Preparation and performance of Co2+-doped CeO2-based laminar composite solid-state electrolyte

doi:10.19799/j.cnki.2095-4239.2022.0465

Abstract

Abstract:

Developing thin solid-state electrolytes with high ionic conductivity and mechanical properties is essential for preparing high-performance all-solid-state lithium metal batteries. Here, Co²⁺-doped CeO₂ (Co²⁺@CeO₂) nanosheets were first prepared, which were subsequently mixed with polyethylene oxide (PEO) to fabricate a thickness of only 32 μm Co²⁺@CeO₂-based laminar composite solid-state electrolyte (L-CSE) through vacuum filtration. The oxygen-vacancy-rich Co²⁺@CeO₂ nanosheets are critical to enhancing ionic conductivity and mechanical properties, while PEO acts as a binder to ensure close contact between electrolytes and electrodes and enhance flexibility. The oxygen-vacancy content on the nanosheets was controlled by changing the doping amount of Co. Meanwhile, the structural composition, mechanical properties, and electrochemical properties of L-CSE were systematically studied, emphasizing the influence of oxygen-vacancy content on Li⁺ transport properties. The results show that the oxygen-vacancy content on the nanosheets can be accurately controlled by adjusting the doping amount of Co, and the oxygen-vacancy content of 0.33Co²⁺@CeO₂ nanosheets is the highest. The prepared L-CSE displays a thin thickness (32 μm) and good mechanical properties (the elastic modulus reaches 1.147 GPa). At 30 ℃, the ionic conductivity reaches 5.81×10^-5 S/cm. The Li⁺ transference number is 0.59 at 60 ℃. Concurrently, due to the good interfacial stability between the electrolyte and Li anode, the assembled Li symmetric cell can operate stably for more than 40 h at a high current density of 0.7 mA/cm². Moreover, the assembled LFP/L-CSE/Li solid-state battery exhibited excellent cycling stability and rate performance. It could cycle stably for 200 cycles with a capacity retention rate of 83.6% at 0.5 C and 60 ℃. Meanwhile, the discharge-specific capacity of LFP/L-CSE/Li cells can reach 120.7 mAh/g at 2 C and 60 ℃.

Key words: laminar composite solid-state electrolyte, lithium metal battery, oxygen vacancy, interface, lithium ion conduction

CLC Number:

TM 912

Qingwen GAO, Zhihao YANG, Wenpeng LI, Wenjia WU, Jingtao WANG. Preparation and performance of Co²⁺-doped CeO₂-based laminar composite solid-state electrolyte[J]. Energy Storage Science and Technology, 2022, 11(12): 3776-3786.

Figures/Tables 13

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References 22

1	FERGUS J W. Ceramic and polymeric solid electrolytes for lithium-ion batteries[J]. Journal of Power Sources, 2010, 195(15): 4554-4569.
2	邹文洪, 樊佑, 张焱焱, 等. 安全固态锂电池室温聚合物基电解质的研究进展[J]. 化工进展, 2021, 40(9): 5029-5044.
	ZOU W H, FAN Y, ZHANG Y Y, et al. Research progress on room-temperature polymer-based electrolytes for safe solid-state lithium batteries[J]. Chemical Industry and Engineering Progress, 2021, 40(9): 5029-5044.
3	潘迪, 孔江榕, 刘欣楠, 等. 湿化学法制备石榴石型固态电解质Li₇La₃Zr₂O₁₂[J]. 化工进展, 2021, 40(S2): 334-339.
	PAN D, KONG J R, LIU X N, et al. Preparation Li₇La₃Zr₂O₁₂ garnet solid-state electrolyte by wet-chemical technique[J]. Chemical Industry and Engineering Progress, 2021, 40(S2): 334-339.
4	贺子建, 刘亚飞, 陈彦彬. 无机有机复合固态电解质研究进展[J]. 山东化工, 2020, 49(12): 58-59.
	HE Z J, LIU Y F, CHEN Y B. Research progress of inorganic-organic composite solid electrolyte[J]. Shandong Chemical Industry, 2020, 49(12): 58-59.
5	WANG Y J, PAN Y, KIM D. Conductivity studies on ceramic Li_1.3Al_0.3Ti_1.7(PO₄)₃-filled PEO-based solid composite polymer electrolytes[J]. Journal of Power Sources, 2006, 159(1): 690-701.
6	习磊, 张德超, 刘军. 应用于全固态锂电池的复合固态电解质研究进展[J]. 中国材料进展, 2021, 40(8): 607-617.
	XI L, ZHANG D C, LIU J. Research progress of composite solid electrolytes for all-solid-state lithium batteries[J]. Materials China, 2021, 40(8): 607-617.
7	DING L, LI L B, LIU Y C, et al. Effective ion sieving with Ti₃C₂Tx MXene membranes for production of drinking water from seawater[J]. Nature Sustainability, 2020, 3(4): 296-302.
8	THEBO K H, QIAN X T, ZHANG Q, et al. Highly stable graphene-oxide-based membranes with superior permeability[J]. Nature Communications, 2018, 9: 1486.
9	WU X L, CUI X L, WU W J, et al. Elucidating ultrafast molecular permeation through well-defined 2D nanochannels of lamellar membranes[J]. Angewandte Chemie International Edition, 2019, 58(51): 18524-18529.
10	LIU G Z, SHEN J, LIU Q, et al. Ultrathin two-dimensional MXene membrane for pervaporation desalination[J]. Journal of Membrane Science, 2018, 548: 548-558.
11	ZHAI P F, PENG N, SUN Z Y, et al. Thin laminar composite solid electrolyte with high ionic conductivity and mechanical strength towards advanced all-solid-state lithium-sulfur battery[J]. Journal of Materials Chemistry A, 2020, 8(44): 23344-23353.
12	JIANG S H, ZHANG R Y, LIU H X, et al. Promoting formation of oxygen vacancies in two-dimensional cobalt-doped ceria nanosheets for efficient hydrogen evolution[J]. Journal of the American Chemical Society, 2020, 142(14): 6461-6466.
13	DESHPANDE S, PATIL S, KUCHIBHATLA S V, et al. Size dependency variation in lattice parameter and valency states in nanocrystalline cerium oxide[J]. Applied Physics Letters, 2005, 87(13): doi: 10.1063/1.2061873.
14	CHEN S Q, LI L P, HU W B, et al. Anchoring high-concentration oxygen vacancies at interfaces of CeO_2- x/Cu toward enhanced activity for preferential CO oxidation[J]. ACS Applied Materials & Interfaces, 2015, 7(41): 22999-23007.
15	AO X, WANG X T, TAN J W, et al. Nanocomposite with fast Li⁺ conducting percolation network: Solid polymer electrolyte with Li⁺ non-conducting filler[J]. Nano Energy, 2021, 79: doi:10.1016/j.nanoen.2020.105475.
16	CHEN H, ADEKOYA D, HENCZ L, et al. Stable seamless interfaces and rapid ionic conductivity of Ca-CeO₂/LiTFSI/PEO composite electrolyte for high-rate and high-voltage all-solid-state battery[J]. Advanced Energy Materials, 2020, 10(21): doi: 10.1002/aenm.202000049.
17	LI W W, ZHANG S P, WANG B R, et al. Nanoporous adsorption effect on alteration of the Li⁺ diffusion pathway by a highly ordered porous electrolyte additive for high-rate all-solid-state lithium metal batteries[J]. ACS Applied Materials & Interfaces, 2018, 10(28): 23874-23882.
18	SHENG O W, JIN C B, LUO J M, et al. Mg₂B₂O₅ nanowire enabled multifunctional solid-state electrolytes with high ionic conductivity, excellent mechanical properties, and flame-retardant performance[J]. Nano Letters, 2018, 18(5): 3104-3112.
19	WENG Y T, LIU H W, PEI A, et al. An ultrathin ionomer interphase for high efficiency lithium anode in carbonate based electrolyte[J]. Nature Communications, 2019, 10: 5824.
20	SHIM J, KIM H J, KIM B G, et al. 2D boron nitride nanoflakes as a multifunctional additive in gel polymer electrolytes for safe, long cycle life and high rate lithium metal batteries[J]. Energy & Environmental Science, 2017, 10(9): 1911-1916.
21	WAN J, XIE J, MACKANIC D G, et al. Status, promises, and challenges of nanocomposite solid-state electrolytes for safe and high performance lithium batteries[J]. Materials Today Nano, 2018, 4: 1-16.
22	LU Y, ZHAO C Z, YUAN H, et al. Critical current density in solid-state lithium metal batteries: Mechanism, influences, and strategies[J]. Advanced Functional Materials, 2021, 31(18): doi: 10.1002/adfm.202009925.

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Preparation and performance of Co²⁺-doped CeO₂-based laminar composite solid-state electrolyte

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