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A LaCl3-based lithium superionic conductor compatible with lithium metal

Nature volume 616, pages 77–83 (2023)Cite this article

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Abstract

Inorganic superionic conductors possess high ionic conductivity and excellent thermal stability but their poor interfacial compatibility with lithium metal electrodes precludes application in all-solid-state lithium metal batteries1,2. Here we report a LaCl3-based lithium superionic conductor possessing excellent interfacial compatibility with lithium metal electrodes. In contrast to a Li3MCl6 (M = Y, In, Sc and Ho) electrolyte lattice3,4,5,6, the UCl3-type LaCl3 lattice has large, one-dimensional channels for rapid Li+ conduction, interconnected by La vacancies via Ta doping and resulting in a three-dimensional Li+ migration network. The optimized Li0.388Ta0.238La0.475Cl3 electrolyte exhibits Li+ conductivity of 3.02 mS cm−1 at 30 °C and a low activation energy of 0.197 eV. It also generates a gradient interfacial passivation layer to stabilize the Li metal electrode for long-term cycling of a Li–Li symmetric cell (1 mAh cm−2) for more than 5,000 h. When directly coupled with an uncoated LiNi0.5Co0.2Mn0.3O2 cathode and bare Li metal anode, the Li0.388Ta0.238La0.475Cl3 electrolyte enables a solid battery to run for more than 100 cycles with a cutoff voltage of 4.35 V and areal capacity of more than 1 mAh cm−2. We also demonstrate rapid Li+ conduction in lanthanide metal chlorides (LnCl3; Ln = La, Ce, Nd, Sm and Gd), suggesting that the LnCl3 solid electrolyte system could provide further developments in conductivity and utility.

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Fig. 1: Proposed structural model of a LaCl3 lattice-based Li+ superionic conductor and corresponding Li+ migration mechanism.
Fig. 2: Li+ conductivity and identification of Li+ chemical environments in LixTayLazCl3.
Fig. 3: Interfacial stability of Li0.388Ta0.238La0.475Cl3 SE against Li metal electrode.
Fig. 4: Electrochemical performance of Li/Li0.388Ta0.238La0.475Cl3/NCM523 ASSLMB.

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

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Acknowledgements

We acknowledge funding support from the Strategic Priority Research Programme of the Chinese Academy of Sciences (grant no. XDB0450000), the National Natural Science Foundation of China (grant nos. 52073271, 22161142004, 52225208 and 21825302), the USTC Research Funds of the Double First-Class Initiative (no. YD2060002034) and the Open Funds of the State Key Laboratory of Rare Earth Resource Utilization (no. RERU2022003). All theoretical simulations and calculations in this paper were performed at Hefei Advanced Computing Centre. This work was partially carried out at the USTC Center for Micro and Nanoscale Research and Fabrication. Y.-C.Y. thanks L.-J. Wang for assistance with FIB processing. We thank the Shanghai Synchrotron Radiation Facility for providing the BL14B1 beamtime. We also thank W. Yin, H.-C. Chen and J.-P. Xu for beamtime support at MPI.

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Author notes

  1. These authors contributed equally: Yi-Chen Yin, Jing-Tian Yang, Jin-Da Luo and Gong-Xun Lu

Authors and Affiliations

  1. Hefei National Research Center for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, China

    Yi-Chen Yin, Pai Li, Feng Li, Te Tian, Yu-Feng Meng, Tao Ma, Ke Gong, Lin-Jun Wang & Hong-Bin Yao

  2. Department of Applied Chemistry, University of Science and Technology of China, Hefei, China

    Yi-Chen Yin, Jing-Tian Yang, Jin-Da Luo, Jian-Ping Wang, Ye-Chao Wu, Hong-Sheng Mo, Yong-Hui Song, Jun-Nan Yang, Li-Zhe Feng & Hong-Bin Yao

  3. Key Laboratory of Precision and Intelligent Chemistry, University of Science and Technology of China, Hefei, China

    Yi-Chen Yin & Zhenyu Li

  4. College of Materials Science and Engineering, Zhejiang University of Technology, Hangzhou, Zhejiang, China

    Gong-Xun Lu & Xinyong Tao

  5. School of Advanced Materials, Peking University, Shenzhen Graduate School, Shenzhen, China

    Zhongyuan Huang & Yinguo Xiao

  6. Institute of Engineering Research, Hefei Gotion High-Tech Co. Ltd, Hefei, China

    Ye-Chao Wu

  7. Shanghai Synchroton Radiation Facility, Shanghai Advanced Research Institute, Chinese Academy of Sciences, Shanghai, China

    Wen Wen

  8. PHI China Analytical Laboratory, CoreTech Integrated Ltd, Nanjing, China

    Huan-Xin Ju

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Contributions

H.-B.Y. and Y.-C.Y. conceived the concept of the LaCl3 lattice as a Li+ conduction framework and directed the project. Y.-C.Y., J.-T.Y., J.-P.W. and T.M. designed experiments and conducted material synthesis and electrochemical tests. J.-D.L., Z.L. and P.L. carried out DFT and AIMD simulations. X.T., G.-X.L., Y.-H.S. and J.-N.Y. collected and analysed HRTEM images and STEM-EDX data. K.G. and J.-T.Y. carried out 1D and 2D NMR tests and analyses. H.-X.J. and Y.-C.Y. collected and analysed XPS data. Y.-C.Y. and L.-Z.F. collected SEM images. W.W., Y.-F.M., J.-T.Y. and Y.-C.Y. collected PXRD data and conducted XRD refinement. Y.X. and Z.H. collected NPD data and conducted NPD refinement. Y.-C.W., F.L. and H.-S.M. prepared the NCM523 cathode and carried out electrochemical tests. L.-J.W. and Y.-C.Y. conducted FIB processing. All authors discussed the results and commented on the manuscript.

Corresponding authors

Correspondence to Zhenyu Li, Xinyong Tao or Hong-Bin Yao.

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Competing interests

H.-B.Y., Y.-C.Y., J.-T.Y. and J.-D.L. are named as inventors on CN patent no. 202111056096.X, held by the University of Science and Technology of China, that covers the synthesis and applications of UCl3-type ion conductors in all-solid-state batteries.

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Extended data figures and tables

Extended Data Fig. 1 PXRD patterns of ball milled LixTayLazCl3 powders.

a, Schematic of the PXRD testing device with quartz cell and Kapton polyimide (PI) film (left figure) and the background XRD pattern of the testing device and the standard XRD peaks of LaCl3 (right figure). b-e, PXRD patterns of LixTayLazCl3 with different Li contents at different Ta/La ratio of 1/1.50 (b), 1/1.75 (c), 1/2.00 (d) and 1/2.25 (e).

Extended Data Fig. 2 Comparison of ionic conductivity near room temperature and activation energy among typical inorganic oxide (grey ellipse), sulfide (yellow ellipse) and chloride (blue ellipse) solid electrolytes3,4,5,10,11,16,18,19,20,21.

The obtained Li0.388Ta0.238La0.475Cl3 SE exhibits a comparable room temperature σ but lower Ea among oxide and chloride SEs. But, in comparison to sulfide SEs, the σ of Li0.388Ta0.238La0.475Cl3 is lower despite its low Ea.

Extended Data Fig. 3 Structure of Li0.388Ta0.238La0.475Cl3 obtained from combined refinement of X-ray and Neutron diffraction.

a-b, Combined refinement results of the SRXRD (a) and NPD patterns (b). c, Structure of Li0.388Ta0.238La0.475Cl3 obtained from combined refinement. d-e, Coordination conditions of Li1 (2b) (d) and Li2 (6h1) (e) from combined refinement results. The red polyhedrons stand for [LiCl6] polyhedron in d and [LiCl5] polyhedron in e, and red-green sticks stand for Li-Cl coordination. It should be noted that the site positions in the lattice are represented by the average occupancy probability of ions not meaning the real existence of ions. The synchrotron diffraction wavelength is 0.687 Å. Due to insufficient sensitivity of X-ray to Li atom and low amount of LiCl in our sample, the diffraction pattern belonging to LiCl possesses too weak the intensity for quantitative analysis, thus the SRXRD pattern in a only confirms the existence of trace-amount LiCl but cannot give the exact content as determined by the NPD pattern.

Extended Data Fig. 4 The structural model and Li+ migration mechanism of the Li0.388Ta0.238La0.475Cl3.

a, Normalized electrostatic energy of 100 Li-free configurations in Li0.388Ta0.238La0.475Cl3 supercell model with representative high-energy (upper) and low-energy (lower), and corresponding radial distribution functions g(r) of Ta-Ta pair as well as vacancy-vacancy (2c site) pair are plotted. For the low-energy structure, Ta and vacancy are evenly distributed in the LaCl3 framework, shown by fewer peaks at short distances. b, Li0.388Ta0.238La0.475Cl3 model (upper panel) and Li3La5□1Cl18 model (lower panel) obtained after 500 K AIMD simulation for 20 ps (Li ions were removed for clearer exhibition). Compared with the vacancy-contained LaCl3 framework, the vibration of Ta doped framework ions is very severe, leading to the collapse of the framework. c, Side view and top view of three-dimensional Li+ migration pathway in a low-energy Li0.388Ta0.238La0.475Cl3 model calculated by BVSE method, viewed as the white isosurface of constant EBVSE (Li). d, Corresponding energy profile of the migration pathways in panel c, and the red and blue line corresponds to the path in the same color. e, BVSE energy barrier statistics for all 100 structures with different cation arrangements from panel a (after adding Li+). In the BVSE model, the 1D energy barrier is the lowest energy required for Li+ migration along the [001] direction and the 2D energy barriers are the energy corresponding to all possible paths for Li+ to migrate from one channel to another (like the [Li1-Li3-Li4] chain in panel c). The corresponding energy barriers for the structure shown in panel c-d have been marked in this panel using a red pentagram.

Extended Data Fig. 5 Depth-dependent XPS analysis of Ta on the Li0.388Ta0.238La0.475Cl3 surface at the Li/SE interface.

a, Depth-dependent XPS analysis of Ta on the pristine Li0.388Ta0.238La0.475Cl3 pellet to distinguish electrochemically reduced Ta (orange peaks in Fig. 4c) from etching-caused reduced Ta (purple peaks). b, Depth-dependent chemical state changes of Ta on the Li0.388Ta0.238La0.475Cl3 after 50 h cycling in the Li/Li0.388Ta0.238La0.475Cl3/Li symmetric cell. Please see Methods for detailed description of sample preparation.

Extended Data Fig. 6 Morphologies of interface during cycling.

SEM images of Li/SE interface (1st row), SE surface (2nd row) and Li surface (3rd row) after cycling for 50 h (1st column), 100 h (2nd column) and 150 h (3rd column).

Extended Data Fig. 7 Galvanostatic cycling performance of Li/Li0.495Zr0.259Ca0.086La0.432Cl3/Li symmetric cell.

Voltage profile of Li/Li0.495Zr0.259Ca0.086La0.432Cl3/Li symmetric cell cycled under a current density of 2 mA cm−2 with the capacity of 2 mAh cm−2 at 30 °C. The insets show corresponding magnified voltage profiles, indicating the steady Li plating/stripping voltages.

Extended Data Table 1 Structural information of Li0.388Ta0.238La0.475Cl3 from the combined refinement of the SRXRD and NPD data collected at room temperature (~298 K)
Full size table
Extended Data Table 2 Comparison of all-solid-state lithium batteries using recently reported Li3MCl6 system electrolytes or our LaCl3-based electrolyte. The traditional Li-M-Cl electrolytes includes Li3YCl6 ref. 3, Li3InCl6 ref. 4, Li3ScCl6 ref. 5, Li3HoCl6 ref. 45, Li2ZrCl6 ref. 39, Li2In1/3Sc1/3Cl4 ref. 46 and Li2.7Yb0.7Zr0.3Cl6 ref. 17
Full size table

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Yin, YC., Yang, JT., Luo, JD. et al. A LaCl3-based lithium superionic conductor compatible with lithium metal. Nature 616, 77–83 (2023). https://doi.org/10.1038/s41586-023-05899-8

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