In-situ Polymerization Integrating 3D Ceramic Framework in All Solid-state Lithium Battery

doi:10.15541/jim20200152

Abstract

Abstract:

Organic/inorganic composites have been considered as promising electrolyte candidates in all solid-state lithium batteries. Aiming at improving the conductivity significantly by increasing the frequently-used 0D or 1D ceramic nano-fillers to high content is unsuccessful due to the particle tendency to agglomeration. What's worse, the loose contact between the solid electrolyte and solid electrodes is much of a serious barrier to the performance and thus to the application of all solid-state lithium batteries. Herein, self-supported 3D porous Li_6.4Al_0.1La₃Zr_1.7Ta_0.3O₁₂ frameworks are employed to provide percolated fast Li⁺ conductive pathway while in-situ polymerization of poly(ethylene glycol) methyl ether acrylate can integrate the loose solid-solid interface and reduce the interfacial resistance efficiently. Inspiringly, the Li⁺ conductivity of the composite exhibits 1.9×10^-4 S·cm^-1 at room temperature. The interfacial resistance in Li-Li batteries decreases significantly from 1540 to 449 Ω·cm ², rendering good capacity and cyclability of the 4.3 V (vs. Li⁺/Li) LiCoO₂|Li all solid-state lithium battery.

Key words: solid composite electrolyte, in-situ polymerization, porous framework, all solid-state battery

CLC Number:

TQ174

YAN Yiyuan, JU Jiangwei, YU Meiyan, CHEN Shougang, CUI Guanglei. In-situ Polymerization Integrating 3D Ceramic Framework in All Solid-state Lithium Battery[J]. Journal of Inorganic Materials, 2020, 35(12): 1357-1364.

Figures/Tables 8

Fig. 1 Schematic illustration of ASLB structure prepared via (a) ex-situ and (b) in-situ methods with p-LLZTO as ceramic fillers

Fig. 2 (a) XRD patterns of standard LLZO, the as-prepared LLZTO powders and p-LLZTO; (b) Cross sectional SEM image of p-LLZTO; (c) Pore size distribution of p-LLZTO; (d) EIS plots of dense LLZTO and p-LLZTO at room temperature with inset showing the partial magnified spectrum of the dense LLZTO

Fig. 3 (a) FT-IR spectra of PEGMEA, P(PEGMEA), and P(PEGMEA) from the 3D composite; (b) 1H NMR spectra of PEGMEA and P(PEGMEA) from the 3D composite(the solvents are deuterated N,N-dimethylformamide) with insets showing the corresponding structural formula of PEGMEA and P(PEGMEA); (c) Thermal evolution of ohmic resistance at 60 ℃ for steel|3D composite|steel symmetrical cell with inset showing the digital image of PEGMEA with/without p-LLZTO after heat-treatment at 60 ℃ for 24 h; (d) Relation between ionic conductivity of electrolyte and temperature for P(PEGMEA) and 3D composite; (e) Cross sectional SEM image and element mapping analysis of the 3D composite

Table 1 Conductivities $(\sigma_{Li^+})$ of different solid electrolytes at room temperature

Electrolyte	Lithium salt	EO^a : Li⁺	Conductivity of polymer/(S·cm^-1)	Conductivity of composite/(S·cm^-1)	Promotion factor	Ref.
PEO/LATP particles	LiClO₄	15 : 1	1.3×10^-6	9.5×10^-6	7.5	[25]
PEO/LLZO fibers	LiTFSI^b	-	2.5×10^-6	2.7×10^-5	11	[26]
PEO/LATP^c fibers	LiTFSI	8 : 1	3.2×10^-6	4.9×10^-5	15	[27]
PEO/3D LLZO	LiTFSI	10 : 1	1.8×10^-6	8.5×10^-5	47	[19]
PEO/3D LLTO^d	LiTFSI	10 : 1	2.2×10^-6	8.8×10^-5	40	[18]

Fig. S1 Linear sweep voltammetry measurement for 3D composite at room temperature

Fig. S2 Current variation with time during polarization of (a) Li|P(PEGMEA)|Li and (b) Li|3D composite|Li symmetrical cell at room temperature

Fig. 4 EIS plots of (a-c) pre- and (d-f) post-treated Li-Li symmetrical batteries based on (a, d) PEGMEA, (b, e) LLZTO, (c, f) 3D composites; (g) Ohmic and (h) interfacial resistance comparison of pre- and post-treated Li-Li symmetrical cells; (i) DC galvanostatic cycle of Li-Li symmetrical batteries based on P(PEGMEA) and the 3D composite under room temperature at 0.1 mA·cm-2 with insets showing D.C. galvanostatic cycle of Li-Li symmetrical battery based on LLZTO(up) and the magnified profile of Li|3D composite|Li(down)

References 34

[1]	GAO Z, SUN H, FU L, et al. Promises, challenges, and recent progress of inorganic solid-state electrolytes for all-solid-state lithium batteries. Advanced Materials, 2018,30(17):e1705702. DOI URL PMID
[2]	BACHMAN J C, MUY S, GRIMAUD A, et al. Inorganic solid-state electrolytes for lithium batteries: mechanisms and properties governing ion conduction. Chemical Reviews, 2016,116(1):140-162. DOI URL PMID
[3]	ZHENG F, KOTOBUKI M, SONG S, et al. Review on solid electrolytes for all-solid-state lithium-ion batteries. Journal of Power Sources, 2018,389:198-213.
[4]	ZHANG B, TAN R, YANG L, et al. Mechanisms and properties of ion-transport in inorganic solid electrolytes. Energy Storage Materials, 2018,10:139-159.
[5]	CHEN R, QU W, GUO X, et al. The pursuit of solid-state electrolytes for lithium batteries: from comprehensive insight to emerging horizons. Materials Horizons, 2016,3(6):487-516.
[6]	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.
[7]	YUE L, MA J, ZHANG J, et al. All solid-state polymer electrolytes for high-performance lithium ion batteries. Energy Storage Materials, 2016,5:139-164.
[8]	MANTHIRAM A, YU X, WANG S. Lithium battery chemistries enabled by solid-state electrolytes. Nature Reviews Materials, 2017,2(4):16103
[9]	GAO Y, WANG D, LI Y C, et al. Salt-based organic-inorganic nanocomposites: towards a stable lithium metal/Li₁₀GeP₂S₁₂ solid electrolyte interface. Angew. Chem. Int. Ed., 2018,57(41):13608-13612.
[10]	BUANNIC L, ORAYECH B. Dual substitution strategy to enhance Li⁺ ionic conductivity in Li₇La₃Zr₂O₁₂ solid electrolyte. Chemistry of Materials, 2017,29(4):1769-1778.
[11]	ZHANG Z, SHAO Y, LOTSCH B, et al. New horizons for inorganic solid state ion conductors. Energy & Environmental Science, 2018,11(8):1945-1976.
[12]	CHENG X B, ZHAO C Z, YAO Y X, et al. Recent advances in energy chemistry between solid-state electrolyte and safe lithium- metal anodes. Chem, 2019,5(1):74-96.
[13]	ZHA W, CHEN F, YANG D, et al. High-performance Li_6.4La₃Zr_1.4Ta_0.6O₁₂/poly(ethylene oxide)/succinonitrile composite electrolyte for solid-state lithium batteries. Journal of Power Sources, 2018,397:87-94. DOI URL
[14]	ZHU P, YAN C, DIRICAN M, et al. Li_0.33La_0.557TiO₃ ceramic nanofiber- enhanced polyethylene oxide-based composite polymer electrolytes for all-solid-state lithium batteries. Journal of Materials Chemistry A, 2018,6(10):4279-4285. DOI URL
[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.
[16]	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”. Nano Energy, 2018,46:176-184.
[17]	XIE H, YANG C, FU K K, et al. Flexible, scalable, and highly conductive garnet-polymer solid electrolyte templated by bacterial cellulose. Advanced Energy Materials, 2018,8(18):1703474.
[18]	BAE J, LI Y, ZHANG J, et al. A 3D nanostructured hydrogel- framework-derived high-performance composite polymer lithium-ion electrolyte. Angew. Chem. Int. Ed., 2018,57(8):2096-2100.
[19]	BAE J, LI Y, ZHAO F, et al. Designing 3D nanostructured garnet frameworks for enhancing ionic conductivity and flexibility in composite polymer electrolytes for lithium batteries. Energy Storage Materials, 2018,15:46-52.
[20]	LIU Y, SUN Q, ZHAO Y, et al. Stabilizing the interface of NASICON solid electrolyte against Li metal with atomic layer deposition. ACS Applied Materials & Interfaces, 2018,10(37):31240-31248. DOI URL PMID
[21]	JU J, WANG Y, CHEN B, et al. Integrated interface strategy toward room temperature solid-state lithium batteries. ACS Applied Materials & Interfaces, 2018,10(16):13588-13597. DOI URL PMID
[22]	ZHAO Q, LIU X, STALIN S, et al. Solid-state polymer electrolytes with in-built fast interfacial transport for secondary lithium batteries. Nature Energy, 2019,4(5):365-373.
[23]	DUAN H, YIN Y X, SHI Y, et al. Dendrite-free Li-metal battery enabled by a thin asymmetric solid electrolyte with engineered layers. Journal of the American Chemical Society, 2018,140(1):82-85. DOI URL PMID
[24]	PARANJAPE N, MANDADAPU P C, WU G, et al. Highly- branched cross-linked poly(ethylene oxide) with enhanced ionic conductivity. Polymer, 2017,111:1-8.
[25]	BAN X, ZHANG W, CHEN N, et al. A high-performance and durable poly(ethylene oxide)-based composite solid electrolyte for all solid-state lithium battery. The Journal of Physical Chemistry C, 2018,122(18):9852-9858.
[26]	GONG Y, FU K, XU S, et al. Lithium-ion conductive ceramic textile: a new architecture for flexible solid-state lithium metal batteries. Materials Today, 2018,21(6):594-601.
[27]	LI D, CHEN L, WANG T, et al. 3D fiber-network-reinforced bicontinuous composite solid electrolyte for dendrite-free lithium metal batteries. ACS Applied Materials & Interfaces, 2018,10(8):7069-7078. DOI URL PMID
[28]	LI Z, HUANG H M, ZHU J K, et al. Ionic conduction in composite polymer electrolytes: case of PEO:Ga-LLZO composites. ACS Applied Materials & Interfaces, 2019,11(1):784-791. DOI URL PMID
[29]	WANG Q, WEN Z, JIN J, et al. A gel-ceramic multi-layer electrolyte for long-life lithium sulfur batteries. Chem. Commun. (Camb), 2016,52(8):1637-1640.
[30]	HAN X, GONG Y, FU K K, et al. Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nature Materials, 2017,16(5):572-579. DOI URL PMID
[31]	JU J, CHEN F, XIA C. Ionic conductivity of impregnated samaria doped ceria for solid oxide fuel cells. Electrochimica Acta, 2014,136:422-429.
[32]	WU B, WANG S, LOCHALA J, et al. The role of the solid electrolyte interphase layer in preventing Li dendrite growth in solid-state batteries. Energy & Environmental Science, 2018,11(7):1803-1810.
[33]	HU J L, TIAN J, Li C L. Nanostructured carbon nitride polymer- reinforced electrolyte to enable dendrite-suppressed lithium metal batteries. ACS Applied Materials & Interfaces, 2017,9:11615-11625. DOI URL PMID
[34]	HU J L, YAO Z G, CHEN K Y, et al. High-conductivity open framework fluorinated electrolyte bonded by solidified ionic liquid wires for solid-state Li metal batteries. Energy Storage Materials, 2020,28:37-46.