Crystalline zinc-ion solid-state electrolytes based on weak coordination environments

doi:10.19799/j.cnki.2095-4239.2024.0236

Abstract

Abstract:

Secondary zinc batteries represent a low-cost, environmentally friendly, and highly safe energy storage technology. However, the insufficient compatibility of zinc-metal anodes with traditional aqueous electrolytes and the growth of zinc dendrites have long posed challenges to their energy density and operational lifespan. Developing solid-state secondary zinc batteries presents a practical pathway to address this bottleneck. However, the high-charge density of divalent zinc ions renders solid-state zinc-ion conduction in conventional ceramic and polymer electrolytes at room temperature exceedingly challenging. In this study, we leveraged zinc trifluoromethyl sulfonate [Zn(TFO)₂] with an intrinsic layered crystal structure as the primary ionic salt framework. We reshaped the coordination environment of zinc ions by incorporating succinonitrile (SN), a bidentate, weakly coordinating ligand recognized for its soft base properties. We designed a new class of crystalline coordination compounds for zinc-ion solid electrolytes [Zn(TFO)₂(SN) _n ]. The co-coordination structure of the cyano group (—CN) and the trifluoromethyl anion (TFO^-) significantly reduce the electrostatic constraint of the anion framework to zinc ions, leading to three orders of magnitude improvement in the room-temperature ion conductivity (from 1.1 × 10^-9 S/cm for Zn(TFO)₂ to approximately 1.8 × 10^-6 S/cm). This solid electrolyte can support long-term zinc-plating/stripping cycles with low polarization voltages (0.08 V, 0.05 mA/cm²) and the reversible charging and discharging of a solid zinc-air battery at room temperature.

Key words: crystalline coordination compounds, weak coordination, zinc-ion solid-state electrolytes, solid-state zinc-ion conduction, secondary zinc batteries

CLC Number:

TM 911

Chaofeng XU, Xiaolei HAN, Jinzhi WANG, Xiaojun WANG, Zhiming LIU, Jingwen ZHAO. Crystalline zinc-ion solid-state electrolytes based on weak coordination environments[J]. Energy Storage Science and Technology, 2024, 13(8): 2519-2528.

Figures/Tables 6

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Table 1

References 57

1	MA T H, WANG Z X, WU D X, et al. High-areal-capacity and long-cycle-life all-solid-state battery enabled by freeze drying technology[J]. Energy & Environmental Science, 2023, 16(5): 2142-2152. DOI: 10.1039/D3EE00420A.
2	LIU W, ZHAO Q W, YU H M, et al. Metallic particles-induced surface reconstruction enabling highly durable zinc metal anode[J]. Advanced Functional Materials, 2023, 33(38): 2302661. DOI: 10.1002/adfm.202302661.
3	PARKER J F, CHERVIN C N, PALA I R, et al. Rechargeable nickel-3D zinc batteries: An energy-dense, safer alternative to lithium-ion[J]. Science, 2017, 356(6336): 415-418. DOI: 10.1126/science.aak9991.
4	ZHENG J X, ZHAO Q, TANG T, et al. Reversible epitaxial electrodeposition of metals in battery anodes[J]. Science, 2019, 366(6465): 645-648. DOI: 10.1126/science.aax6873.
5	SHEN Y H, LIU B, LIU X R, et al. Water-in-salt electrolyte for safe and high-energy aqueous battery[J]. Energy Storage Materials, 2021, 34: 461-474. DOI: 10.1016/j.ensm.2020.10.011.
6	ZHANG L, RODRÍGUEZ-PÉREZ I A, JIANG H, et al. ZnCl₂ "water-in-salt" electrolyte transforms the performance of vanadium oxide as a Zn battery cathode[J]. Advanced Functional Materials, 2019, 29(30): 1902653. DOI: 10.1002/adfm.201902653.
7	SUN L, YAO Y Q, DAI L X, et al. Sustainable and high-performance Zn dual-ion batteries with a hydrogel-based water-in-salt electrolyte[J]. Energy Storage Materials, 2022, 47: 187-194. DOI: 10.1016/j.ensm.2022.02.012.
8	ZHANG Y N, WU D S, HUANG F L, et al. "Water-in-salt" nonalkaline gel polymer electrolytes enable flexible zinc-air batteries with ultra-long operating time[J]. Advanced Functional Materials, 2022, 32(34): 2203204. DOI: 10.1002/adfm.202203204.
9	WANG J, TIAN J X, LIU G X, et al. In situ insight into the interfacial dynamics in "water-in-salt" electrolyte-based aqueous zinc batteries[J]. Small Methods, 2023, 7(6): 2300392. DOI: 10.1002/smtd.202300392.
10	DI S L, NIE X Y, MA G Q, et al. Zinc anode stabilized by an organic-inorganic hybrid solid electrolyte interphase[J]. Energy Storage Materials, 2021, 43: 375-382. DOI: 10.1016/j.ensm. 2021.09.021.
11	CHEN J Z, ZHOU W J, QUAN Y H, et al. Ionic liquid additive enabling anti-freezing aqueous electrolyte and dendrite-free Zn metal electrode with organic/inorganic hybrid solid electrolyte interphase layer[J]. Energy Storage Materials, 2022, 53: 629-637. DOI: 10.1016/j.ensm.2022.10.004.
12	HOU Z G, ZHANG X Q, DONG M F, et al. A large format aqueous rechargeable LiMn₂O₄/Zn battery with high energy density and long cycle life[J]. Science China Materials, 2021, 64(3): 783-788. DOI: 10.1007/s40843-020-1503-7.
13	KUNDU D P, HOSSEINI VAJARGAH S, WAN L W, et al. Aqueous vs. nonaqueous Zn-ion batteries: Consequences of the desolvation penalty at the interface[J]. Energy & Environmental Science, 2018, 11(4): 881-892. DOI: 10.1039/C8EE00378E.
14	WANG F, BORODIN O, GAO T, et al. Highly reversible zinc metal anode for aqueous batteries[J]. Nature Materials, 2018, 17: 543-549. DOI: 10.1038/s41563-018-0063-z.
15	KANG L Z, ZHENG J L, YUE K, et al. Amino-functionalized interfacial layer enables an ultra-uniform amorphous solid electrolyte interphase for high-performance aqueous zinc-based batteries[J]. Small, 2023, 19(44): DOI: 10.1002/smll.202304094.
16	LIN Y X, LI Y, MAI Z X, et al. Interfacial regulation via anionic surfactant electrolyte additive promotes stable (002)-textured zinc anodes at high depth of discharge[J]. Advanced Energy Materials, 2023, 13(38): 2301999. DOI: 10.1002/aenm.202301999.
17	AN Y L, XU B G, TIAN Y, et al. Reversible Zn electrodeposition enabled by interfacial chemistry manipulation for high-energy anode-free Zn batteries[J]. Materials Today, 2023, 70: 93-103. DOI: 10.1016/j.mattod.2023.09.008.
18	XIE S Y, LI Y, DONG L B. Stable anode-free zinc-ion batteries enabled by alloy network-modulated zinc deposition interface[J]. Journal of Energy Chemistry, 2023, 76: 32-40. DOI: 10.1016/j.jechem.2022.08.040.
19	CAO L S, LI D, HU E Y, et al. Solvation structure design for aqueous Zn metal batteries[J]. Journal of the American Chemical Society, 2020, 142(51): 21404-21409. DOI: 10.1021/jacs.0c09794.
20	ZHENG J X, ARCHER L A. Controlling electrochemical growth of metallic zinc electrodes: Toward affordable rechargeable energy storage systems[J]. Science Advances, 2021, 7(2): eabe0219. DOI: 10.1126/sciadv.abe0219.
21	DUERAMAE I, OKHAWILAI M, KASEMSIRI P, et al. Properties enhancement of carboxymethyl cellulose with thermo-responsive polymer as solid polymer electrolyte for zinc ion battery[J]. Scientific Reports, 2020, 10(1): 12587. DOI: 10.1038/s41598-020-69521-x.
22	YANG P H, FENG C Z, LIU Y P, et al. Thermal self-protection of zinc-ion batteries enabled by smart hygroscopic hydrogel electrolytes[J]. Advanced Energy Materials, 2020, 10(48): 2002898. DOI: 10.1002/aenm.202002898.
23	ZHU J C, YAO M J, HUANG S, et al. Thermal-gated polymer electrolytes for smart zinc-ion batteries[J]. Angewandte Chemie International Edition, 2020, 59(38): 16480-16484. DOI: 10.1002/anie.202007274.
24	LIU Y, ZOU H Q, HUANG Z L, et al. In situ polymerization of 1, 3-dioxane as a highly compatible polymer electrolyte to enable the stable operation of 4.5 V Li-metal batteries[J]. Energy & Environmental Science, 2023, 16(12): 6110-6119. DOI: 10.1039/D3EE02797J.
25	LI J C, MA C, CHI M F, et al. Solid electrolyte: The key for high-voltage lithium batteries[J]. Advanced Energy Materials, 2015, 5(4): 1401408. DOI: 10.1002/aenm.201401408.
26	BAN A H, PARK M S, PARK T H, et al. Nonflammable ionic liquid-based quasi-solid-state electrolytes for highly safe sodium-ion batteries[J]. ECS Meeting Abstracts, 2021, (6): 405. DOI: 10. 1149/ma2021-016405mtgabs.
27	LI Y S, YANG X D, HE Y, et al. A novel ultrathin multiple-kinetics-enhanced polymer electrolyte editing enabled wide-temperature fast-charging solid-state zinc metal batteries[J]. Advanced Functional Materials, 2024, 34(4): 2307736. DOI: 10.1002/adfm. 202307736.
28	QIU B, LIANG K Y, HUANG W, et al. Crystal-facet manipulation and interface regulation via TMP-modulated solid polymer electrolytes toward high-performance Zn metal batteries[J]. Advanced Energy Materials, 2023, 13(32): 2301193. DOI: 10. 1002/aenm.202301193.
29	黄渭彬, 张彪, 范金成, 等. ZIF-8复合PEO基固态电解质的制备与改性研究[J]. 储能科学与技术, 2023, 12(4): 1083-1092. DOI: 10.19799/j.cnki.2095-4239.2022.0532.
	HUANG W B, ZHANG B, FAN J C, et al. Preparation and modification of ZIF-8 composite PEO based solid electrolyte[J]. Energy Storage Science and Technology, 2023, 12(4): 1083-1092. DOI: 10.19799/j.cnki.2095-4239.2022.0532.
30	IMANAKA N, TAMURA S. Development of multivalent ion conducting solid electrolytes[J]. Bulletin of the Chemical Society of Japan, 2011, 84(4): 353-362. DOI: 10.1246/bcsj.20100178.
31	IKEDA S, KANBAYASHI Y, NOMURA K, et al. Solid electrolytes with multivalent cation conduction (2): Zinc ion conduction in Zn-Zr-PO₄ system[J]. Solid State Ionics, 1990, 40: 79-82. DOI: 10.1016/0167-2738(90)90291-X.
32	JOHNSON D A, NELSON P G. Factors determining the ligand field stabilization energies of the hexaaqua 2+ complexes of the first transition series and the Irving-williams order[J]. Inorganic Chemistry, 1995, 34(22): 5666-5671. DOI: 10.1021/ic00126a041.
33	HOU Z G, DONG M F, XIONG Y L, et al. A high-energy and long-life aqueous Zn/birnessite battery via reversible water and Zn²⁺ coinsertion[J]. Small, 2020, 16(26): e2001228. DOI: 10.1002/smll.202001228.
34	RICHENS D T. Ligand substitution reactions at inorganic centers[J]. Chemical Reviews, 2005, 105(6): 1961-2002. DOI: 10.1021/cr030705u.
35	PRAKASH P, FALL B, AGUIRRE J, et al. A soft co-crystalline solid electrolyte for lithium-ion batteries[J]. Nature Materials, 2023, 22(5): 627-635. DOI: 10.1038/s41563-023-01508-1.
36	WANG J, ZHAO Z, LU G, et al. Room-temperature fast zinc-ion conduction in molecule-flexible solids[J]. Materials Today Energy, 2021, 20: 100630. DOI: 10.1016/j.mtener.2020.100630.
37	ALARCO P J, ABU-LEBDEH Y, ABOUIMRANE A, et al. The plastic-crystalline phase of succinonitrile as a universal matrix for solid-state ionic conductors[J]. Nature Materials, 2004, 3: 476-481. DOI: 10.1038/nmat1158.
38	GOODENOUGH J B, HONG H Y P, KAFALAS J A. Fast Na⁺-ion transport in skeleton structures[J]. Materials Research Bulletin, 1976, 11(2): 203-220. DOI: 10.1016/0025-5408(76)90077-5.
39	HONG H Y P. Crystal structures and crystal chemistry in the system Na₁₊ xZr₂SixP_3- xO₁₂[J]. Materials Research Bulletin, 1976, 11(2): 173-182. DOI: 10.1016/0025-5408(76)90073-8.
40	DINNEBIER R, SOFINA N, HILDEBRANDT L, et al. Crystal structures of the trifluoromethyl sulfonates M(SO₃CF₃)₂ (M=Mg, Ca, Ba, Zn, Cu) from synchrotron X-ray powder diffraction data[J]. Acta Crystallographica Section B, Structural Science, 2006, 62(Pt 3): 467-473. DOI: 10.1107/S0108768106009517.
41	MANTHIRAM A, GOODENOUGH J B. Layered lithium cobalt oxide cathodes[J]. Nature Energy, 2021, 6: 323. DOI: 10.1038/s41560-020-00764-8.
42	ROEDERN E, KÜHNEL R S, REMHOF A, et al. Magnesium ethylenediamine borohydride as solid-state electrolyte for magnesium batteries[J]. Scientific Reports, 2017, 7: 46189. DOI: 10.1038/srep 46189.
43	IMANAKA N, TAMURA S. Development of multivalent ion conducting solid electrolytes[J]. Bulletin of the Chemical Society of Japan, 2011, 84(4): 353-362. DOI: 10.1246/bcsj.20100178.
44	SHEN Y N, DENG G H, GE C Q, et al. Solvation structure around the Li⁺ ion in succinonitrile-lithium salt plastic crystalline electrolytes[J]. Physical Chemistry Chemical Physics, 2016, 18(22): 14867-14873. DOI: 10.1039/C6CP02878K.
45	UMAR Y, MORSY M A. Ab initio and DFT studies of the molecular structures and vibrational spectra of succinonitrile[J]. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 2007, 66(4/5): 1133-1140. DOI: 10.1016/j.saa. 2006.05.026.
46	DAIGLE J C, ARNOLD A, VIJH A, et al. Solid-state NMR study of new copolymers as solid polymer electrolytes[J]. Magnetochemistry, 2018, 4(1): 13. DOI: 10.3390/magnetochemistry4010013.
47	FREITAG K M, KIRCHHAIN H, VAN WÜLLEN L, et al. Enhancement of Li ion conductivity by electrospun polymer fibers and direct fabrication of solvent-free separator membranes for Li ion batteries[J]. Inorganic Chemistry, 2017, 56(4): 2100-2107. DOI: 10.1021/acs.inorgchem.6b02781.
48	BOTTKE P, RETTENWANDER D, SCHMIDT W, et al. Ion dynamics in solid electrolytes: NMR reveals the elementary steps of Li⁺ hopping in the garnet Li_6.5La₃Zr_1.75Mo_0.25O₁₂[J]. Chemistry of Materials, 2015, 27(19): 6571-6582. DOI: 10.1021/acs.chemmater.5b02231.
49	YANG H, HUQ R, FARRINGTON G C. Conductivity in PEO-based Zn(II) polymer electrolytes[J]. Solid State Ionics, 1990, 40: 663-665. DOI: 10.1016/0167-2738(90)90093-7.
50	VIJAYAKUMAR V, GHOSH M, KURIAN M, et al. An in situ cross-linked nonaqueous polymer electrolyte for zinc-metal polymer batteries and hybrid supercapacitors[J]. Small, 2020, 16(35): e2002528. DOI: 10.1002/smll.202002528.
51	ZENG Z Q, LIU G Z, JIANG Z P, et al. Zinc bis(2-ethylhexanoate), a homogeneous and bifunctional additive, to improve conductivity and lithium deposition for poly (ethylene oxide) based all-solid-state lithium metal battery[J]. Journal of Power Sources, 2020, 451: 227730. DOI: 10.1016/j.jpowsour. 2020.227730.
52	KARAN S, SAHU T B, SAHU M, et al. Characterization of ion transport property in hot-press cast solid polymer electrolyte (SPE) films: [PEO: Zn(CF₃SO₃)₂][J]. Ionics, 2017, 23(10): 2721-2726. DOI: 10.1007/s11581-017-2036-7.
53	OVERBURY S H, BERTRAND P A, SOMORJAI G A. Surface composition of binary systems. Prediction of surface phase diagrams of solid solutions[J]. Chemical Reviews, 1975, 75(5): 547-560. DOI: 10.1021/cr60297a001.
54	BRUNO M. A revised thermodynamic model for crystal surfaces. I. Theoretical aspects[J]. CrystEngComm, 2017, 19(42): 6314-6324. DOI: 10.1039/C7CE01397C.
55	CHEN Z, LI X L, WANG D H, et al. Grafted MXene/polymer electrolyte for high performance solid zinc batteries with enhanced shelf life at low/high temperatures[J]. Energy & Environmental Science, 2021, 14(6): 3492-3501. DOI: 10.1039/D1EE00409C.
56	PLANCHA M J C, RANGEL C M, SEQUEIRA C A C. Pseudo-equilibrium phase diagrams for PEO-Zn salts-based electrolytes[J]. Solid State Ionics, 1999, 116(3/4): 293-300. DOI: 10.1016/S0167-2738(98)00356-7.
57	YANG H, FARRINGTON G C. Poly(ethylene oxide)-based Zn(II) halide electrolytes[J]. Journal of the Electrochemical Society, 1992, 139(6): 1646-1654. DOI: 10.1149/1.2069471.

锌离子固态电解质	离子电导率 /(S/cm)	电流密度/(mA/cm²)/极化电压/V	参考文献
Zn(TFO)₂(SN)₄	4.4×10^-6(RT)	0.05/0.08	本工作
PVHF-Zn(TFO)₂	1.99×10^-6(RT)	0.2/0.4(寿命＜40 h)	[55]
PEO-Zn(TFO)₂	1.09×10^-6(RT)	—	[52]
ZnCl₂(PEO)₂₄	10^-9～10^-8(RT)	—	[56]
ZnX₂(PEO)₂₀(X=Br, I)	10^-9～10^-8(RT)	—	[57]
ZnCl₂PEO _n (n=4～16)	10^-8～10^-7(RT)	—	[57]

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