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A dynamic stability design strategy for lithium metal solid state batteries

Nature volume 593, pages 218–222 (2021)Cite this article

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Abstract

A solid-state electrolyte is expected to suppress lithium (Li) dendrite penetration with high mechanical strength1,2,3,4. However, in practice it still remains challenging to realise a lithium metal anode for batteries, because micrometre- or submicrometre-sized cracks in ceramic pellets can frequently be generated during battery assembly or long-time cycling3,5. Once cracks form, lithium dendrite penetration is inevitable6,7. Here we describe a solid-state battery design with a hierarchy of interface stabilities (to lithium metal responses), to achieve an ultrahigh current density with no lithium dendrite penetration. Our multilayer design has the structure of a less-stable electrolyte sandwiched between more-stable solid electrolytes, which prevents any lithium dendrite growth through well localized decompositions in the less stable electrolyte layer. A mechanism analogous to the expansion screw effect is proposed, whereby any cracks are filled by dynamically generated decompositions that are also well constrained, probably by the ‘anchoring’ effect the decompositions induce. The cycling performance of the lithium metal anode paired with a LiNi0.8Mn0.1Co0.1O2 cathode is very stable, with an 82 per cent capacity retention after 10,000 cycles at a 20C rate (8.6 milliamps per centimetre squared) and 81.3 per cent capacity retention after 2,000 cycles at a 1.5C rate (0.64 milliamps per centimetre squared). Our design also enables a specific power of 110.6 kilowatts per kilogram and specific energy up to 631.1 watt hours per kilogram at the micrometre-sized cathode material level.

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Fig. 1: Superior symmetric battery cycling performance from the multilayer design.
Fig. 2: Structure, chemistry and morphology of solid electrolyte after cycling.
Fig. 3: Cycling performance of solid-state batteries with the multilayer design.
Fig. 4: Versatility, specific power and energy of the multilayer design.

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Data availability

The data that support the findings of this study are available from the corresponding author upon reasonable request.

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Acknowledgements

The work was supported by the Dean’s Competitive Fund for Promising Scholarship at Harvard University and the Harvard Data Science Initiative Competitive Research Fund. The SEM and XPS experiments were conducted at the Center for Nanoscale Systems (CNS) at Harvard University, supported by the National Science Foundation.

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Authors and Affiliations

  1. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, MA, USA

    Luhan Ye & Xin Li

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  1. Luhan Ye
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  2. Xin Li
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Contributions

X.L. and L.Y. conceived the multilayer design. X.L. supervised all aspects of the research. L.Y. performed the experiments. L.Y. and X.L. analysed the results and wrote the manuscript.

Corresponding author

Correspondence to Xin Li.

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Competing interests

X.L. and L.Y. report a US provisional patent application of Batteries with Solid State Electrolyte Multilayers filed on 30 October 2020. Application serial no. 63/108,075.

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Peer review information Nature thanks the anonymous reviewer(s) for their contribution to the peer review of this work. Peer reviewer reports are available.

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Extended data figures and tables

Extended Data Fig. 1 SEM images of LPSCl, LGPS and LSPS particles.

a–c, SEM images of LPSCl (a), LGPS (b) and LSPS (c) particles.

Extended Data Fig. 2 Electrochemical voltage profiles, optical and SEM images of lithium discharged asymmetric batteries with different electrolytes.

Asymmetric batteries with Li/G as anode (lithium capacity loading = 3 mAh cm−2), stainless steel (SS) current collector as cathode, and solid electrolytes as separator were assembled. Lithium was enforced to deposit on the surface of solid electrolytes at 0.25 mA cm−2. Different electrochemical behaviours and surface information were observed. a, Short-circuiting happened immediately after lithium was deposited on the surface of pure LPSCl pellet. A metallic colour (silver or grey) was observed from the optical image and a small level of cracking was observed from the SEM image. b, Voltage ramping up quickly after lithium was deposited on the surface of pure LGPS pellet in a few hours. Decomposition (dark black) was observed from the optical image and no crack was observed from the SEM image. c, Voltage ramping up gradually, reaching cut-off voltage after lithium was fully deposited on the surface of the LGPS separated LPSCl pellet. Metallic colour (silver or grey) on large area was observed from the optical image and cracks were observed from the SEM image.

Extended Data Fig. 3 XPS characterization on the dark region of LGPS and LPSCl after lithium discharge.

a–c, XPS data of the black region on the LGPS surface after lithium discharging at 0.25 mA cm−2 (shown in Supplementary Fig. 2b) with the chemical information of S (a), P (b) and Ge (c). d–f, XPS data of the silver region on the LPSCl surface after lithium discharging (shown in Supplementary Fig. 2c) with the chemical information of S (d), P (e) and Cl (f). The beam size of XPS is 400 μm.

Extended Data Fig. 4 Performance difference of LSPS as the single layer and the central layer of multilayer in symmetric battery configurations.

a, Symmetric battery with Li9.54Si1.74(P0.9Sb0.1)1.44S11.7Cl0.3 (LSPS) as electrolyte and graphite covered lithium (Li/G) as electrodes. b, Symmetric battery with the combination of Li9.54Si1.74(P0.9Sb0.1)1.44S11.7Cl0.3 (LSPS) and Li5.5PS4.5Cl1.5 (LPSCl) in the configuration of LPSCl–LSPS–LPSCl as electrolyte and graphite covered lithium as electrodes.

Extended Data Fig. 5 Cycling performance of symmetric batteries with LGPS or LPSCl as the single solid electrolyte layer.

a, High rate (10 mA cm−2) cycling for Li10Ge1P2S12 (LGPS) symmetric battery with Li/G as electrodes. The over potential starts from 0.6 V and quickly ramp up to over 1.5 V in the first few cycles. b, High rate (15 mA cm−2) cycling for LGPS symmetric battery with Li/G as electrodes. The over potential ramping up to over 5 V in the first cycle. c, Symmetric battery with LPSCl as electrolyte and Li/G as electrodes, cycling at 0.25 mA cm−2. Short-circuiting shows up in the first two cycles.

Extended Data Fig. 6 Optical image, XRD and XPS of cross-sections of symmetric batteries before and after cycling.

a, Optical image of cross-section of Li/G-LPSCl-LGPS-LPSCl-G/Li after 300 h cycling at 0.25 mA cm−2 at room temperature, showing another region without decomposition. b, Post-treated image of a in only black and white. c, Optical image of cross-section of Li/G–LPSCl–LGPS–LPSCl–G/Li after 30 cycles at 20 mA cm−2 at 55 °C. XPS spot size is marked in the black region for a comparison with the size of the black region. d, Optical image of the cross-section of the LPSCl–LGPS–LPSCl pellet before cycling. e, Optical image of the cross-section of the LPSCl–LGPS–LPSCl pellet after 300 h cycling at 0.25 mA cm−2 (e1) and 30 cycles at 20 mA cm−2 (e2). The images in d and e are from the same pellet in a and c in a larger view, which were taken by an optical microscope in the glovebox. f, XRD of LGPS before and after cycling at 0.25 mA cm−2 for 300 h, with features of XRD peaks shown in g1–g5. h–j, XPS measurement of S 2p (h), P 2p (i) and Ge 3d (j) on the black region in the cross-section of the sandwich pellet after battery cycling at 0.25 mA cm−2 for 300 h. The beam size of the XPS is 70 μm.

Extended Data Fig. 7 Morphology difference of LGPS and LPSCl before and after cycling.

SEM images of the solid electrolytes before cycling (first row), and after cycling for 100 h (second row) and 300 h (third row) in the region of LPSCl, LGPS, and their transition areas. The fourth column: LPSCl side with a 10-μm scale bar. The SEM images were from the symmetric battery in the configuration of Li/G–LPSCl–LGPS–LPSCl–G/Li.

Extended Data Fig. 8 Half-battery cycling performance using pure LGPS and/or LPSCl as electrolytes.

a, The discharging profiles of graphite covered Li paired with LiNi0.8Mn0.1Co0.1O2 (Li/G-NMC811) batteries, using Li5.5PS4.5Cl1.5 (LPSCl, green 10C), Li9.54Si1.74(P0.9Sb0.1)1.44S11.7Cl0.3 (LSPS, blue 10C), and multilayer LPSCl-LSPS-LPSCl configuration (purple 10C, black 1C, red 0.1C) as the electrolyte. The batteries were first charged at 0.1C and then discharged at various rates at room temperature. b, c, The cycling performance of the same multilayer battery at 5C (b) and 10C (c) in the range of 2.5–4.3 V in the environment without humidity control (55 °C). d, e, The first charge and discharge profiles of Li-LiCoO2 (Li-LCO) batteries with (d) Li5.5PS4.5Cl1.5 (LPSCl) and (e) Li10Ge1P2S12 (LGPS) as the electrolyte. Uncoated LCO and LiNbO3-coated LCO is applied for LPSCl and LGPS, respectively. f, g, The first charge and discharge profiles of graphite covered Li paired with LiNi0.8Mn0.1Co0.1O2 (Li/G-NMC811) batteries with LPSCl as the electrolyte at (f) 0.3C and (g) 0.5C; along with the cycling performance at (h) 0.3C (LCO at 0.1C is also shown) and (i) 0.5C. All batteries in d–i were tested at room temperature. The battery configuration and materials used are summarized in Supplementary Table 2. j, Cycling performance of solid-state battery with multilayer electrolytes at different Li/graphite capacity ratios of 10:1, 5:1 and 2.5:1. k, Cycling performance of solid-state battery with multilayer electrolytes under different operating pressures of 50–75 MPa, 150 MPa and 250 MPa. l, Cycling performance of solid-state battery with thin multilayer: Li/G–LPSCl (100 μm)–LSPS (50 μm)–LPSCl (50 μm)–NMC811. m, High-power voltage profile of the Li/G–LPSCl–LSPS–LPSCl–NMC811 battery at 100C–500C at 55 °C with a cut-off voltage of 2–4.3 V. Red, blue and pink curves are from batteries first charged at 0.5C and then discharged at high C rates, and black curves are at 100C charge and discharge. 1C = 0.43 mA cm−2.

Extended Data Table 1 Mechanical and (electro)chemical properties of different electrolytes
Full size table
Extended Data Table 2 Battery configurations and materials ratios applied in this work
Full size table

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Ye, L., Li, X. A dynamic stability design strategy for lithium metal solid state batteries. Nature 593, 218–222 (2021). https://doi.org/10.1038/s41586-021-03486-3

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