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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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.
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
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  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.
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.
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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