Fast Ion Conductor Nanofibers and Aramid Nanofibers with Hydrogen Bonds Synergistically Enhanced Composite Solid Electrolytes

Abstract

The low ionic conductivities, poor high-voltage stabilities, and lithium dendrite formation of polymer solid electrolytes preclude their use in all-solid-state lithium metal batteries (ASSLMBs). This work provides a simple and scalable technique for constructing fast ion conductor nanofibers (FICNFs) and poly-m-phenyleneisophthalamide (PMIA) nanofibers synergistically enhanced polyethylene oxide (PEO)-based composite solid electrolytes (CSEs) for ASSLMBs. The FICNFs, which were mainly composed of high loadings of ZrO₂ or Li_6.4La₃Zr_1.4Ta_0.6O₁₂ nanoparticles, had a percolated ceramic phase inside the nanofibers, while the exposed nanoparticles formed continuous organic–inorganic interfaces with the PEO matrix to enable Li⁺ transport. The interfacial transport rate between ZrO₂ and PEO was calculated as 4.78 × 10^–5 cm² s⁻¹ with ab initio molecular dynamics (AIMD) simulations. Besides, the PMIA nanofibers provided strong skeletal support for the CSEs, ensuring excellent mechanical strength and safety for thin CSEs even at high temperatures. More importantly, the amide groups in PMIA provided abundant hydrogen bonds with TFSI⁻, which lowered the lowest unoccupied molecular orbital (LUMO) level of lithium salts, thus promoting the generation of lithium fluoride-rich solid electrolyte interphase. Consequently, the modified CSEs exhibited satisfactory ionic conductivities (5.38 × 10^–4 S cm⁻¹ at 50 °C) and notable Li dendrite suppression (> 1500 h at 0.3 mAh cm⁻²). The assembled LiFePO₄||Li full cells display ultra-long cycles (> 2000 cycles) at 50 °C and 40 °C. More strikingly, the LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811)||Li cell also can stably run for 500 cycles, and the LiFePO₄||Li flexible pouch cells also cycled normally, demonstrating tremendous potential for practical application.

Keywords

Composite solid electrolytes / Multiple continuous Li⁺ transmission channels / Rich hydrogen bond interactions / Ultra-long stable cycle performance / Flexible pouch cells

References

[1] Cheng X-B, Zhao C-Z, Yao Y-X, Liu H, Zhang Q. Recent advances in energy chemistry between solid-state electrolyte and safe lithium-metal anodes. Chem, 2019, 5: 74-96,

[2] Zhou L, Tufail MK, Liao Y, Ahmad N, Yu P, Song T, Chen R, Yang W. Tailored carrier transport path by interpenetrating networks in cathode composite for high performance all-solid-state Li–SeS₂ batteries. Adv Fiber Mater, 2022, 4: 487-502,

[3] Wang Z, Shen L, Deng S, Cui P, Yao X. 10 μm-thick high-strength solid polymer electrolytes with excellent interface compatibility for flexible all-solid-state lithium-metal batteries. Adv Mater, 2021, 33: 2100353,

[4] Zhao W, Yi J, He P, Zhou H. Solid-state electrolytes for lithium-ion batteries: fundamentals, challenges and perspectives. Electrochem Energy Rev, 2019, 2: 574-605,

[5] Zhang Z, Huang Y, Gao H, Hang J, Li C, Liu P. MOF-derived ionic conductor enhancing polymer electrolytes with superior electrochemical performances for all solid lithium metal batteries. J Membr Sci, 2020, 598,

[6] Culver SP, Koerver R, Krauskopf T, Zeier WG. Designing ionic conductors: the interplay between structural phenomena and interfaces in thiophosphate-based solid-state batteries. Chem Mater, 2018, 30: 4179-4192,

[7] Guo Q, Xu F, Shen L, Deng S, Wang Z, Li M, Yao X. 20 μm-Thick Li_6.4La₃Zr_1.4Ta_0.6O₁₂-based flexible solid electrolytes for all-solid-state lithium batteries. Energy Mater Adv, 2022,

[8] Famprikis T, Canepa P, Dawson JA, Islam MS, Masquelier C. Fundamentals of inorganic solid-state electrolytes for batteries. Nat Mater, 2019, 18: 1278-1291,

[9] Kato Y, Hori S, Saito T, Suzuki K, Hirayama M, Mitsui A, Yonemura M, Iba H, Kanno R. High-power all-solid-state batteries using sulfide superionic conductors. Nat Energy, 2016, 1: 16030,

[10] Li Z, Fu J, Zhou X, Gui S, Wei L, Yang H, Li H, Guo X. Ionic conduction in polymer-based solid electrolytes. Adv Sci, 2023, 10: 2201718,

[11] Xu F, Deng S, Guo Q, Zhou D, Yao X. Quasi-ionic liquid enabling single-phase poly(vinylidene fluoride)-based polymer electrolytes for solid-state LiNi_0.6Co_0.2Mn_0.2O₂||Li batteries with rigid-flexible coupling interphase. Small Methods, 2021, 5: 2100262,

[12] Ju J, Wang Y, Chen B, Ma J, Dong S, Chai J, Qu H, Cui L, Wu X, Cui G. Integrated interface strategy toward room temperature solid-state lithium batteries. ACS Appl Mater Interfaces, 2018, 10: 13588-13597,

[13] Li C, Huang Y, Feng X, Zhang Z, Liu P. High electrochemical performance poly(ethylene oxide)/2,4-toluene diisocyante/polyethylene glycol as electrolytes for all-solid-state lithium batteries. J Membr Sci, 2019, 587,

[14] Guo Q, Xu F, Shen L, Wang Z, Wang J, He H, Yao X. Poly(ethylene glycol) brush on Li_6.4La₃Zr_1.4Ta_0.6O₁₂ towards intimate interfacial compatibility in composite polymer electrolyte for flexible all-solid-state lithium metal batteries. J Power Sources, 2021, 498,

[15] Roman HE, Bunde A, Dieterich W. Conductivity of dispersed ionic conductors: a percolation model with two critical points. PhRvB, 1986, 34: 3439-3445

[16] Li Z, Huang H-M, Zhu J-K, Wu J-F, Yang H, Wei L, Guo X. Ionic conduction in composite polymer electrolytes: Case of PEO:Ga-LLZO composites. ACS Appl Mater Interfaces, 2019, 11: 784-791,

[17] Zheng J, Hu Y-Y. New insights into the compositional dependence of li-ion transport in polymer-ceramic composite electrolytes. ACS Appl Mater Interfaces, 2018, 10: 4113-4120,

[18] Hu C, Shen Y, Shen M, Liu X, Chen H, Liu C, Kang T, Jin F, Li L, Li J, Li Y, Zhao N, Guo X, Lu W, Hu B, Chen L. Superionic conductors via bulk interfacial conduction. J Am Chem Soc, 2020, 142: 18035-18041,

[19] Wang J, Yang J, Shen L, Guo Q, He H, Yao X. Synergistic effects of plasticizer and 3D framework toward high-performance solid polymer electrolyte for room-temperature solid-state lithium batteries. ACS Appl Energy Mater, 2021, 4: 4129-4137,

[20] Zhang Z, Zhang Q, Ren C, Luo F, Ma Q, Hu Y-S, Zhou Z, Li H, Huang X, Chen L. A ceramic/polymer composite solid electrolyte for sodium batteries. J Mater Chem A, 2016, 4: 15823-15828,

[21] Li Q, Sun X, Cao D, Wang Y, Luan P, Zhu H. Versatile electrospinning for structural designs and ionic conductor orientation in all-solid-state lithium batteries. Electrochem Energy Rev, 2022, 5: 18,

[22] Cheng H, Yan C, Orenstein R, Dirican M, Wei S, Subjalearndee N, Zhang X. Polyacrylonitrile nanofiber-reinforced flexible single-ion conducting polymer electrolyte for high-performance, room-temperature all-solid-state Li-metal batteries. Adv Fiber Mater, 2022, 4: 532-546,

[23] Wang Y, Wu L, Lin Z, Tang M, Ding P, Guo X, Zhang Z, Liu S, Wang B, Yin X, Chen Z, Amine K, Yu H. Hydrogen bonds enhanced composite polymer electrolyte for high-voltage cathode of solid-state lithium battery. Nano Energy, 2022, 96,

[24] Zhang D, Liu Z, Wu Y, Ji S, Yuan Z, Liu J, Zhu M. In Situ Construction a stable protective layer in polymer electrolyte for ultralong lifespan solid-state lithium metal batteries. Adv Sci (Weinh), 2022, 9,

[25] Park G, Lee K, Yoo D-J, Choi JW. Strategy for stable interface in lithium metal batteries: free solvent derived vs anion derived. ACS Energy Lett, 2022, 7: 4274-4281,

[26] Tang S, Guo W, Fu Y. Advances in composite polymer electrolytes for lithium batteries and beyond. Adv Energy Mater, 2021, 11: 2000802,

[27] Li S, Zhang S-Q, Shen L, Liu Q, Ma J-B, Lv W, He Y-B, Yang Q-H. Progress and perspective of ceramic/polymer composite solid electrolytes for lithium batteries. Adv Sci, 2020, 7: 1903088,

[28] Miao X, Guan S, Ma C, Li L, Nan C-W. Role of interfaces in solid-state batteries. Adv Mater, 2023, 35: 2206402,

[29] Da X, Chen J, Qin Y, Zhao J, Jia X, Zhao Y, Deng X, Li Y, Gao N, Su Y, Rong Q, Kong X, Xiong J, Hu X, Ding S, Gao G. CO2-Assisted induced self-assembled aramid nanofiber aerogel composite solid polymer electrolyte for all-solid-state lithium-metal batteries. Adv Energy Mater, 2024,

[30] Liu W, Liu N, Sun J, Hsu P-C, Li Y, Lee H-W, Cui Y. Ionic conductivity enhancement of polymer electrolytes with ceramic nanowire fillers. Nano Lett, 2015, 15: 2740-2745,

[31] Cai X, Ding J, Chi Z, Wang W, Wang D, Wang G. Rearrangement of ion transport path on nano-cross-linker for all-solid-state electrolyte with high room temperature ionic conductivity. ACS Nano, 2021, 15: 20489-20503,

[32] Liu L, Lyu J, Mo J, Yan H, Xu L, Peng P, Li J, Jiang B, Chu L, Li M. Comprehensively-upgraded polymer electrolytes by multifunctional aramid nanofibers for stable all-solid-state Li-ion batteries. Nano Energy, 2020, 69,

[33] Gao L, Liang H, Li J, Cheng B, Deng N, Kang W. The high-strength and ultra-thin composite electrolyte using one-step electrospinning/electrostatic spraying process for interface control in all-solid-state lithium metal battery. J Power Sources, 2021, 515,

[34] Yue L, Ma J, Zhang J, Zhao J, Dong S, Liu Z, Cui G, Chen L. All solid-state polymer electrolytes for high-performance lithium ion batteries. Energy Storage Mater, 2016, 5: 139-164,

[35] Li Z, Wang S, Shi J, Liu Y, Zheng S, Zou H, Chen Y, Kuang W, Ding K, Chen L, Lan Y-q, Cai Y-p, Zheng Q. A 3D interconnected metal-organic framework-derived solid-state electrolyte for dendrite-free lithium metal battery. Energy Storage Mater, 2022, 47: 262-270,

[36] Li J, Zhang X, Lu Y, Linghu K, Wang C, Ma Z, He X. Electrospun fluorinated polyimide/polyvinylidene fluoride composite membranes with high thermal stability for lithium ion battery separator. Adv Fiber Mater, 2021, 4: 108-118,

[37] He A, Xing T, Liang Z, Luo Y, Zhang Y, Wang M, Huang Z, Bai J, Wu L, Shi Z, Zuo H, Zhang W, Chen F, Xu W. Advanced aramid fibrous materials: fundamentals, advances, and beyond. Adv Fiber Mater, 2023,

[38] Liu K, Zhang R, Sun J, Wu M, Zhao T. Polyoxyethylene (PEO)|PEO–Perovskite|PEO composite electrolyte for all-solid-state lithium metal batteries. ACS Appl Mater Interfaces, 2019, 11: 46930-46937,

[39] Xu R, Xiao Y, Zhang R, Cheng X-B, Zhao C-Z, Zhang X-Q, Yan C, Zhang Q, Huang J-Q. Dual-phase single-ion pathway interfaces for robust lithium metal in working batteries. Adv Mater, 2019, 31: 1808392,

[40] Hu J, Chen K, Yao Z, Li C. Unlocking solid-state conversion batteries reinforced by hierarchical microsphere stacked polymer electrolyte. Sci Bull, 2021, 66: 694-707,

[41] Lei M, Wu X, Liu Y, Chen K, Hu J, Li C. Polymer electrolytes reinforced by 2D fluorinated filler for all-solid-state Li–Fe–F conversion-type lithium metal batteries. Nano Res, 2023, 16: 8469-8477,

[42] Chen H, Adekoya D, Hencz L, Ma J, Chen S, Yan C, Zhao H, Cui G, Zhang S. Stable seamless interfaces and rapid ionic conductivity of Ca–CeO₂/LiTFSI/PEO composite electrolyte for high-rate and high-voltage all-solid-state battery. Adv Energy Mater, 2020, 10: 2000049,

[43] Lin D, Liu W, Liu Y, Lee HR, Hsu P-C, Liu K, Cui Y. High ionic conductivity of composite solid polymer electrolyte via in situ synthesis of monodispersed SiO₂ nanospheres in poly(ethylene oxide). Nano Lett, 2016, 16: 459-465,

[44] Zhang X, Xie J, Shi F, Lin D, Liu Y, Liu W, Pei A, Gong Y, Wang H, Liu K, Xiang Y, Cui Y. Vertically aligned and continuous nanoscale ceramic-polymer interfaces in composite solid polymer electrolytes for enhanced ionic conductivity. Nano Lett, 2018, 18: 3829-3838,

[45] Hatzell KB, Chen XC, Cobb CL, Dasgupta NP, Dixit MB, Marbella LE, McDowell MT, Mukherjee PP, Verma A, Viswanathan V, Westover AS, Zeier WG. Challenges in lithium metal anodes for solid-state batteries. ACS Energy Lett, 2020, 5: 922-934,

[46] Lu Y, Zhao C-Z, Yuan H, Cheng X-B, Huang J-Q, Zhang Q. Critical current density in solid-state lithium metal batteries: mechanism, influences, and strategies. Adv Funct Mater, 2021, 31: 2009925,

[47] Liu Y, Xu X, Kapitanova OO, Evdokimov PV, Song Z, Matic A, Xiong S. Electro-chemo-mechanical modeling of artificial solid electrolyte interphase to enable uniform electrodeposition of lithium metal anodes. Adv Energy Mater, 2022, 12: 2103589,

[48] Xu X, Liu Y, Kapitanova OO, Song Z, Sun J, Xiong S. Electro–chemo–mechanical failure of solid electrolytes induced by growth of internal lithium filaments. Adv Mater, 2022, 34: 2207232,

[49] Zhou X, Zhang B, Huang F, Li F, Ma Z, Liu J. Difunctional MOF for dendrite-free all-solid-state lithium metal batteries by synergistic effect of hydrogen bond and electrostatic interaction. Nano Energy, 2023, 108,

[50] Zhou X, Li C, Zhang B, Huang F, Zhou P, Wang X, Ma Z. Difunctional NH2-modified MOF supporting plentiful ion channels and stable LiF-rich SEI construction via organocatalysis for all-solid-state lithium metal batteries. J Mater Sci Technol, 2023, 136: 140-148,

[51] Zhang X, Su Q, Du G, Xu B, Wang S, Chen Z, Wang L, Huang W, Pang H. Stabilizing solid-state lithium metal batteries through in situ generated Janus-heterarchical LiF-rich SEI in ionic liquid confined 3D MOF/polymer membranes. Angew Chem Int Ed, 2023, 62,

[52] Yan C, Zhu P, Jia H, Du Z, Zhu J, Orenstein R, Cheng H, Wu N, Dirican M, Zhang X. Garnet-rich composite solid electrolytes for dendrite-free, high-rate, solid-state lithium-metal batteries. Energy Storage Mater, 2020, 26: 448-456,

[53] Ma J-l, Meng F-l, Yu Y, Liu D-p, Yan J-m, Zhang Y, Zhang X-b, Jiang Q. Prevention of dendrite growth and volume expansion to give high-performance aprotic bimetallic Li–Na alloy–O2 batteries. Nat Chem, 2019, 11: 64-70,

[54] Zhou W, Wang Z, Pu Y, Li Y, Xin S, Li X, Chen J, Goodenough JB. Double-layer polymer electrolyte for high-voltage all-solid-state rechargeable batteries. Adv Mater, 2019, 31: 1805574,

Funding

National Natural Science Foundation of China(22005216); Tianjin Natural Science Foundation(18JCQNJC02900); National innovation and entrepreneurship training program for college students(202310058007); Tianjin Municipal college students’ innovation and entrepreneurship training program(202310058088); Tianjin Enterprise Science and Technology Commissioner Project(23YDTPJC00490); China Postdoctoral Science Foundation Grant(2023M742135); Key Laboratory of Rare Earths, Chinese Academy of Sciences