm.202105253
  13. S.L. Liu, W.Y. Liu, D.L. Ba, Y.Z. Zhao, Y.H. Ye et al., Filler-integrated composite polymer electrolyte for solid-state lithium batteries. Adv. Mater. 35(2), 2110423 (2023). https://doi.org/10.1002/adma.202110423
  14. A.G. Nguyen, C.J. Park, Insights into tailoring composite solid polymer electrolytes for solid-state lithium batteries. J. Membr. Sci. 675, 121552 (2023). https://doi.org/10.1016/j.memsci.2023.121552
  15. S. Abouali, C.H. Yim, A. Merati, Y. Abu-Lebdeh, V. Thangadurai, Garnet-based solid-state Li batteries: from materials design to battery architecture. ACS Energy Lett. 6(5), 1920–1941 (2021). https://doi.org/10.1021/acsenergylett.1c00401
  16. F. Liang, Y.L. Sun, Y.F. Yuan, J. Huang, M.J. Hou et al., Designing inorganic electrolytes for solid-state Li-ion batteries: a perspectine of LGPS and garnet. Mater. Today 50, 418–441 (2021). https://doi.org/10.1016/j.mattod.2021.03.013
  17. A. Paolella, X. Liu, A. Daali, W.Q. Xu, I. Hwang et al., Enabling high-performance NASICON-based solid-state lithium metal batteries towards practical conditions. Adv. Funct. Mater. 31(30), 2102765 (2021). https://doi.org/10.1002/adfm.202102765
  18. W. Xia, Y. Zhao, F.P. Zhao, K.G. Adair, R. Zhao et al., Antiperovskite electrolytes for solid-state batteries. Chem. Rev. 122(3), 3763–3819 (2022). https://doi.org/10.1021/acs.chemrev.1c00594
  19. C.H. Wang, K. Adair, X.L. Sun, All-solid-state lithium metal batteries with sulfide electrolytes: understanding interfacial ion and electron transport. Acc. Mater. Res. 3(1), 21–32 (2022). https://doi.org/10.1021/accountsmr.1c00137
  20. J.S. Park, C.H. Jo, S.T. Myung, Comprehensive understanding on lithium argyrodite electrolytes for stable and safe all-solid-state lithium batteries. Energy Storage Mater. 61, 102869 (2023). https://doi.org/10.1016/j.ensm.2023.102869
  21. J.W. Liang, E. van der Maas, J. Luo, X.N. Li, N. Chen et al., A series of ternary metal chloride superionic conductors for high-performance all-solid-state lithium batteries. Adv. Energy Mater. 12(21), 2103921 (2022). https://doi.org/10.1002/aenm.202103921
  22. S.H. Wang, X.W. Xu, C. Cui, C. Zeng, J.N. Liang et al., Air sensitivity and degradation evolution of halide solid state electrolytes upon exposure. Adv. Funct. Mater. 32(7), 2108805 (2022). https://doi.org/10.1002/adfm.202108805
  23. P.N. Didwal, R. Verma, A.G. Nguyen, H.V. Ramasamy, G.H. Lee et al., Improving cyclability of all-solid-state batteries via stabilized electrolyte-electrode interface with additive in poly(propylene carbonate) based solid electrolyte. Adv. Sci. 9(13), 2105448 (2022). https://doi.org/10.1002/advs.202105448
  24. B.B. Wei, S. Huang, Y.H. Song, X. Wang, M. Liu et al., A three-in-one C-60-integrated PEO-based solid polymer electrolyte enables superior all-solid-state lithium-sulfur batteries. J. Mater. Chem. A 11(21), 11426–11435 (2023). https://doi.org/10.1039/d3ta01226c
  25. X.Y. Yang, J.X. Liu, N.B. Pei, Z.Q. Chen, R.Y. Li et al., The critical role of fillers in composite polymer electrolytes for lithium battery. Nano-Micro Lett. 15(1), 74 (2023). https://doi.org/10.1007/s40820-023-01051-3
  26. H.M. Liang, L. Wang, A.P. Wang, Y.Z. Song, Y.Z. Wu et al., Tailoring practically accessible polymer/inorganic composite electrolytes for all-solid-state lithium metal batteries: a review. Nano-Micro Lett. 15(1), 42 (2023). https://doi.org/10.1007/s40820-022-00996-1
  27. Y. Su, F. Xu, X. Zhang, Y. Qiu, H. Wang, Rational design of high-performance PEO/ceramic composite solid electrolytes for lithium metal batteries. Nano-Micro Lett. 15(1), 82 (2023). https://doi.org/10.1007/s40820-023-01055-z
  28. Y.A. Xu, K. Wang, X.D. Zhang, Y.B. Ma, Q.F. Peng et al., Improved Li-ion conduction and (electro)chemical stability at garnet-polymer interface through metal-nitrogen bonding. Adv. Energy Mater. 13(14), 2204377 (2023). https://doi.org/10.1002/aenm.202204377
  29. J. Yu, X.D. Lin, J.P. Liu, J.T.T. Yu, M.J. Robson et al., In situ fabricated quasi-solid polymer electrolyte for high-energy-density lithium metal battery capable of subzero operation. Adv. Energy Mater. 12(2), 2102932 (2022). https://doi.org/10.1002/aenm.202102932
  30. Y.T. Wang, J.W. Ju, S.M. Dong, Y.Y. Yan, F. Jiang et al., Facile design of sulfide-based all solid-state lithium metal battery: in situ polymerization within self-supported porous argyrodite skeleton. Adv. Funct. Mater. 31(28), 2101523 (2021). https://doi.org/10.1002/adfm.202101523
  31. A.G. Nguyen, R. Verma, G.C. Song, J. Kim, C.J. Park, In situ polymerization on a 3D ceramic framework of composite solid electrolytes for room-temperature solid-state batteries. Adv. Sci. (2023). https://doi.org/10.1002/advs.202207744
  32. X.Z. Chen, W.J. He, L.X. Ding, S.Q. Wang, H.H. Wang, Enhancing interfacial contact in all solid state batteries with a cathode-supported solid electrolyte membrane framework. Energ. Environ. Sci. 12(3), 938–944 (2019). https://doi.org/10.1039/c8ee02617c
  33. C.K. Fu, Y.L. Ma, S.F. Lou, C. Cui, L.Z. Xiang et al., A dual-salt coupled fluoroethylene carbonate succinonitrile-based electrolyte enables Li-metal batteries. J. Mater. Chem. A 8(4), 2066–2073 (2020). https://doi.org/10.1039/c9ta11341j
  34. C.K. Fu, Y.L. Ma, P.J. Zuo, W. Zhao, W.C. Tang et al., In-situ thermal polymerization boosts succinonitrile-based composite solid-state electrolyte for high performance Li-metal battery. J. Power. Sources 496, 229861 (2021). https://doi.org/10.1016/j.jpowsour.2021.229861
  35. P. Giannozzi, O. Baseggio, P. Bonfa, D. Brunato, R. Car et al., Quantum ESPRESSO toward the exascale. J. Chem. Phys. 152(15), 154105 (2020). https://doi.org/10.1063/5.0005082
  36. P. Giannozzi, S. Baroni, N. Bonini, M. Calandra, R. Car et al., QUANTUM ESPRESSO: a modular and open-source software project for quantum simulations of materials. J. Phys. Condens. Mat. 21(39), 395502 (2009). https://doi.org/10.1088/0953-8984/21/39/395502
  37. P. Giannozzi, O. Andreussi, T. Brumme, O. Bunau, M.B. Nardelli et al., Advanced capabilities for materials modelling with QUANTUM ESPRESSO. J. Phys. Condens. Mat. 29(46), 465901 (2017). https://doi.org/10.1088/1361-648X/aa8f79
  38. K. Momma, F. Izumi, VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data. J. Appl. Crystallogr. 44, 1272–1276 (2011). https://doi.org/10.1107/S0021889811038970
  39. A. Kokalj, XCrySDen-a new program for displaying crystalline structures and electron densities. J. Mol. Graph. Model. 17(3–4), 176–179 (1999). https://doi.org/10.1016/S1093-3263(99)00028-5
  40. S.H. Jiao, X.D. Ren, R.G. Cao, M.H. Engelhard, Y.Z. Liu et al., Stable cycling of high-voltage lithium metal batteries in ether electrolytes. Nat. Energy 3(9), 739–746 (2018). https://doi.org/10.1038/s41560-018-0199-8
  41. K. Ishiguro, H. Nemori, S. Sunahiro, Y. Nakata, R. Sudo et al., Ta-doped Li7La3Zr2O12 for water-stable lithium electrode of lithium-air batteries. J. Electrochem. Soc. 161(5), A668–A674 (2014). https://doi.org/10.1149/2.013405jes
  42. L.Q. Xu, J.Y. Li, W.T. Deng, H.L. Shuai, S. Li et al., Garnet solid electrolyte for advanced all-solid-state Li batteries. Adv. Energy Mater. 11(2), 2000648 (2021). https://doi.org/10.1002/aenm.202000648
  43. B.J. Sung, P.N. Didwal, R. Verma, A.G. Nguyen, D.R. Chang et al., Composite solid electrolyte comprising poly(propylene carbonate) and Li1.5Al0.5Ge1.5(PO4)(3) for long-life all-solid-state Li-ion batteries. Electrochim. Acta 392, 139007 (2021). https://doi.org/10.1016/j.electacta.2021.139007
  44. J.R. Wu, X.S. Wang, Q. Liu, S.W. Wang, D. Zhou et al., A synergistic exploitation to produce high-voltage quasi-solid-state lithium metal batteries. Nat. Commun. 12(1), 5746 (2021). https://doi.org/10.1038/s41467-021-26073-6
  45. H. Fujimoto, S. Satoh, Orbital interactions and chemical hardness. J. Phys. Chem. 98(5), 1436–1441 (1994). https://doi.org/10.1021/j100056a011
  46. T.L. Jiang, P.G. He, G.X. Wang, Y. Shen, C.W. Nan et al., Solvent-free synthesis of thin, flexible, nonflammable garnet-based composite solid electrolyte for all-solid-state lithium batteries. Adv. Energy Mater. 10(12), 1903376 (2020). https://doi.org/10.1002/aenm.201903376
  47. C.S. Bao, C.J. Zheng, M.F. Wu, Y. Zhang, J. Jin et al., 12 mu m-thick sintered garnet ceramic skeleton enabling high-energy-density solid-state lithium metal batteries. Adv. Energy Mater. 13(13), 2204028 (2023). https://doi.org/10.1002/aenm.202204028
  48. Y.Y. Yan, J.W. Ju, S.M. Dong, Y.T. Wang, L. Huang et al., In situ polymerization permeated three-dimensional Li+-percolated porous oxide ceramic framework boosting all solid-state lithium metal battery. Adv. Sci. 8(9), 2003887 (2021). https://doi.org/10.1002/advs.202003887
  49. F. Jiang, Y.T. Wang, J.W. Ju, Q. Zhou, L.F. Cui et al., Percolated sulfide in salt-concentrated polymer matrices extricating high-voltage all-solid-state lithium-metal batteries. Adv. Sci. 9(25), 2202474 (2022). https://doi.org/10.1002/advs.202202474
  50. X.Y. Li, Y. Wang, K. Xi, W. Yu, J. Feng et al., Quasi-solid-state ion-conducting arrays composite electrolytes with fast ion transport vertical-aligned interfaces for all-weather practical lithium-metal batteries. Nano-Micro Lett. 14(1), 210 (2022). https://doi.org/10.1007/s40820-022-00952-z
  51. M. Yao, Q.Q. Ruan, T.H. Yu, H.T. Zhang, S.J. Zhang, Solid polymer electrolyte with in-situ generated fast Li+ conducting network enable high voltage and dendrite-free lithium metal battery. Energy Storage Mater. 44, 93–103 (2022). https://doi.org/10.1016/j.ensm.2021.10.009
  52. X.D. Lin, J. Yu, M.B. Effat, G.D. Zhou, M.J. Robson et al., Ultrathin and non-flammable dual-salt polymer electrolyte for high-energy-density lithium-metal battery. Adv. Funct. Mater. 31(17), 2010261 (2021). https://doi.org/10.1002/adfm.202010261
  53. P.R. Shi, J.B. Ma, M. Liu, S.K. Guo, Y.F. Huang et al., A dielectric electrolyte composite with high lithium-ion conductivity for high-voltage solid-state lithium metal batteries. Nat. Nanotechnol. 18(6), 602 (2023). https://doi.org/10.1038/s41565-023-01341-2
  54. H. Yang, B. Zhang, M.X. Jing, X.Q. Shen, L. Wang et al., In situ catalytic polymerization of a highly homogeneous PDOL composite electrolyte for long-cycle high-voltage solid-state lithium batteries. Adv. Energy Mater. 12(39), 2201762 (2022). https://doi.org/10.1002/aenm.202201762
  55. J. Yu, J.P. Liu, X.D. Lin, H.M. Law, G.D. Zhou et al., A solid-like dual-salt polymer electrolyte for Li-metal batteries capable of stable operation over an extended temperature range. Energy Storage Mater. 37, 609–618 (2021). https://doi.org/10.1016/j.ensm.2021.02.045
Read More
Author biographies are not available.
Download this PDF file
PDF SUPPLEMENTARY FILE
Statistic
Read Counter : 2710 Download : 2004