Jointing of Cathode Coating and Interface Modification for Stabilizing Poly(ethylene oxide) Electrolytes Against High-voltage Cathodes

doi:10.15541/jim20230215

Abstract

Abstract:

Poly(ethylene oxide) (PEO)-based solid electrolytes are deemed as the most promising alternatives for solid-state lithium batteries on account of their low cost, good stability against Li metal, and easy large-scale production. However, the instability of PEO against high-voltage cathodes severely limits its application in the fields needing high energy density. In this work, a discontinuous cyclized polyacrylonitrile (cPAN) nanolayer, served as an electron-conducting shell, is partially coated on LiNi_0.6Co_0.2Mn_0.2O₂ (NCM) cathode particles, while an ionic liquid acted as ion-conducting pathway is introduced at NCM/PEO interface, enabling the high compatibility of PEO against high-voltage NCM cathode. The cPAN layer not only physically isolates the direct contact of PEO electrolyte from NCM cathode, but also contributes to the electronic transfer inside the cathode due to the formation of delocalized sp² π bond during coating process. Meanwhile, the mobile ionic liquid with good ionic conductivity fully wets cathodic interface, followed by decomposition into cathode-electrolyte interphase (CEI) of LiF and Li₃N, further restricting the oxidation-failure of PEO electrolyte. By taking the combined strategy, the corresponding solid-state NCM/Li battery delivers an excellent electrochemical performance with a capacity retention of 85.3% after 100 cycles at rate of 0.1C (1C=0.18 A·g^-1) under a cutoff voltage of 4.30 V. This work opens up a new direction to address the interfacial stability issues of PEO-based electrolyte against high-voltage cathodes through surface coating and interface modification.

Key words: poly(ethylene oxide), cyclization, high-voltage cathode, interface engineering, solid-state lithium battery

CLC Number:

TM911

TAN Shuyu, LIU Xiaoning, BI Zhijie, WAN Yong, GUO Xiangxin. Jointing of Cathode Coating and Interface Modification for Stabilizing Poly(ethylene oxide) Electrolytes Against High-voltage Cathodes[J]. Journal of Inorganic Materials, 2023, 38(12): 1466-1474.

Figures/Tables 14

Fig. 1 (a) Preparation process of NCM@cPAN powder, (b) schematic representation of as-prepared NCM@cPAN particle, and (c) schematic diagram of the solid-state NCM@cPAN+IL/PEO/Li cell

Fig. 2 (a) FT-IR spectra of pristine PAN and PAN treated at 400 ℃, (b) schematic diagrams of pristine PAN and cPAN, and (c) Raman spectra of PAN, cPAN, NCM, and NCM@cPAN

Fig. 3 (a) XRD patterns of NCM, NCM@PAN, and NCM@cPAN powders; SEM images of (b, c) NCM, (d, e) NCM@PAN, and (f, g) NCM@cPAN powders; (h, i) TEM images of NCM@cPAN; (j) EDS mappings of C, N, O, Mn, Co and Ni elements of the region in (f)

Fig. 4 Cycling performance of solid-state NCM@cPAN+IL/PEO/Li batteries Typical charge-discharge curves and the corresponding specific capacities with cutoff voltages of (a, d) 4.20 V, (b, e) 4.25 V, and (c, f) 4.30 V

Fig. 5 (a) Charge-discharge curves, and (b) corresponding specific capacities for solid-state NCM@cPAN+IL/PEO/Li batteries at various current densities; (c) Typical charge-discharge curves and (d) corresponding specific capacities and Coulombic efficiency for solid-state NCM@cPAN+IL/PEO/Li batteries with high cathode loading of ~6.2 mg·cm-2

Fig. 6 (a, c) F1s and (b, d) N1s XPS spectra of PP13-TFSI (a, b) before and (c, d) after cycling; (e) Schematic diagram of TFSI− decomposition during cycling

Fig. 7 (a) FT-IR spectra of PEO electrolyte before and after cycling; SEM images of NCM@cPAN cathodes (b) before and (c) after cycling; (d) Ni2p XPS spectra of NCM@cPAN cathode before and after cycling

Fig. S1 (a) Nyquist plots of PEO-based electrolyte at different temperatures; (b) Arrhenius plot of PEO-based electrolyte

Fig. S2 LSV curve of PEO-based electrolyte

Fig. S3 Charge-discharge curve of NCM/PEO/Li batteries without IdiL at 50 ℃

Fig. S4 Rate performance of solid NCM@cPAN+IL/PEO/Li batteries at various current densities (a, c) Typical charge-discharge curves and (b, d) corresponding specific capacities with the cutoff voltages of (a, b) 4.25 V, and (c, d) 4.30 V

Fig. S5 Charge-discharge curve of NCM@cPAN/PEO/Li batteries without IL at 50 ℃

Fig. S6 Charge-discharge curve of NCM/PEO/Li batteries with IL at 50 ℃

Fig. S7 XRD patterns of PEO electrolytes before and after cycling

References 40

[1]	CHENG X B, ZHANG R, ZHAO C Z, et al. Toward safe lithium metal anode in rechargeable batteries: a review. Chemical Reviews, 2017, 117(15): 10403. DOI URL
[2]	LIU J, BAO Z, CUI Y, et al. Pathways for practical high-energy long-cycling lithium metal batteries. Nature Energy, 2019, 4(3): 180. DOI
[3]	MA G, GUO L, DING X, et al. Effect of dual-functional electrolyte additive on high temperature and high voltage performance of Li-ion battery. Journal of Inorganic Materials, 2022, 37(7): 710. DOI
[4]	XU H, SHI J, HU G, et al. Hybrid electrolytes incorporated with dandelion-like silane-Al₂O₃ nanoparticles for high-safety high- voltage lithium ion batteries. Journal of Power Sources, 2018, 391: 113.
[5]	COMMARIEU B, PAOLELLA A, DAIGLE J C, et al. Toward high lithium conduction in solid polymer and polymer-ceramic batteries. Current Opinion in Electrochemistry, 2018, 9: 56.
[6]	LI Y, MAO J, WEI C, et al. In-situ modification of carbon nanotubes with metallic bismuth nanoparticles for uniform lithium deposition. Journal of Inorganic Materials, 2022, 37(12): 1337. DOI URL
[7]	WANG J, GE B, LI H, et al. Challenges and progresses of lithium-metal batteries. Chemical Engineering Journal, 2021, 420: 129739.
[8]	ZHANG H, DAI R, ZHU S, et al. Bimetallic nitride modified separator constructs internal electric field for high-performance lithium-sulfur battery. Chemical Engineering Journal, 2022, 429: 132454.
[9]	WEN Z, LIANG F. MOF/poly(ethylene oxide) composite polymer electrolyte for solid-state lithium battery. Journal of Inorganic Materials, 2021, 36(3): 332. DOI
[10]	FAN L, WEI S, LI S, et al. Recent progress of the solid-state electrolytes for high-energy metal-based batteries. Advanced Energy Materials, 2018, 8(11): 1702657. DOI URL
[11]	LIN D, YUEN P Y, LIU Y, et al. A silica-aerogel-reinforced composite polymer electrolyte with high ionic conductivity and high modulus. Advanced Materials, 2018, 30(32): 1802661. DOI URL
[12]	ZHAO Y, ZHENG K, SUN X. Addressing interfacial issues in liquid-based and solid-state batteries by atomic and molecular layer deposition. Joule, 2018, 2(12): 2583. DOI URL
[13]	WU J, RAO Z, CHENG Z, et al. Ultrathin, flexible polymer electrolyte for cost-effective fabrication of all-solid-state lithium metal batteries. Advanced Energy Materials, 2019, 9(46): 1902767. DOI URL
[14]	CHEN R, LI Q, YU X, et al. Approaching practically accessible solid-state batteries: stability issues related to solid electrolytes and interfaces. Chemical Reviews, 2020, 120(14): 6820. DOI PMID
[15]	WAN Z, LEI D, YANG W, et al. Low resistance-integrated all- solid-state battery achieved by Li₇La₃Zr₂O₁₂ nanowire upgrading polyethylene oxide (PEO) composite electrolyte and PEO cathode binder. Advanced Functional Materials, 2019, 29(1): 1805301. DOI URL
[16]	BALAISH M, GONZALEZ-ROSILLO J C, KIM K J, et al. Processing thin but robust electrolytes for solid-state batteries. Nature Energy, 2021, 6(3): 227. DOI
[17]	LIU X Y, LIU B D, JIANG Y N, et al. In-situ synthesis of perovskite SrTiO₃ nanostructures with modified morphology and tunable optical absorption property. Journal of Inorganic Materials, 2019, 34(1): 65. DOI URL
[18]	NIE K, WANG X, QIU J, et al. Increasing poly(ethylene oxide) stability to 4.5 V by surface coating of the cathode. ACS Energy Letters, 2020, 5(3): 826. DOI URL
[19]	HUO H, CHEN Y, LUO J, et al. Rational design of hierarchical “ceramic-in-polymer” and “polymer-in-ceramic” electrolytes for dendrite-free solid-state batteries. Advanced Energy Materials, 2019, 9(17): 1804004. DOI URL
[20]	YANG X, JIANG M, GAO X, et al. Determining the limiting factor of the electrochemical stability window for PEO-based solid polymer electrolytes: main chain or terminal -OH group? Energy & Environmental Science, 2020, 13(5): 1318.
[21]	YANG Q, HUANG J, LI Y, et al. Surface-protected LiCoO₂ with ultrathin solid oxide electrolyte film for high-voltage lithium ion batteries and lithium polymer batteries. Journal of Power Sources, 2018, 388: 65.
[22]	LIANG J, SUN Y, ZHAO Y, et al. Engineering the conductive carbon/PEO interface to stabilize solid polymer electrolytes for all-solid-state high voltage LiCoO₂ batteries. Journal of Materials Chemistry A, 2020, 8(5): 2769. DOI URL
[23]	XU H, CHIEN P H, SHI J, et al. High-performance all-solid-state batteries enabled by salt bonding to perovskite in poly(ethylene oxide). Proceedings of the National Academy of Sciences of the United States of America, 2019, 116(38): 18815. DOI PMID
[24]	WANG Y, LIU B N, ZHOU G, et al. Improved electrochemical performance of Li(Ni_0.6Co_0.2Mn_0.2)O₂ at high charging cut-off voltage with Li_1.4Al_0.4Ti_1.6(PO₄)₃ surface coating. Chinese Physics B, 2019, 28(6): 068202. DOI
[25]	QIU J, YANG L, SUN G, et al. A stabilized PEO-based solid electrolyte via a facile interfacial engineering method for a high voltage solid-state lithium metal battery. Chemical Communications, 2020, 56(42): 5633. DOI URL
[26]	FENG W, LI J, LIU H, et al. In-situ modification of ultrathin and uniform layer on LiCoO₂ particles for 4.2 V polyethylene oxide based solid-state lithium batteries with excellent cycle performance. Electrochimica Acta, 2022, 421: 140473.
[27]	LI Z, LI A, ZHANG H, et al. Interfacial engineering for stabilizing polymer electrolytes with 4 V cathodes in lithium metal batteries at elevated temperature. Nano Energy, 2020, 72: 104655.
[28]	FU F, ZHENG Y, JIANG N, et al. A dual-salt PEO-based polymer electrolyte with cross-linked polymer network for high-voltage lithium metal batteries. Chemical Engineering Journal, 2022, 450: 137776.
[29]	ZHOU W, WANG Z, PU Y, et al. Double-layer polymer electrolyte for high-voltage all-solid-state rechargeable batteries. Advanced Materials, 2019, 31(4): 1805574. DOI URL
[30]	SUN Y, DONG H, XU Y, et al. Incorporating cyclized- polyacrylonitrile with Li₄Ti₅O₁₂ nanosheet for high performance lithium ion battery anode material. Electrochimica Acta, 2017, 246: 106.
[31]	SUN X L, LIU Z, CHENG Z L. Design and fabrication of in-situ N-doped paper-like carbon nanofiber film for thiophene removal from a liquid model fuel. Journal of Hazardous Materials, 2020, 389: 121879.
[32]	HONG Y, HU Q, DONG H, et al. N-doped carbon coated porous hierarchical MnO microspheres as superior additive-free anode materials for lithium-ion batteries. Scripta Materialia, 2022, 211: 114495.
[33]	HAMEDANI A A, OW-YANG C W, HAYAT SOYTAS S. Silicon nanocrystals-embedded carbon nanofibers from hybrid polyacrylonitrile-TEOS precursor as high-performance lithium-ion battery anodes. Journal of Alloys and Compounds, 2022, 909: 164734.
[34]	FENG W, LIU H, ZHAO M, et al. Improving interfacial stability by in situ protective layer formation in 4.2 V poly(ethylene oxide) based solid state lithium batteries. Journal of Power Sources, 2022, 523: 231062.
[35]	XIE Z, WU Z, AN X, et al. 2-Fluoropyridine: a novel electrolyte additive for lithium metal batteries with high areal capacity as well as high cycling stability. Chemical Engineering Journal, 2020, 393: 124789.
[36]	CHEN K, SUN Y, ZHAO C, et al. A semi-interpenetrating network polymer electrolyte membrane prepared from non-self- polymerized precursors for ambient temperature all-solid-state lithium-ion batteries. Journal of Solid State Chemistry, 2021, 296: 121958.
[37]	YAN C, YAO Y X, CHEN X, et al. Lithium nitrate solvation chemistry in carbonate electrolyte sustains high-voltage lithium metal batteries. Angewandte Chemie International Edition, 2018, 57(43): 14055. DOI URL
[38]	LI T, ZHANG X Q, SHI P, et al. Fluorinated solid-electrolyte interphase in high-voltage lithium metal batteries. Joule, 2019, 3(11): 2647. DOI URL
[39]	POLU A R, RHEE H W. Ionic liquid doped PEO-based solid polymer electrolytes for lithium-ion polymer batteries. International Journal of Hydrogen Energy, 2017, 42(10): 7212. DOI URL
[40]	SONG G, ZHONG H, WANG Z, et al. Interfacial film Li_1.3Al_0.3Ti_1.7PO₄-coated LiNi_0.6Co_0.2Mn_0.2O₂ for the long cycle stability of lithium-ion batteries. ACS Applied Energy Materials, 2019, 2(11): 7923. DOI URL