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Elastomeric electrolytes for high-energy solid-state lithium batteries

Nature volume 601, pages 217–222 (2022)Cite this article

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An Addendum to this article was published on 30 August 2022

Abstract

The use of lithium metal anodes in solid-state batteries has emerged as one of the most promising technologies for replacing conventional lithium-ion batteries1,2. Solid-state electrolytes are a key enabling technology for the safe operation of lithium metal batteries as they suppress the uncontrolled growth of lithium dendrites. However, the mechanical properties and electrochemical performance of current solid-state electrolytes do not meet the requirements for practical applications of lithium metal batteries. Here we report a class of elastomeric solid-state electrolytes with a three-dimensional interconnected plastic crystal phase. The elastomeric electrolytes show a combination of mechanical robustness, high ionic conductivity, low interfacial resistance and high lithium-ion transference number. The in situ-formed elastomer electrolyte on copper foils accommodates volume changes for prolonged lithium plating and stripping processes with a Coulombic efficiency of 100.0 per cent. Moreover, the elastomer electrolytes enable stable operation of the full cells under constrained conditions of a limited lithium source, a thin electrolyte and a high-loading LiNi0.83Mn0.06Co0.11O2 cathode at a high voltage of 4.5 volts at ambient temperature, delivering a high specific energy exceeding 410 watt-hours per kilogram of electrode plus electrolyte. The elastomeric electrolyte system presents a powerful strategy for enabling stable operation of high-energy, solid-state lithium batteries.

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Fig. 1: Design of plastic-crystal-embedded elastomer electrolyte.
Fig. 2: Properties of the built-in PCEE.
Fig. 3: Built-in PCEE in symmetric Li and asymmetric Li||Cu cells.
Fig. 4: Towards a high-energy all-solid-state LMB with elastomeric electrolyte.

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Data availability

The data that support the findings of this study are available from the corresponding authors upon reasonable request. Source data are provided with this paper.

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Acknowledgements

This work was performed in part at the Georgia Tech Institute for Electronics and Nanotechnology, a member of the National Nanotechnology Coordinated Infrastructure (NNCI), which is supported by the National Science Foundation (ECCS-2025462). This work was partially supported by KRICT core project (BSF20-242). J.H., Y.J.L. and B.J.K. acknowledge the support from the National Research Foundation of Korea (NRF-2019R1A2B5B03101123, 2017M3D1A1039553 and 2020RlA4A1018516).

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Author notes

  1. These authors contributed equally: Michael J. Lee, Junghun Han

Authors and Affiliations

  1. George W. Woodruff School of Mechanical Engineering, Georgia Institute of Technology, Atlanta, GA, USA

    Michael J. Lee, Kyungbin Lee & Seung Woo Lee

  2. Department of Chemical and Biomolecular Engineering, Korea Advanced Institute of Science and Technology (KAIST), Daejeon, Republic of Korea

    Junghun Han, Young Jun Lee & Bumjoon J. Kim

  3. Division of Advanced Materials, Korea Research Institute of Chemical Technology, Daejeon, Republic of Korea

    Byoung Gak Kim

  4. Renewable Energy Institute, Korea Institute of Energy Research, Daejeon, Republic of Korea

    Kyu-Nam Jung

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Contributions

S.W.L., B.J.K., M.J.L. and J.H. conceived the ideas and designed the experiments. K.L., Y.J.L., B.G.K. and K.-N.J. were involved with the methods and characterizations of materials. S.W.L., B.J.K., M.J.L. and J.H. co-wrote the manuscript. All authors reviewed the manuscript.

Corresponding authors

Correspondence to Bumjoon J. Kim or Seung Woo Lee.

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Competing interests

S.W.L., B.J.K., M.J.L. and J.H. have filed a US provisional patent application (63/209,140) covering the materials and lithium metal battery application described in this paper.

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Extended data figures and tables

Extended Data Fig. 1 Fabrication process of in situ-polymerized PCEE within the electrochemical cell.

a, Digital photo images of a homogeneous solution consisting of BA, SN, LiTFSI, PEGDA and AIBN for built-in polymerization (left) and haze-coloured PCEE on the bottom of a glass vial after polymerization at 70 °C for 2 h (right). b, Photo image of PCEE showing mechanical elasticity. c, Schematic illustration of the built-in polymerization process. The solution was injected into the electrochemical cells and then heated in an oven for built-in polymerization.

Extended Data Fig. 2 Comparison of morphology, ion conductivity and mechanical property between polymerization induced-PCEE and blend systems.

a, Morphology of PCEE. SEM image of PCEE shows the continuously-connected SN phases within the elastomeric matrix that was uniformly developed over a large area through PIPS. b, Morphology of blend consisting of elastomeric polymer (cross-linked poly(butylacrylate) and PEGDA) and plastic crystal (SN) with LiTFSI. A blend is prepared from a mixture of elastomeric polymers and SN–LiTFSI in chloroform, followed by a drying process. The same weight ratios of BA, SN, PEGDA and LiTFSI are used for constructing the PCEE and blend systems. SEM image of blend shows a macrophase separation with a length-scale of over μm. c–d, Comparison of ionic conductivity (c) and toughness (d) between the PCEE and blend systems.

Source data

Extended Data Fig. 3 Electrochemical characterization for the symmetric Li cells with built-in PCEE.

a, Time-dependent Nyquist plots of the symmetric Li cells configured with built-in PCEE. b, Nyquist plots of the symmetric Li cells configured with built-in PCEE after 25, 75, and 100 cycles. c, Cycling performance of the symmetric Li cells configured with built-in PCEE at different current densities. d, Voltage hysteresis of Li plating/stripping for built-in PCEE compared with previously reported literature data8,12,16,38,39,47,48,49,50,51,52. e, Nyquist plots of the symmetric Li cells before and after polarization of 10 mV. f, Steady-state current measurement of the symmetric Li cells under 10 mV polarization for 10 h. EIS was measured at open-circuit voltage in the range of 105 to 10° Hz with an amplitude of 10 mV.

Source data

Extended Data Fig. 4 Characterization of the SEI components on the cycled Li metal anodes with built-in PCEE and SN100 by XPS.

The high-resolution Li 1s, C 1s, O 1s, N 1s, and F 1s XPS spectra of the Li metal anodes were measured after 100 cycles of the symmetric Li cells with built-in PCEE and SN100 at a current density of 1 mA cm–2 with a capacity of 1 mAh cm–2.

Source data

Extended Data Fig. 5 Li plating and stripping behaviour of built-in PCEE on bare Cu.

a, Cycling performance of the asymmetric Li||Cu cells at current densities of 0.5 and 1 mA cm–2, respectively. b–c, Li stripping and plating profiles for built-in PCEE at a current density of 0.5 mA cm–2 with a capacity of 1 mAh cm–2 (b), and a current density of 1 mA cm–2 with a capacity of 2 mAh cm–2 (c).

Extended Data Fig. 6 Electrochemical stability of built-in PCEE paired with high-voltage NMC-622 cathode.

a, Electrochemical floating experiment was performed using Li||NMC-622 with built-in PCEE. The cell was charged to 4.2 V at 0.2C (1 C = 180 mA g–1) and then held at gradually higher voltages for 10 h up to 4.7 V. b, Rate capability of the full cell (35-μm-thick Li anode; 25-μm-thick built-in PCEE; high-loading NMC-622 (9.7 mg cm–2) in the voltage range of 2.7–4.5 V at equal current densities. (Inset: the capacity utilization at different areal current densities). c, Cycling performance of the full cell (excess Li; 25-μm-thick built-in PCEE; NMC-622 (2.1 mg cm–2)) as a function of cycle number in the voltage range of 2.7–4.5 V. The cell maintained a high capacity of ~140 mAh g–1 (82% capacity retention) with high CEs of 99.5% for 100 cycles, confirming the stable operation at high voltage. Cells were performed at 20 °C.

Extended Data Fig. 7 Cycling performance of the Li||LiFePO4 cell at 1 C without voltage holding.

a, Capacity and Coulombic efficiency as a function of cycle number. b, Corresponding voltage profiles. 1 C = 170 mA g–1.

Extended Data Fig. 8 Electrochemical performances of the full cells with high-voltage NMC-83 cathode.

a, The charge and discharge profiles of the full cell in the voltage range of 2.7–4.3V at 0.1 mA cm–2. b, Temperature-dependent voltage profiles of the full cell charged/discharged at equal temperatures (60 to 0 °C) in the voltage range of 2.7–4.5 V. (Inset: the capacity utilization at different temperatures). All full cells were configured with 35-μm-thick Li anode; 25-μm-thick built-in PCEE; high-loading NMC-83 (>10 mg cm–2).

Extended Data Table 1 Comparison of battery performance with previously reported solid-state LMBs
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Lee, M.J., Han, J., Lee, K. et al. Elastomeric electrolytes for high-energy solid-state lithium batteries. Nature 601, 217–222 (2022). https://doi.org/10.1038/s41586-021-04209-4

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