Solvothermal synthesis of three-dimensional petaloid garnet electrolyte and its application in solid polymer electrolytes

doi:10.19799/j.cnki.2095-4239.2021.0058

Abstract

Abstract:

Under the considerations of superior ionic conductivities, excellent stable interphase with lithium metal anode, and low cost, lithium-stuffed garnets have been recognized as one of the most promising solid-state lithium electrolytes. Research on garnets and their composite electrolytes inspired the battery community over the past 10 years. However, the exploration of the unique morphologies of garnet-type electrolytes derived from new synthesis methods has received hardly any attention thus far, although the morphologies of garnet electrolytes are important for their applications in solid polymer electrolytes. Herein, we report a solvothermal method to synthesize a unique nanostructured garnet-type electrolyte, viz. cubic three-dimensional petaloid garnet electrolytes. Uniform aluminum-lanthanum-zirconium glycerate solid spheres are first synthesized as precursors and subsequently chemically transformed into three-dimensional petaloid garnet electrolytes. A composite solid polymer electrolyte containing 10% three-dimensional petaloid garnet exhibits a practically useful conductivity of 5.59 × 10^-5 S·cm^-1 at 25 ℃. For comparison, a composite solid polymer electrolyte containing 10% garnet nanoparticle shows a conductivity of 1.45 × 10^-5 S·cm^-1. This finding provides a strategy to explore superionic conductors.

Key words: solid-state battery, three-dimensional petaloid garnet electrolyte, solvothermal method, solid polymer electrolyte, conductivity

CLC Number:

TQ 02

Yanfang ZHAI, Guanming YANG, Wangshu HOU, Jianyao YAO, Zhaoyin WEN, Shufeng SONG, Ning HU. Solvothermal synthesis of three-dimensional petaloid garnet electrolyte and its application in solid polymer electrolytes[J]. Energy Storage Science and Technology, 2021, 10(3): 905-913.

Figures/Tables 6

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References 35

1	ZHANG X, WANG S, XUE C, et al. Self-suppression of lithium dendrite in all-solid-state lithium metal batteries with poly(vinylidene difluoride)-based solid electrolytes[J]. Advanced Materials, 2019, 31(11): doi: 10.1002/adma.201806082.
2	QUARTARONE E, MUSTARELLI P. Electrolytes for solid-state lithium rechargeable batteries: Recent advances and perspectives[J]. Chemical Society Reviews, 2011, 40(5): 2525-2540.
3	ZHANG Q Q, LIU K, DING F, et al. Recent advances in solid polymer electrolytes for lithium batteries[J]. Nano Research, 2017, 10(12): 4139-4174.
4	WANG H, SHENG L, YASIN G, et al. Reviewing the current status and development of polymer electrolytes for solid-state lithium batteries[J]. Energy Storage Materials, 2020, 33: 188-215.
5	MURUGAN R, THANGADURAI V, WEPPNER W. Fast lithium ion conduction in garnet-type Li₇La₃Zr₂O₁₂[J]. Angewandte Chemie-International Edition, 2007, 46(41): 7778-7781.
6	THANGADURAI V, NARAYANAN S, PINZARU D. Garnet-type solid-state fast Li ion conductors for Li batteries: Critical review[J]. Chemical Society Reviews, 2014, 43(13): 4714-4727.
7	RAMAKUMAR S, DEVIANNAPOORANI C, DHIVYA L, et al. Lithium garnets: Synthesis, structure, Li⁺ conductivity, Li⁺ dynamics and applications[J]. Progress in Materials Science, 2017, 88: 325-411.
8	AWAKA J, KIJIMA N, HAYAKAWA H, et al. Synthesis and structure analysis of tetragonal Li₇La₃Zr₂O₁₂ with the garnet-related type structure[J]. Journal of Solid State Chemistry, 2009, 182(8): 2046-2052.
9	WOLFENSTINE J, RANGASAMY E, ALLEN J L, et al. High conductivity of dense tetragonal Li₇La₃Zr₂O₁₂[J]. Journal of Power Sources, 2012, 208: 193-196.
10	RANGASAMY E, WOLFENSTINE J, SAKAMOTO J. The role of Al and Li concentration on the formation of cubic garnet solid electrolyte of nominal composition Li₇La₃Zr₂O₁₂[J]. Solid State Ionics, 2012, 206: 28-32.
11	LI Y, HAN J T, WANG C A, et al. Optimizing Li⁺ conductivity in a garnet framework[J]. Journal of Materials Chemistry, 2012, 22(30): 15357-15361.
12	SONG S, SHEPTYAKOV D, KORSUNSKY A M, et al. High Li ion conductivity in a garnet-type solid electrolyte via unusual site occupation of the doping Ca ions[J]. Materials & Design, 2016, 93: 232-237.
13	DENG F, WU Y, TANG W, et al. Conformal, nanoscale gamma-Al₂O₃ coating of garnet conductors for solid-state lithium batteries[J]. Solid State Ionics, 2019, 342: doi: 10.1016/j.ssi.2019.115063.
14	SONG S, WU Y, DONG Z, et al. Multi-substituted garnet-type electrolytes for solid-state lithium batteries[J]. Ceramics International, 2020, 46(4): 5489-5494.
15	ZHENG J, DANG H, FENG X, et al. Li-ion transport in a representative ceramic-polymer-plasticizer composite electrolyte: Li₇La₃Zr₂O₁₂-polyethylene oxide-tetraethylene glycol dimethyl ether[J]. Journal of Materials Chemistry A, 2017, 5(35): 18457-18463.
16	FU K K, GONG Y, DAI J, et al. Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries[J]. Proceedings of the National Academy of Sciences of the United States of America, 2016, 113(26): 7094-7099.
17	LI Y, ZHANG W, DOU Q Q, et al. Li₇La₃Zr₂O₁₂ ceramic nanofiber-incorporated composite polymer electrolytes for lithium metal batteries[J]. Journal of Materials Chemistry A, 2019, 7(7): 3391-3398.
18	YANG T, ZHENG J, CHENG Q, et al. Composite polymer electrolytes with Li₇La₃Zr₂O₁₂ garnet-type nanowires as ceramic fillers: Mechanism of conductivity enhancement and role of doping and morphology[J]. ACS Applied Materials & Interfaces, 2017, 9(26): 21773-21780.
19	KOTOBUKI M, KOISHI M. Preparation of Li_1.5Al_0.5Ge_1.5(PO₄)₃ solid electrolytes via the co-precipitation method[J]. Journal of Asian Ceramic Societies, 2019, 7(4): 551-557.
20	ZHAI H, XU P, NING M, et al. A flexible solid composite electrolyte with vertically aligned and connected ion-conducting nanoparticles for lithium batteries[J]. Nano Letters, 2017, 17(5): 3182-3187.
21	LIU K, WU M, JIANG H, et al. An ultrathin, strong, flexible composite solid electrolyte for high-voltage lithium metal batteries[J]. Journal of Materials Chemistry A, 2020, 8(36): 18802-18809.
22	ZHANG X, LIU T, ZHANG S, et al. Synergistic coupling between Li_6.75La₃Zr_1.75Ta_0.25O₁₂ and poly(vinylidene fluoride) induces high ionic conductivity, mechanical strength, and thermal stability of solid composite electrolytes[J]. Journal of the American Chemical Society, 2017, 139(39): 13779-13785.
23	XU D, SU J, JIN J, et al. In situ generated fireproof gel polymer electrolyte with Li_6.4Ga_0.2La₃Zr₂O₁₂ as initiator and ion-conductive filler[J]. Advanced Energy Materials, 2019, 9 (25): doi: 10.1002/aenm.201900611.
24	YANG X, SUN Q, ZHAO C, et al. High-areal-capacity all-solid-state lithium batteries enabled by rational design of fast ion transport channels in vertically-aligned composite polymer electrodes[J]. Nano Energy, 2019, 61: 567-575.
25	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[J]. Advanced Functional Materials, 2019, 29(1): doi: 10.1002/adfm.201805301.
26	CHEN L, LI Y, LI S P, et al. PEO/garnet composite electrolytes for solid-state lithium batteries: From "ceramic-in-polymer" to "polymer-in-ceramic"[J]. Nano Energy, 2018, 46: 176-184.
27	LI W W, SUN C Z, JIN J, et al. Realization of the Li⁺ domain diffusion effect via constructing molecular brushes on the LLZTO surface and its application in all-solid-state lithium batteries[J]. Journal of Materials Chemistry A, 2019, 7(48): 27304-27312.
28	ZHU L, ZHU P, FANG Q, et al. A novel solid PEO/LLTO-nanowires polymer composite electrolyte for solid-state lithium-ion battery[J]. Electrochimica Acta, 2018, 292: 718-726.
29	SONG S, WU Y, TANG W, et al. Composite solid polymer electrolyte with garnet nanosheets in poly(ethylene oxide)[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(7): 7163-7170.
30	WANG X, ZHANG Y, ZHANG X, et al. Lithium-salt-rich PEO/Li_0.3La_0.557TiO₃ interpenetrating composite electrolyte with three-dimensional ceramic nano-backbone for all-solid-state lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2018, 10(29): 24791-24798.
31	SAPTIAMA I, KANETI Y V, SUZUKI Y, et al. Template-free fabrication of mesoporous alumina nanospheres using post-synthesis water-ethanol treatment of monodispersed aluminium glycerate nanospheres for molybdenum adsorption[J]. Small, 2018, 14(21): doi: 10.1002/smll.201800474.
32	MA F X, HU H, WU H B, et al. Formation of uniform Fe₃O₄ hollow spheres organized by ultrathin nanosheets and their excellent lithium storage properties[J]. Advanced Materials, 2015, 27(27): 4097-4101.
33	SEPTIANI N L W, KANETI Y V, FATHONI K B, et al. Self-assembly of nickel phosphate-based nanotubes into two-dimensional crumpled sheet-like architectures for high-performance asymmetric supercapacitors[J]. Nano Energy, 2020, 67: doi: 10.1016/j.nanoen.2019.104270.
34	SHEN L, YU L, WU H B, et al. Formation of nickel cobalt sulfide ball-in-ball hollow spheres with enhanced electrochemical pseudocapacitive properties[J]. Nature Communications, 2015, 6: doi: 10.1038/ncomms7694.
35	LI Z, HUANG H M, ZHU J K, et al. Ionic conduction in composite polymer electrolytes: Case of PEO: Ga-LLZO composites[J]. ACS Applied Materials & Interfaces, 2019, 11(1): 784-791.

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