Enhancing ionic conductivity in solid electrolyte by relocating diffusion ions to under-coordination sites

Lei Zhu; Youwei Wang; Junchao Chen; Wenlei Li; Tiantian Wang; Jie Wu; Songyi Han; Yuanhua Xia; Yongmin Wu; Mengqiang Wu; Fangwei Wang; Yi Zheng; Luming Peng; Jianjun Liu; Liquan Chen; Weiping Tang

doi:10.1126/sciadv.abj7698

. 2022 Mar 18;8(11):eabj7698. doi: 10.1126/sciadv.abj7698

Enhancing ionic conductivity in solid electrolyte by relocating diffusion ions to under-coordination sites

Lei Zhu ^1,^†, Youwei Wang ^2,^3,^†, Junchao Chen ^1,^4,^†,^*, Wenlei Li ⁵, Tiantian Wang ^2,³, Jie Wu ¹, Songyi Han ¹, Yuanhua Xia ⁶, Yongmin Wu ¹, Mengqiang Wu ⁵, Fangwei Wang ⁷, Yi Zheng ¹, Luming Peng ⁴, Jianjun Liu ^2,^3,^8,^*, Liquan Chen ⁷, Weiping Tang ^1,^9,^*

¹State Key Laboratory of Space Power-Sources Technology, Shanghai Institute of Space Power-Sources, Shanghai 200245, China.

²State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China.

³Center of Materials Science and Optoelectronics Engineering, College of Materials Science and Optoelectronic Technology, University of Chinese Academy of Sciences, Beijing 100049, China.

⁴Key Laboratory of Mesoscopic Chemistry of MOE and Collaborative Innovation Center of Chemistry for Life Sciences, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.

⁵Center for Advanced Electric Energy Technologies, School of Materials and Energy, University of Electronic Science and Technology of China, Chengdu 611731, China.

⁶Key Laboratory of Neutron Physics, Institute of Nuclear Physics and Chemistry, China Academy of Engineering Physics, Mianyang 621999, China.

⁷Beijing National Laboratory for Condensed Mater Physics, Institute of Physics, Chinese Academy of Sciences, Beijing 100190, China.

⁸School of Chemistry and Materials Science, Hangzhou Institute for Advanced Study, University of Chinese Academy of Science, Hangzhou 310024, China.

⁹School of Chemistry and Chemical Engineering, Shanghai Jiao Tong University, Shanghai 200240, China.

Corresponding author. Email: cjcnuaa@163.com (J.C.); jliu@mail.sic.ac.cn (J.L.); tangweiping@vip.sina.com (W.T.)

^†

These authors contributed equally to this work.

Roles

Lei Zhu: Conceptualization, Formal analysis, Investigation, Methodology, Validation, Visualization, Writing - original draft, Writing - review & editing

Youwei Wang: Conceptualization, Formal analysis, Investigation, Methodology, Writing - original draft

Junchao Chen: Conceptualization, Formal analysis, Investigation, Methodology, Project administration, Validation, Visualization, Writing - original draft, Writing - review & editing

Wenlei Li: Conceptualization, Investigation, Methodology

Tiantian Wang: Investigation, Methodology, Validation, Writing - original draft, Writing - review & editing

Jie Wu: Formal analysis, Investigation, Methodology

Songyi Han: Formal analysis, Investigation, Validation

Yuanhua Xia: Investigation, Resources

Yongmin Wu: Formal analysis, Investigation, Resources

Mengqiang Wu: Conceptualization, Data curation, Formal analysis, Investigation, Methodology, Project administration, Resources, Visualization, Writing - original draft, Writing - review & editing

Fangwei Wang: Formal analysis, Investigation, Resources, Visualization, Writing - original draft, Writing - review & editing

Yi Zheng: Methodology, Project administration, Resources, Validation, Visualization

Luming Peng: Methodology, Supervision, Writing - original draft

Jianjun Liu: Conceptualization, Data curation, Funding acquisition, Investigation, Methodology, Project administration, Resources, Supervision, Validation, Writing - original draft, Writing - review & editing

Liquan Chen: Investigation, Writing - review & editing

Weiping Tang: Conceptualization, Data curation, Formal analysis, Funding acquisition, Investigation, Methodology, Project administration, Resources, Supervision, Validation, Visualization, Writing - original draft, Writing - review & editing

PMCID: PMC8932667 PMID: 35302845

Abstract

Solid electrolytes are highly important materials for improving safety, energy density, and reversibility of electrochemical energy storage batteries. However, it is a challenge to modulate the coordination structure of conducting ions, which limits the improvement of ionic conductivity and hampers further development of practical solid electrolytes. Here, we present a skeleton-retained cationic exchange approach to produce a high-performance solid electrolyte of Li₃Zr₂Si₂PO₁₂ stemming from the NASICON-type superionic conductor of Na₃Zr₂Si₂PO₁₂. The introduced lithium ions stabilized in under-coordination structures are facilitated to pass through relatively large conduction bottlenecks inherited from the Na₃Zr₂Si₂PO₁₂ precursor. The synthesized Li₃Zr₂Si₂PO₁₂ achieves a low activation energy of 0.21 eV and a high ionic conductivity of 3.59 mS cm⁻¹ at room temperature. Li₃Zr₂Si₂PO₁₂ not only inherits the satisfactory air survivability from Na₃Zr₂Si₂PO₁₂ but also exhibits excellent cyclic stability and rate capability when applied to solid-state batteries. The present study opens an innovative avenue to regulate cationic occupancy and make new materials.

Ionic conductivity of solid electrolytes is enhanced with expanded bottleneck and reduced coordination for conductive ions.

INTRODUCTION

All-solid-state batteries (ASSBs) are attracting ever increasing attention for solving the intrinsic drawbacks of current Li-ion batteries, such as leakage and flammability of liquid electrolytes, and limited energy densities (1, 2). The success of ASSBs depends on solid electrolytes with satisfying Li-ionic conductivities. A high electrochemical stability at the interface of the solid electrolytes with electrode materials in a wide range of working potentials also plays an important role in designing ASSBs, for any electrochemical instability of solid electrolytes may result in interfacial decomposition products with a low ionic conductivity (3, 4). Recent studies on ASSBs have made considerable progress in high-conductivity inorganic solid electrolytes, which are generally classified into sulfide and oxide solid electrolytes (5). The most remarkable features of sulfide solid electrolytes such as Li₁₀GeP₂S₁₂ (6) and Li₆PS₅X (X = Cl, Br, I) (7, 8) are their high ionic conductivity, comparable with organic liquid electrolytes at room temperatures, but low stability against Li metal to decompose into interfacial side product of Li₂S (9). Oxide solid electrolytes such as Li₇La₃Zr₂O₁₂ (10) and LiPON (11) usually exhibit higher electrochemical stability at the interface in working potentials (12). Despite tremendous research advancements in oxide solid electrolytes, it still faces a large challenge to further improve their ionic conductivity to meet the requirement of practicable application (13).

In the past decades, a great deal of effort has been made for developing oxide solid electrolytes such as LISICON (14), NASICON (15, 16), perovskite (17, 18), garnet (10, 19), and LiPON (20) systems. The basic step in diffusion paths is Li-ion migration between two stable sites through the high-energy transition state. In these compounds, Li-ions usually occupy the lower-energy hexahedral sites and commonly surmounting high-energy and narrow bottleneck (transition state) into tetrahedral sites (Fig. 1A). Reducing the activation energy heights of transition states along the long-range diffusion path is of much importance in increasing ionic conductivity. For many years, optimization of these solid electrolytes has largely proceeded by substituting skeleton structural elements to enlarge the bottleneck and reduce the migration barrier (3, 21), which only achieve the ionic conductivities of the order of 10⁻⁶ to 10⁻³ S cm⁻¹ at room temperature and the activation energy of 0.25 to 0.6 eV. Achieving a low migration barrier requires the bottleneck between two different polyhedrons to satisfy a very specific size. Statistical analysis indicates that those NASION-type lithium solid electrolytes with a bottleneck size of >2.05 Å exhibit a much lower migration barrier (Fig. 1B) (22). Intrinsically, regulating bottleneck size corresponds to change of polyhedron size, which may lead to Li⁺ occupancy changes from high-coordination to under-coordination sites for retaining structural stabilization (Fig. 1C). Therefore, the regulating coordination structure between Li⁺ ions and O²⁻ anions provides an important strategy for breaking through this contradiction between occupancy stability and ionic conductivity.

Fig. 1. — (A) Structural schematic of coordination engineering for the transition between LiO₆ hexahedrons and LiO₄ tetrahedrons. (B) Migration barrier of Li⁺ ions from LiO₆ hexahedrons to LiO₄ adjacent tetrahedrons. (C) Relations between bottleneck and the migration energy barrier of lithium-ion in NASICON-type lithium solid electrolytes (22).

In this work, a skeleton-retained cationic exchange approach based on Na₃Zr₂Si₂PO₁₂ (NZSP) is proposed to synthesize advanced solid electrolyte Li₃Zr₂Si₂PO₁₂ (LZSP), in which Li⁺ ions self-adaptively occupy under-coordinated sites and maintain relatively large bottleneck sizes by inheriting the pristine framework. The obtained LZSP is quite distinct from the low-ionic conductivity LiZr₂(PO₄)₃ system, which is prepared by the common sol-gel method or solid-state method with a high calcination temperature of 900° to 1200°C (12, 23, 24). In combination with electrochemical impedance spectroscopy (EIS) and density functional theory (DFT) calculations, we demonstrate that the designed LZSP material with under-coordination Li-ions achieves a bulk ionic conductivity of up to 3.59 × 10⁻³ S cm⁻¹ at room temperature and further performs excellent electrochemical, thermal, and air stability, which shows potential promising for practical application. The present work opens an innovative avenue to design new solid electrolytes by skeleton-retained cationic exchange approach.

RESULTS

Synthesis and local coordination of Li⁺ ions

The NASICON-type superionic conductor NZSP has both relatively high sodium ionic conductivity, ~10⁻⁴ S cm⁻¹, and excellent structural stability with strong resistance against air and exceptional thermal stability (25, 26). Previous studies reveal that two-thirds of Na⁺ ions occupy the hexa-coordinated sites in the NZSP lattice structure, while the others occupy the octa-coordinated sites (25). In the three-dimensional (3D) channels enclosed by SiO₄⁴⁻/PO₄³⁻ and ZrO₆⁸⁻ polyhedrons, the hexa-coordinated Na⁺ ions contribute to the ionic conductivity by following the migration path of occupied octahedrons and unoccupied tetrahedrons. However, the octa-coordinated Na⁺ ions perform poor transport activity. Therefore, the structure-stable NZSP is used as a precursor to synthesize the corresponding solid electrolyte of LZSP through a skeleton-retained cationic exchange approach.

The sodium superionic conductor NZSP was synthesized by a sol-gel method (27). To accomplish full cationic exchange from Na⁺ to Li⁺, two basic principles about the selection and usage of solid electrolyte precursor, liquid carrier, and lithium compound [NZSP, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl) imide (EMIIM), and bis(trifluoromethane) sulfonimide lithium (LiTFSI; Li⁺ cation coordinating with the N element of the TFSI⁻ anion), respectively] should be satisfied: (i) The selected liquid carrier (EMIIM in this work) is capable of dissolving the lithium compound (LiTFSI in this work) and simultaneously would not dissolve the solid electrolyte precursor; (ii) except for cation exchange, no other chemical reaction takes place. EMIIM and LiTFSI are selected as the solution environment and lithium source, respectively, to drive the cation exchange process. The operation temperature and concentration difference are intrinsically two key driving forces for promoting the cation substitution. Therefore, optimizing concentration difference and operation temperature is of great importance to balance in exchange effectiveness and damaging the skeleton of the solid electrolyte precursor due to inadequate and excessive additive. As shown in fig. S1, Na⁺ ions inside NZSP are thoroughly replaced by Li⁺ ions within LiTFSI dissolved EMIIM at 453 K (NZSP is not soluble in EMIIM). Unlike the commonly adopted molten salt ion-exchange method that requires high-temperature calcination (>673 K) (28), this approach can be conducted at a relatively low temperature (≤453 K), giving rise to the ability to restrain phase transition and keep the pristine framework. The usage of liquid carrier, ionic liquid—an essential Li⁺ ionic conductor, enables the fast removal of Na⁺ ions and continuous entry of Li⁺ ions, where liquids without ionic conductivity (e.g., water) may fail. In addition, the NZSP powders are more readily dispersed evenly in ionic liquids than solidified Li⁺ carrier, which further facilitates the Li⁺/Na⁺ ionic exchange.

The textures of “precursor” NZSP and “product” LZSP nanocrystals are determined by diffraction techniques and Rietveld refinement analysis (Fig. 2). The refined powder synchrotron x-ray diffraction (XRD) and neutron powder diffraction (NPD) patterns of NZSP and LZSP nanopowders (Fig. 2, A and B) crystallize with a monoclinic phase, which belongs to the crystal group of C12/c1 (space group #15). In the locally amplified synchrotron XRD patterns in Fig. 2A (see untruncated data in fig. S2), the peaks of (200) and (400) as well as the (020) and (021) facets all shift to higher angles from NZSP to LZSP, manifesting the lattice contraction of the a and b axis (a axis: 15.6 → 14.9 Å; b axis: 9.1 → 8.6 Å), respectively. Compared to those peaks, the signal of (111) facet just shows a less offset degree, corresponding to the slight elongation along the c axis (9.2 → 9.3 Å). NPD was then used to investigate the coordination evolution of conductive ions during the replacement of Na⁺ ions with Li⁺ ions. The NPD patterns of NZSP and LZSP (Fig. 2B) are deconvoluted by Rietveld refinements, from which the Wyckoff sites of each atom and the structural parameters consistent with the above results obtained from synchrotron XRD (tables S1 to S4). Particularly, the NPD technique is powerful in revealing the accurate atomic coordination of light elements (e.g., H and Li) (29, 30). Three intense diffraction peaks [(200), (021), and (130) facets] aroused by Na⁺ ions and Li⁺ ions are extracted (Fig. 2B and fig. S3). These characterizations show that the retained skeleton performs a little contraction to accommodate the small size of Li⁺ ions. Scanning electron microscopy (SEM) images (Fig. 2B, inset) exhibit the similar sizes of NZSP and LZSP particles (around 600 nm), indicating the maintained microscopic structure at the submicrometer level during cationic exchange. Energy-dispersive x-ray spectroscopy shows a homogeneous distribution of all constituent elements for NZSP and LZSP solids (fig. S4).

Fig. 2. — (A) Refined powder synchrotron XRD and (B) NPD patterns of NZSP and LZSP powders with the Rietveld method. The SEM images of NZSP and LZSP are inserted in (B). All these patterns are recorded at room temperature. (C) Retained polyhedral skeletons containing the evolution path of Na⁺ ions to Li⁺ ions. (D) Evolution of Na⁺ ion to Li⁺ ion polyhedrons within unchanged skeleton.

The retained skeleton structure is further supported with ¹⁷O solid-state nuclear magnetic resonance (ssNMR), which is a high-sensitive technique to characterize the local structure of oxides at the atomic level (31, 32). As shown in fig. S5, their alike resonances observed in the ¹⁷O ssNMR spectra show that NZSP and LZSP crystals have a similar skeleton structure. In the skeleton structure, Wyckoff sites of Zr, Si/P, and O ions fully occupy the Wyckoff sites of 8f, 4e/8f, and 8f, respectively (figs. S6 and S7 and tables S1 and S2). In contrast, Na⁺ and Li⁺ occupancy sites in NZSP and LZSP exhibit an obvious difference, respectively. For NZSP, Na⁺ ions are distributed in three Wyckoff sites, fractional occupancy 4d (80%), full occupancy 4e (100%), and 8f (60%), respectively, corresponding to hexa-coordinated Na^I, octa-coordinated Na^II, and hexa-coordinated Na^III (fig. S2 and table S1) (22, 25). These high-coordinated polyhedrons with Na⁺ occupancy are connected with under-coordinated tetrahedrons, forming 3D migration channels such as -octahedron-tetrahedron-octahedron-, -dodecahedron-tetrahedron-dodecahedron-, and, -octahedron-tetrahedron-dodecahedron-. When cationic exchange is fully accomplished, Li⁺ ions either invade Na⁺-occupied polyhedrons (Li^II → Na^II) or create pioneering occupancy in tetrahedrons following the migration channels of -octahedron-tetrahedron (Li^IV)-octahedron- and -dodecahedron-tetrahedron (Li^IV)-dodecahedron-. These Li⁺ ions in polyhedrons are relaxed into equivalent under-coordination structures with penta-coordinated Li^II and tetra-coordinated Li^III, Li^IV, and Li^V sites (fig. S7 and table S2). Our XRD and NPD analysis indicates that cationic exchange induces coordination transformation from high-coordinated occupancy (hexa- and octa-coordinated) of Na⁺ ions into under-coordinated occupancy (tetra- and penta-coordinated Li⁺) of Li⁺ ions. Except for 6% occupancy Na^IIIO₆ → Li^IIIO₄, most of the NaO₆ octahedrons become vacant and Li⁺ ions are fully occupied in the tetrahedrons connected with two octahedrons. The Li⁺ replacement makes 100% occupancy Na^IIO₈ dodecahedrons into 43.8% occupancy Li^IIO₅ (V denotes vacancy site; fig. S7). As shown in Fig. 2 (C and D), the ionic substitution from Na⁺ to Li⁺ ions does not result in skeleton structure change. However, Na⁺ ions in NZSP occupy high-coordination structures (hexa-/octahedral sites), while exchanged Li⁺ ions in LZSP preferably occupy under-coordination structures such as tetrahedron and pentahedron. Their occupancy structure stability is further discussed in the DFT calculations.

Detailed coordination evolution and ion transport from Na⁺ ions to Li⁺ ions during the cationic exchange were studied through quantitative ²³Na ssNMR and DFT calculations. As the process of Li⁺ ions substituting Na⁺ ions undergoes, the peaks in the ²³Na ssNMR spectra move from high frequencies to low frequencies in fig. S8, which means that under-coordinated Na⁺ ions are more preferential to be substituted by Li⁺ ions than high-coordinated ones. The NMR results are in accord with the thermodynamic calculations in fig. S9, in which the formation energies of Li⁺-substituted under-coordinated Na⁺ ions (Na^I sites and Na^III sites) are about 0.06 eV lower per Li⁺-substituted Na⁺ than those of Li⁺-substituted high-coordinated Na⁺ ions (Na^II sites). In addition, except for NZSP and LZSP, two intermediate compounds, LiNa₂Zr₂Si₂PO₁₂ and Li₂NaZr₂Si₂PO₁₂, were further identified by controlling exchange temperature and time, and then tested with EIS (fig. S10). The presence of intermediates indicates that the skeleton-retained cationic exchange approach can also be used to develop hybrid inorganic superionic conductors (see figs. S10 to S14 and more discussions in text S1).

Ionic conductivity of the LZSP solid electrolyte

Before electrochemical tests, the content of unswapped Na⁺ ions and residual ionic liquid was determined to evaluate their potential influences. As shown in fig. S15 and table S5, there are no detectable Na, N, and F relevant impurity; their potential influence on electrochemical performances is therefore not considered further. The ionic conductivity of LZSP solid electrolyte was subsequently tested with EIS. In Fig. 3A, the Nyquist plots record from 10° to 60°C comprised one semicircle at the high- to medium-frequency region and a tail at the low-frequency region, which are attributed to the impedance of grain boundary (R_gb) and the Li⁺ transfer resistance between electrolyte and Au blocking electrodes. The semicircle corresponding to the bulk resistance (R_bulk) is missing, which is limited by the frequency measuring range. The values of R_bulk and R_gb, however, can be fitted with an equivalent circuit of the form R_bulk, R_gb, Q_gb, and Q_electrode, where R is the resistance and Q is the constant phase element (10, 33). LZSP pellets were used to assemble Au/LZSP/Au symmetric cells. Generally, to densify powdered ceramic solid electrolytes, the most commonly used approach is to press the powders into pellets and then sinter the pellets under high temperatures (typically 1200°C or higher) (19, 34). However, thermal analysis indicates that LZSP powders would undergo phase transition after 742°C (fig. S16). Although its phase stability temperature of 742°C is lower than that (1000°C) of usual NASICON-type solid electrolytes (12, 35), this temperature is much higher than the reported cathode dissociation temperature in the previous literature (36). Therefore, a hot-pressing sintering process at 700°C for 1 hour under a fixed pressure of 70 MPa was carried out to prepare LZSP pellets (the synchrotron XRD and ¹⁷O ssNMR spectra in fig. S17 prove that the structure of LZSP annealed under 700°C keeps unchanged). The prepared LZSP pellet (fig. S18) is characterized to have a thickness of 2.4 mm and a relative density of about 83% (the porosity is 17%). At 20°C, it exhibits the bulk and total Li⁺ conductivities of 3.59 × 10⁻³ (fig. S19) and 8.75 × 10⁻⁶ S cm⁻¹, respectively. When temperature is increased to 60°C, the bulk and total Li⁺ conductivities of LZSP are enhanced to 9.0 × 10⁻³ and 1.64 × 10⁻⁵ S cm⁻¹, respectively. Two approaches could be applied to make denser pellet and improve total ionic conductivity (37–39). On the one hand, we prepared composite pellets for solid-state batteries, where SN and LiTFSI were added to fill the pores between LZSP particles. With a higher relative density of 95%, the total ionic conductivity increases to 8.71 × 10⁻⁴ S cm⁻¹ at 20°C, as shown in fig. S20. On the other hand, the denser LZSP pellet could be prepared through advanced vacuum hot-pressing technique. The outstanding conductivity benefits from the expanded bottleneck sizes and the improved Li⁺ transportation. Moreover, the ionic conductivity increases in line with elevated temperature, which accords with the Arrhenius curves (40). A reliable activation energy for the mobility of Li⁺ ions in LZSP is accordingly normalized to be 0.21 eV (Fig. 3B). The comparative study indicates that LZSP has the top value of bulk ionic conductivity among all reported NASICON-type solid electrolytes and is superior to other undoped oxide solid electrolytes (which are marked with horizontal lines in Fig. 3C).

Fig. 3. — (A) Nyquist plots of LZSP pellets from 10° to 60°C. (B) Arrhenius plot of the ionic conductivity of LZSP. (C) Summary of bulk ionic conductivities of oxide solid electrolytes at room temperature; the materials are extracted from previous studies whose details are displayed in table S6.

Diffusion mechanism and kinetics

To reveal the influence mechanism of under-coordinated Li⁺ configuration (tetra-/penta-coordinated Li⁺ ions) on ionic conductivity of LZSP, DFT calculations combined with ab initio molecular dynamics (AIMD) simulations were carried out to characterize Li⁺ occupancy, structural stability, and ionic conductivity of LZSP. The structural evolution of LZSP was investigated in fig. S14. Compared with the LZSP configuration of Li⁺ ions substituting Na⁺ ions in NZSP without structural relaxation, the LZSP configuration within structural relaxation has a further reduced volume with the contraction from 1.14 to 10.2%. Meanwhile, some of the Li⁺ ions, which take the initial sites of hexa-coordinated Na^I sites and Na^III sites, move to the sites of tetra-coordinated Li^IV sites and the other Li⁺ ions move slightly off the sites of octa-coordinated Na^II sites to form penta-coordinated Li^II sites with Wyckoff site transformation from 4e to 8f (see fig. S21 and table S7). Compared with hexa-coordinated Li⁺ ion in traditional phosphatic solid electrolytes, the coordination of penta-/tetra-coordinated Li⁺ ions in produced LZSP is decreased. The coordination reduction of Li⁺ ions, accompanied by lattice contraction, leads to a 0.19 eV/formula lower free energy. Furthermore, different LZSP configurations, by tuning Li^II occupancies from 50 to 31.25% with a constant difference of 6.25%, are built to screen the thermodynamically stable structure. The configuration with 43.8% occupancy Li^II sites is found to have the lowest free energy, of which the ab place is compressed and the c axis is expanded compared with other LZSP configurations (fig. S14). The kinetic stability of screened LZSP configuration was investigated by mean square displacement (MSD) from AIMD simulations in canonical ensemble (NVT). As the temperature increases from 300 to 1000 K, the MSDs of Si/P and Zr atoms are near invariable and the maximal MSD of O atoms is ~0.2 Å² (fig. S22). Furthermore, the phonon spectrum of screened LZSP configuration was calculated. As shown in figs. S23 and S24, the imaginary frequencies are largely ascribed to Li atoms and slightly ascribed to O atoms, which have electrostatic interactions with Li atoms. As a result, the frame of screened LZSP configuration with 43.8% occupancy Li^II sites is stable and is used to investigate the Li⁺ ionic conductivity of LZSP.

To reveal the predominance of the under-coordinated structure in high-conductivity solid electrolytes, we calculated Li⁺ and Na⁺ migration barriers within LZSP and NZSP in the dilute limit of single Li⁺/Na⁺ and without other cations presented in corresponding compounds, respectively. The migration paths with corresponding relative energies of NZSP and LZSP are presented in Fig. 4 (A and B), respectively. An obvious discrepancy is different coordination structures of low-energy intermediates. The low-energy intermediates in NZSP have an octa-/hexa-coordinated structure character, whereas those in LZSP are changed into penta-/tetra-coordinated sites. In terms of calculated potential energy profiles, NZSP presents an isolated Na^IV-Na^I-Na^IV-Na^III migration channel in which Na⁺ ions are difficult to surmount the migration barrier of 0.53 eV into Na^II sites. The nonactivity of 100% occupancy Na^II is further characterized by AIMD simulations at 600 K in Fig. 5. In a notable contrast, the Li^II sites with 43.8% occupancy are fully activated by reducing the migration barrier. The Li⁺ migration barrier (0.29 eV) from the penta-coordinated Li^II site to the tetra-coordinated Li^IV site is 0.15 eV lower than the corresponding Na⁺ migration barrier (0.44 eV) from the octa-coordinated Na^II site to the tetra-coordinated Na^IV site. Intrinsically, the active effect in LZSP plays an important role in not only making the run-through channel network structure but also increasing mobile Li-ion, both of which can effectively enhance ionic conductivity.

Fig. 4. — (A) Energy barriers for single-ion migration of Na⁺ ion following the Na^II-Na^IV-Na^I-Na^IV-Na^III trajectory. (B) Energy barriers for single-ion migration of Li⁺ ion following the Li^II-Li^IV-Li^I-Li^IV-Li^III trajectory. The blue and purple balls stand for Na⁺ ions and Li⁺ ions, respectively. The olive, light green, pink, and sky-blue polyhedrons identify the Na^IIO₈ dodecahedron, Li^IIO₅ pentahedron, Na^IVO₄/Li^IVO₄ tetrahedrons, and Na^IO₆/Li^IO₆/ Na^IIIO₆/Li^IIIO₆ octahedrons, respectively.

Fig. 5. — (A) Diffusion pathways in monoclinic NZSP at 600 K. (B) Diffusion pathways in monoclinic LZSP at 600 K. (C) Arrhenius plot of Na⁺ diffusivity D as a function of temperature T in NZSP. (D) Arrhenius plot of Li⁺ diffusivity D as a function of temperature T in LZSP.

The lower migration barrier should be attributed to a suitable bottleneck size for migration ions. Previous studies show that the transition state structure of ionic conduction commonly corresponds to Li⁺ passing through the bottleneck between two polyhedrons (27). According to the Shannon effective ionic radius table, Na⁺ and Li⁺ ions have obviously different critical sizes of the bottleneck, 2.37 Å for Na-O and 1.94 Å for Li-O (41). Those migration paths, of which the bottlenecks are smaller than this critical size, would block the migration of Na⁺/Li⁺ ions. Since cationic exchange leads to little effect on the bottleneck size, 2.16 Å for the migration path of Na^II-Na^IV and 2.13 Å for the migration path of Li^II-Li^IV, Li⁺ ions are capable of passing through the bottleneck but Na⁺ ions fail. The comparison shows that Na^II migration is inactive in NZSP but exchanged Li^II migration is active in LZSP.

In comparison, the transition state along migration paths Li^IV-Li^I-Li^IV and Na^IV-Na^I-Na^IV exhibits clear different structures, although they have a similar barrier height (both are 0.17 eV). The former corresponds to the bottleneck structure between tetrahedron and octahedron, whereas the latter corresponds to the hexa-coordinated Li^I structure. Their bottleneck sizes are very similar, 2.37 Å for the migration path of Na^IV-Na^I and 2.38 Å for the migration path of Li^IV-Li^I. The transition state structure change shows that such a large-size bottleneck does not inhibit Li⁺ migration. This firstly reported migration mechanism, enlarging the bottleneck size to reduce the migration barrier, is of much importance to design the structure of solid electrolytes. Recently, Zhang et al. (27) reported the high-energy site of Na^V in NZSP by increasing the Na⁺-ion concentration. In this work, we also found low-occupancy Li^V sites in LZSP, originating from unoccupied Li^II sites. These high-energy sites of Li^V increase the coulombic repulsions of Li⁺ ions following the trajectory path of -octahedron-tetrahedron (Li^IV)-octahedron- and, depending on the concentration of high-energy sites, enhance the correlated migration of Li⁺ ions.

Direct comparison for two DFT-calculated potential energy profiles (Fig. 5) demonstrates that cationic exchange has made a notably lower migration barrier in under-coordinated Li^II-Li^IV than in high-coordinated Na^II-Na^IV. To verify the activation effect, AIMD simulations at a temperature of 600 K were performed to reveal the migration path change induced by cationic exchange. The Na⁺ and Li⁺ diffusion pathways of NZSP and LZSP from AIMD simulations under the same simulation conditions are presented in Fig. 5 (A and B), respectively. It is obvious that octa-coordinated Na^II sites with 100% occupancy exhibit negligible ionic migration into the Na^I-Na^III pathway. But hexa-coordinated Na^I and Na^III with fractional occupancy present continuous and intertwined diffusion pathways, indicating the 2D migration mechanism. In contrast, LZSP presents the 3D migration mechanism since Li^II sites in the corresponding position of Na^II become active by forming the Li^II-Li^IV migration pathway. The activation effect is attributed to the size of the bottleneck located in the under-coordinated Li^II-Li^IV segment, which is 0.19 Å larger than the sum of Li⁺ and O²⁻ radii.

According to extensive AIMD simulations at different temperatures, diffusion lengths of Na⁺ and Li⁺ ions at different sites in NZSP and LZSP are correlated with simulated temperatures. The fitted activation energies for different sites are also presented in Fig. 5 (C and D). It is obvious that the activation energies from AIMD in Fig. 5 are much lower than the migration barrier of the single-ion direct-hopping mechanism in Fig. 4 because the correlated migration is the preferred conduction mechanism in LZSP and NZSP, which was studied by Zhang et al. (27). The activation energy of Na^II (0.22 eV) is nearly two times of those of Na^I and Na^III (0.12 eV). However, the activation energy of Li^II is comparable with those of Li^III, Li^IV, and Li^V. Octa-coordinated Na^II sites with full occupancy only maintain equivalent vibration and do not exhibit the migration path. In contrast, the Li^II sites in the similar position are turned into active ion migration along the Li^II-Li^IV path, which should be attributed to fractional occupancy and lower migration barrier of Li^II. The activation effect plays an important role in not only turning the 2D into 3D migration path but also increasing the percentage of mobile ion rising from 67% in NZSP to 100% in LZSP. As a result of increased mobile ion and decreased migration barrier, the ionic conductivity of LZSP is theoretically predicted as high as 1.46 × 10⁻² S cm⁻¹.

In addition to thermal stability and ionic conductivity, other properties such as chemical stability against air and the tolerance of voltage are also investigated under electrochemical conditions. At room temperature, the LZSP powders are aged for 0, 100, and 200 hours within air to test the environmental stability. The ⁶Li ssNMR, powder synchrotron XRD, and C 1s x-ray photoelectron spectra (XPS) of these samples were recorded afterward and shown in fig. S25. No Li₂CO₃ relevant signals (a typical production as a result of air erosion) (42) were observed whenever the aged period was manifesting the excellent stability against air (see more discussion in text S2). Similar to the robust NZSP with the advantage of commendable air survivability (the exchange of protons with the surfaces of NZSP is tough, which prevents air-exposed NZSP powders from deteriorating) (43, 44), the derived LZSP electrolyte inherits its excellent stability against moisture and CO₂ and requires no more extra seal measures if used in practical storage and transportation. To further reveal electrochemical stability, first-principles thermodynamic calculations were used to identify the thermal phase equilibria at different potentials for LZSP. According to our calculated reaction enthalpies, the LZSP is identified to have an electrochemical stability window of ~4 V (fig. S26), which is the top value among all the oxide solid electrolytes. This wide electrochemical window may be attributed to a high endothermicity (4.58 eV) of charge reaction formation of SiO₂ + P₂O₅ + ZrO₂ + O₂ and a low exothermicity (0.48 eV) of discharge reaction formation of Li₇Si₃ + Li₃P + Zr₃O + Li₂O.

Electrochemical test of solid-state batteries

To better eliminate the grain boundary impedance among LZSP nanoparticles, a thermal-assisted cold sintering approach was used to prepare dense LZSP composite pellets (45, 46). Furthermore, to negate the high interfacial resistance between the electrolyte and the electrode, soft polyethylene oxide–ethylene carbonate (PEO-EC) buffer layers were coated on the two surfaces of the LZSP composite pellets in the solid-state cells through an in situ solidification method (see more discussion in text S3 and figs. S27 to S30). A Li/LZSP/Li symmetric cell was fabricated to demonstrate the Li-ion transport capability of the LZSP solid electrolyte. As presented in Fig. 6A, lithium plating/stripping in the symmetrical Li/LZSP/Li cell remains stable for 2000 hours at room temperature with a current density of 0.1 mA cm⁻², indicating an excellent stability against lithium metal. In Fig. 6B, measured by an Au/LZSP/Li cell, the electrochemical window of the solid electrolyte is stable up to 6 V versus Li/Li⁺, which is enough for the requirement of lithium batteries (all the subsistent batteries can withstand a charging voltage of up to 5 V) (47).

Fig. 6. — (A) Cycling performance of a Li/LZSP/Li symmetric cell tested at a current density of 0.1 mA cm⁻². (B) Current-voltage curve of an Au/LZSP/Li cell. (C) Initial galvanostatic charge and discharge profile of a LiNi_0.5Co_0.2Mn_0.3O₂(NCM523)/LZSP/Li cell. (D) Cycling performance of a NCM523/LZSP/Li cell. (E) Rate performance of a NCM523/LZSP/Li cell.

High ionic conductivity, good stability against lithium metal and air, and wide stability window make LZSP one of the best candidate electrolytes [e.g., Li₇La₃Zr₂O₁₂ (LLZO) (10), Li₁₀GeP₂S₁₂ (6, 48), and Li₃M(M = Y, Sc, In)Cl₆ (49–53)] for developing commercial solid-state lithium batteries (table S8). A full cell containing the LZSP electrolyte pellet, the buffer layers, the NCM523 cathode, and the anode of Li metal was then designed to make a demonstration. Figure 6C shows the initial charge and discharge curves of the NCM523/LZSP/Li cell at 0.1 C (0.1 C = 15 mA g⁻¹) at room temperature. The discharge specific capacity and coulombic efficiency of the first cycle are 162.0 mAh g⁻¹ and 85.8%, respectively. After 100 cycles, there is a minor capacity fading for the cell and it delivered a specific capacity of 146.0 mAh g⁻¹, equal to 90.1% of the initial discharge capacity (Fig. 6D), which surpasses the relevant performance of NCM523-based (cathode) and Li metal–based (anode) batteries using liquid electrolytes (fig. S31). Besides, rate performance was also tested at the current rate of 0.2, 0.5, 1.0, and 2.0 C, respectively, and high specific discharging capacities of 157.5, 141.8, 116.2, and 96.9 mAh g⁻¹ were maintained (Fig. 6E). Compared to previously reported NCM523/Li cells based on other solid electrolytes (table S9), without any liquid wetting, the rate capacity, cycling performance, and discharge-specific capacity of this NCM523/LZSP/Li solid-state batteries are in the highest tier.

The synthesis approach of skeleton-retained cationic exchange could be commonly used to produce more solid electrolyte, even extensive inorganic materials, by controlling suitable reaction conditions. Several reactions such as Na₃La(PO₄)₂ (NLP) → Li₃La(PO₄)₂ (LLP) and Li_1.3Al_0.3Ti_1.7(PO₄)₃ (LATP) → Na_1.3Al_0.3Ti_1.7(PO₄)₃ (NATP) were attempted and exhibit effective cationic exchange. As shown in fig. S32, after the cationic exchange, the products of LLP and NATP respectively kept the skeleton structures of NLP and LATP completely. Together with detailed LZSP characterizations, it is expected that the approach could be used to synthesize new inorganic compounds with cationic composition and structure change. Its success largely depends on the rational selection of the solid electrolyte precursor, liquid carrier, and lithium compound.

DISCUSSION

In conclusion, skeleton-retained cationic exchange approach is used to produce a high-performance solid electrolyte with under-coordinated conduction Li⁺ ions and expanded bottleneck sizes. Using the NASICON-type solid electrolyte NZSP as a precursor, an unreported solid electrolyte, LZSP, with under-coordinated Li⁺ ions is harvested. The imported lithium cations acclimatize themselves to the relatively large skeleton by the reduction of Li coordination, resulting in low migration barriers for lithium cations to hop along 3D continuous migration channels. As a result, the bulk ionic conductivity of LZSP is up to 3.59 × 10⁻³ S cm⁻¹ at room temperature, which is the top value among the current oxide solid electrolytes. In addition, the LZSP material not only shows satisfactory environmental survivability but also performs wide electrochemical window and long stability against Li metal in the use of LZSP-based solid-state batteries, indicating it as an advanced solid electrolyte with commercial promise. The present study indicates that the synthesis approach of skeleton-retained cationic exchange not only is effective in regulating the coordination structure of diffusion ions for improving ionic conductivity but also could be used to make new inorganic materials.

MATERIALS AND METHODS

Preparation of NZSP

The synthesis of NZSP powders is referenced from Zhang et al. (27). Three milliliters of tetraethyl orthosilicate, 10 ml of water, and 5 ml of ethanol were mixed and then stirred at room temperature for 10 min. After adding in 50 ml of water and 17 g of citric acid, the pH value of this mixed solution was controlled at 1.5 with HNO₃ dropwise. Stirring at 333 K for 1 hour, a solution consisting of 5.132 g of ZrO(NO₃)₂·xH₂O, 2.037 g of NaNO₃, and 1.055 g of (NH₄)₂HPO₄ was added while stirring at 353 K. The resulting solution was then transferred into an oil bath pan to evaporate residual water at 353 K for 24 hours. The obtained yellow dried gel was ball-milled at 600 rpm and then calcined at 1073 K in air. After grinding through an agate mortar, white NZSP powders were harvested.

Process of skeleton-retained cation exchange

In a typical skeleton-retained cation exchange procedure, 22.996 g of LiTFSI was dissolved in 40 ml of EMIIM in an Ar-filled glove box. The mixture was stirred at 333 K for 30 min and then cooled down to room temperature. Afterward, 2.829 g of NZSP was mixed with the above solution. The resulting white suspension was then sealed in a 100-ml reactor and heated in an oven at 453 K for 24 hours with a swing speed of 50 rpm. Subsequently, the white sediment was centrifuged, washed with ethanol, and dried at 353 K for 6 hours. All these above steps should be performed three times to yield pure LZSP powders (without residual sodium cation). After calcination at 773 K for 5 hours to remove the possible residual EMIIM, the target LZSP material is harvested. The exchanged ionic liquid can be reused through renewable process of zeolite adsorption, which is favorable to reduce cost of scale-up production.

Process of ¹⁷O isotopic labeling

In the ¹⁷O isotopic labeling process, 200 mg of NZSP or LZSP was sealed in a glass tube and then annealed at 673 K under 1 × 10⁻⁴ torr for 3 hours to get rid of surface-adsorbed impurities. Cooling down to room temperature, 90% ¹⁷O-enriched O₂ gas (50 mbar, Isotec Inc.) was introduced and the glass tube was sealed again to heat at 673 K for 24 hours. Last, the samples were evacuated at 1 × 10⁻⁴ torr for 30 min to remove residual ¹⁷O-enriched O₂ gas.

Characterization

Synchrotron XRD measurements were performed at the Beamline BL14B1 of Shanghai Synchrotron Radiation Facility (SSRF) in China. A medium-energy (18 keV, k = 0.6887 Å) x-ray beam (200 μm by 200 μm) is used. The NPD experiments were carried out at room temperature using high-resolution neutron powder diffractometer at China Mianyang Research Reactor. The incident beam with a wavelength λ = 1.8846 Å was vertically focused by a Ge (511) monochromator at a fixed take-off angle of 120°. Diffraction patterns were collected from 10° to 150° with a step increment of 0.06°. ²³Na, ¹⁷O, and ⁶Li magic angle spinning NMR (MAS NMR) measurements were recorded on a 9.4-T Bruker Avance III 400 spectrometer at Larmor frequencies of 105.8, 54.2, and 58.8 MHz, respectively. Dry powders to be measured were packed into 4.0-mm ZrO₂ rotors in a N₂-filled glove box. ²³Na, ¹⁷O, and ⁶Li NMR shifts were referenced to H₂O at 0.0 parts per million (ppm), NaCl at 7.21 ppm, and LiCl at 0 ppm, respectively. Thermal gravimetric analysis data were obtained with a NETZSCH STA 449C instrument. XPS were recorded on Thermo ESCALAB 250 X with Al Kα (1486.6 eV) as core excitation. Binding energies expressed in XPS were corrected by referencing C 1s as 284.8 eV.

Computational methods

First-principles calculations were used to calculate the structural and electronic properties as implemented in the Vienna Ab initio Simulation Package (54). The plane-wave projector-augmented wave method (55, 56) with an energy cutoff of 400 eV and Monkhorst-pack k-meshes (57) were used to investigate the structural and transport properties by using generalized gradient approximation with Perdew-Burke-Ernzerh exchange-correlation functional (58). All atomic coordinates and lattice parameters are fully relaxed until the force convergence of 0.01 eV Å⁻¹ and the energy convergence of 10⁻⁴ eV atom⁻¹ are achieved. AIMD calculations were carried out in the canonical ensemble (NVT) using a Nosé thermostat at 300, 600, 800, 1000, and 1200 K with a time step of 3 fs for 30 ps to calculate MSDs and at 600 K for an appropriate time to investigate the diffusion pathways of conductive ions (59). AIMD and climbing image nudged elastic band (CI-NEB) (60) calculations revealed the transport properties of Na⁺ and Li⁺ ions via a correlated migration mechanism.

Fabrication of LZSP pellets

A hot-pressing sintering process was applied to obtain pure LZSP pellets. The LZSP powders were placed into the mold for dry pressing and sintered at 700°C under a fixed pressure of 70 MPa for 1 hour. After natural cooling to room temperature, the LZSP electrolyte pellet with a diameter of 10 mm was obtained. To better eliminate the grain boundary impedance among LZSP nanoparticles in the pure LZSP pellets, a thermal-assisted cold sintering approach was used to prepare dense LZSP composite pellets (45, 46). First, succinonitrile (SN) and LiTFSI with a mass ratio of 85:15 were mixed uniformly. Second, the LZSP powders were added and ground for 30 min. Last, the composite powders [90 weight % (wt %) LZSP, 10 wt % SN, and LiTFSI] were pressed at 130°C for 1 hour, and 810-MPa uniaxial pressure was applied. After natural cooling to room temperature, the LZSP composite pellet with a diameter of 10 mm was obtained. All operations were carried out in a drying room with a dew point at −40°C.

Pure LZSP pellets prepared by the hot-pressing sintering process were used to measure the ionic conductivities. LZSP composite pellets prepared by the thermal-assisted cold sintering approach were used to measure other electrochemical properties.

Electrochemical tests

The ionic conductivities of the electrolyte pellets were calculated from Nyquist plots, which were performed on an electrochemical workstation (Bio-Logic, VSP-300) with an AC amplitude of 50 mV from 7 MHz to 0.1 Hz by sputtering Au blocking electrodes on both sides of the pellets. The bulk and total ionic conductivities were obtained by fitting results using the ZView software. The ionic conductivities were calculated through σ = L/(R ∙ S), where σ, L, R, and S denote the ionic conductivity, the thickness of the pellet, the resistance, and the effective area of the electrode, respectively. For the Li/LZSP/Li symmetric cells, to improve the interface contact between the electrolyte and electrode, a PEO-EC buffer layer precursor solution was prepared by dispersing PEO (M_w = 600,000, Sigma-Aldrich) and EC (99.0%, Adamas) in dimethyl carbonate and stirred for 30 min at 60°C. The PEO-EC buffer layer precursor solution was casted onto on one side of the LZSP composite pellet and naturally volatilized for 12 hours to remove the dimethyl carbonate solvent, and two lithium foils were pasted on the buffer layers. The Li/LZSP/Li symmetric cells were investigated using a LAND battery tester (CT2001A, Wuhan LAND Electronics) under a current density of 0.1 mA cm⁻².

The Au/LZSP/Li coin cells were assembled with a lithium foil pasted on the buffer layer as the counter electrode and a gold film sprayed on the other side of the pellet as the working electrode. The electrochemical window measurement was scanned in a range of −0.5 to 6.0 V at 1 mV s⁻¹ at room temperature using a CHI604E electrochemical workstation.

The charge-discharge properties were evaluated by NCM523/LZSP/Li cells with soft PEO-EC buffer layers adhered to both sides of the LZSP composite pellet. The NCM523 cathode was composed of 77 wt % NCM523, 10 wt % Super P, 10 wt % polyvinylidene difluoride, and 3 wt % LiTFSI. The NCM523/LZSP/Li cell was tested between 2.8 and 4.3 V at current densities of 15, 30, 75, 150, and 300 mA g⁻¹.

Acknowledgments

We would like to thank Y. Xia and W. Feng at Fudan University, T. Liu at Tongji University, X. Zhang at Shanghai Institute of Applied Physics, and X. Xia at Nanjing University of Science and Technology for their invaluable discussions and help in this work.

Funding: This work was financially supported by the National Key Research and Development Program of China (no. 2018YFB0905400), National Natural Science Foundation of China (nos. 21973107, 21972066, 22133005, and 22103093), Shanghai Academic Research Leader Program (20XD1404100), Shanghai Scientific Research Program of China (no. 19511107700), Shanghai Rising-Star Program (no. 18QB1402600), Shanghai Sailing Program (18YF1427300), and Science and Technology Commission of Shanghai Municipality (18511109400 and 18520723000).

Author contributions: L.Z., Y. Wang, J.C., J.L., and W.T. conceived and developed the idea of this project. L.Z., J.C., and W.L. carried out the synthesis of NZSP and LZSP materials. L.Z. and J.C. collected the synchrotron XRD data and analyzed them with Rietveld refinement. Y.X., F.W., and J.C. collected the NPD data and analyzed them with Rietveld method. Y. Wang, T.W., and J.L. conducted the DFT calculations. J.C. and L.P. performed ¹⁷O isotope enrichment and collected and analyzed all the NMR spectra. L.Z., J.W., S.H., W.L., M.W., Y. Wu, Y.Z., and W.L. performed the electrochemical tests. L.Z., Y. Wang, J.C., L.P., J.L., L.C., and W.T. wrote the manuscript, and all authors discussed the experiments and final manuscript.

Competing interests: The authors declare that they have no competing interests.

Data and materials availability: All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials.

Supplementary Materials

This PDF file includes:

Figs. S1 to S32

Tables S1 to S9

Texts S1 to S3

References

Click here for additional data file.^{(4.9MB, pdf)}

REFERENCES AND NOTES

1.Manthiram A., Yu X., Wang S., Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater. 2, 16103 (2017). [Google Scholar]
2.Gao Z., Sun H., Fu L., Ye F., Zhang Y., Luo W., Huang Y., Promises, challenges, and recent progress of inorganic solid-state electrolytes for all-solid-state lithium batteries. Adv. Mater. 30, 1705702 (2018). [DOI] [PubMed] [Google Scholar]
3.Chen R., Li Q., Yu X., Chen L., Li H., Approaching practically accessible solid-state batteries: Stability issues related to solid electrolytes and interfaces. Chem. Rev. 120, 6820–6877 (2019). [DOI] [PubMed] [Google Scholar]
4.Schwietert T. K., Arszelewska V. A., Wang C., Yu C., Vasileiadis A., de Klerk N. J. J., Hageman J., Hupfer T., Kerkamm I., Xu Y., van der Maas E., Kelder E. M., Ganapathy S., Wagemaker M., Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes. Nat. Mater. 19, 428–435 (2020). [DOI] [PubMed] [Google Scholar]
5.Han F., Zhu Y., He X., Mo Y., Wang C., Electrochemical stability of Li₁₀GeP₂S₁₂ and Li₇La₃Zr₂O₁₂ solid electrolytes. Adv. Energy Mater. 6, 1501590 (2016). [Google Scholar]
6.Kamaya N., Homma K., Yamakawa Y., Hirayama M., Kanno R., Yonemura M., Kamiyama T., Kato Y., Hama S., Kawamoto K., Mitsui A., A lithium superionic conductor. Nat. Mater. 10, 682–686 (2011). [DOI] [PubMed] [Google Scholar]
7.Zhao Y., Daemen L. L., Superionic conductivity in lithium-rich anti-perovskites. J. Am. Chem. Soc. 134, 15042–15047 (2012). [DOI] [PubMed] [Google Scholar]
8.Lü X., Howard J. W., Chen A., Zhu J., Li S., Wu G., Dowden P., Xu H., Zhao Y., Jia Q., Antiperovskite Li₃OCl superionic conductor films for solid-state Li-ion batteries. Adv. Sci. 3, 1500359 (2016). [DOI] [PMC free article] [PubMed] [Google Scholar]
9.Wenzel S., Randau S., Leichtweiß T., Weber D. A., Sann J., Zeier W. G., Janek J., Direct observation of the interfacial instability of the fast ionic conductor Li₁₀GeP₂S₁₂ at the lithium metal anode. Chem. Mater. 28, 2400–2407 (2016). [Google Scholar]
10.Murugan R., Thangadurai V., Weppner W., Fast lithium ion conduction in garnet-type Li₇La₃Zr₂O₁₂. Angew. Chem. Int. Ed. 46, 7778–7781 (2007). [DOI] [PubMed] [Google Scholar]
11.Suzuki N., Inaba T., Shiga T., Electrochemical properties of LiPON films made from a mixed powder target of Li₃PO₄ and Li₂O. Thin Solid Films 520, 1821–1825 (2012). [Google Scholar]
12.Li Y., Zhou W., Chen X., Lü X., Cui Z., Xin S., Xue L., Jia Q., Goodenough J. B., Mastering the interface for advanced all-solid-state lithium rechargeable batteries. Proc. Natl. Acad. Sci. U.S.A. 113, 13313–13317 (2016). [DOI] [PMC free article] [PubMed] [Google Scholar]
13.Kim K. J., Balaish M., Wadaguchi M., Kong L. P., Rupp J., Solid-state Li–metal batteries: Challenges and horizons of oxide and sulfide solid electrolytes and their interfaces. Adv. Energy Mater. 11, 2002689 (2020). [Google Scholar]
14.Deng Y., Eames C., Fleutot B., David R., Chotard J., Suard E., Masquelier C., Islam M. S., Enhancing the lithium ion conductivity in lithium superionic conductor (LISICON) solid electrolytes through a mixed polyanion effect. ACS Appl. Mater. Interfaces 9, 7050–7058 (2017). [DOI] [PubMed] [Google Scholar]
15.Hou M., Liang F., Chen K., Dai Y., Xue D., Challenges and perspectives of NASICON-type solid electrolytes for all-solid-state lithium batteries. Nanotechnology 31, 132003 (2020). [DOI] [PubMed] [Google Scholar]
16.Jian Z., Hu Y.-S., Ji X., Chen W., NASICON-structured materials for energy storage. Adv. Mater. 29, 1601925 (2017). [DOI] [PubMed] [Google Scholar]
17.Ladenstein L., Simic S., Kothleitner G., Rettenwander D., Wilkening H. M. R., Anomalies in bulk ion transport in the solid solutions of Li₇La₃M₂O₁₂ (M = Hf, Sn) and Li₅La₃Ta₂O₁₂. J. Phys. Chem. C 124, 16796–16805 (2020). [DOI] [PMC free article] [PubMed] [Google Scholar]
18.Mei A., Jiang Q.-H., Lin Y.-H., Nan C.-W., Lithium lanthanum titanium oxide solid-state electrolyte by spark plasma sintering. J. Alloys Compd. 486, 16796–16805 (2009). [Google Scholar]
19.Wang C., Fu K., Kammampata S. P., McOwen D. W., Samson A. J., Zhang L., Hitz G. T., Nolan A. M., Wachsman E. D., Mo Y., Thangadurai V., Hu L., Garnet-type solid-state electrolytes: Materials, interfaces, and batteries. Chem. Rev. 120, 4257–4300 (2020). [DOI] [PubMed] [Google Scholar]
20.Lacivita V., Westover A. S., Kercher A., Phillip N. D., Yang G., Veith G., Ceder G., Dudney N. J., Resolving the amorphous structure of lithium phosphorus oxynitride (Lipon). J. Am. Chem. Soc. 140, 11029–11038 (2018). [DOI] [PubMed] [Google Scholar]
21.Wang Y., Richards W. D., Ong S. P., Miara L. J., Kim J. C., Mo Y., Ceder G., Design principles for solid-state lithium superionic conductors. Nat. Mater. 14, 1026–1031 (2015). [DOI] [PubMed] [Google Scholar]
22.Bachman J. C., Muy S., Grimaud A., Chang H.-H., Pour N., Lux S. F., Paschos O., Maglia F., Lupart S., Lamp P., Giordano L., Shao-Horn Y., Inorganic solid-state electrolytes for lithium batteries: Mechanisms and properties governing ion conduction. Chem. Rev. 116, 140–162 (2016). [DOI] [PubMed] [Google Scholar]
23.Gao J., Wu J., Han S., Zhang J., Zhu L., Wu Y., Zhao J., Tang W., A novel solid electrolyte formed by NASICON-type Li₃Zr₂Si₂PO₁₂ and poly(vinylidene fluoride) for solid state batteries. Funct. Mater. Lett. 14, 2140001 (2021). [Google Scholar]
24.Belam W., Sol-gel chemistry synthesis and DTA-TGA, XRPD, SIC and ⁷Li, ³¹P, ²⁹Si MAS-NMR studies on the Li-NASICON Li₃Zr_2-ySi_2-4yP_1+4yO₁₂ (0⩽y⩽0.5) system. J. Alloys Compd. 551, 267–273 (2013). [Google Scholar]
25.Shannon R. D., Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. 32, 751–767 (1976). [Google Scholar]
26.Yang K., Chen L., Ma J., He Y.-B., Kang F., Progress and perspective of Li_1+xAl_xTi_2-x(PO₄)₃ ceramic electrolyte in lithium batteries. InfoMat. 3, 1195–1217 (2021). [Google Scholar]
27.Zhang Z., Zou Z., Kaup K., Xiao R., Shi S., Avdeev M., Hu Y.-S., Wang D., He B., Li H., Huang X., Nazar L. F., Chen L., Correlated migration invokes higher Na⁺-ion conductivity in NaSICON-type solid electrolytes. Adv. Energy Mater. 9, 1902373 (2019). [Google Scholar]
28.Vera V. B., Igor L. S., Ion exchange conversion of solid electrolyte, potassium sodiostannate, into isomorphous metastable sodium stannate. Mendeleev Commun. 26, 246–247 (2016). [Google Scholar]
29.Malavasi L., Fisher C. A. J., Islam M. S., Oxide-ion and proton conducting electrolyte materials for clean energy applications: Structural and mechanistic features. Chem. Soc. Rev. 39, 4370–4387 (2010). [DOI] [PubMed] [Google Scholar]
30.Zhang Z., Shao Y., Lotsch B., Hu Y.-S., Li H., Janek J., Nazar L. F., Nan C.-W., Maier J., Armand M., Chen L., New horizons for inorganic solid state ion conductors. Energ. Environ. Sci. 11, 1945–1976 (2018). [Google Scholar]
31.Chen J., Wu X.-P., Hope M. A., Qian K., Halat D. M., Liu T., Li Y., Shen L., Ke X., Wen Y., Du J.-H., Magusin P. C. M. M., Paul S., Ding W., Gong X.-Q., Grey C. P., Peng L., Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy. Nat. Commun. 10, 5420 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]
32.Chen J., Hope M. A., Lin Z., Wang M., Liu T., Halat D. M., Wen Y., Chen T., Ke X., Magusin P. C. M. M., Ding W., Xia X., Wu X.-P., Gong X.-Q., Grey C. P., Peng L., Interactions of oxide surfaces with water revealed with solid-state NMR spectroscopy. J. Am. Chem. Soc. 142, 11173–11182 (2020). [DOI] [PubMed] [Google Scholar]
33.Van Den Broek J., Afyon S., Rupp J. L. M., Interface-engineered all-solid-state Li-ion batteries based on garnet-type fast Li⁺ conductors. Adv. Energy Mater. 6, 1600736 (2016). [Google Scholar]
34.Han X., Gong Y., Fu K. K., He X., Hitz G. T., Dai J., Pearse A., Liu B., Wang H., Rubloff G., Mo Y., Thangadurai V., Wachsman E. D., Hu L., Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nat. Mater. 16, 572–579 (2017). [DOI] [PubMed] [Google Scholar]
35.DeWees R., Wang H., Synthesis and properties of NaSICON-type LATP and LAGP solid electrolytes. ChemSusChem 12, 3713–3725 (2019). [DOI] [PubMed] [Google Scholar]
36.MacNeil D. D., Lu Z., Chen Z., Dahn J. R., A comparison of the electrode/electrolyte reaction at elevated temperatures for various Li-ion battery cathodes. J. Power Sources 108, 8–14 (2002). [Google Scholar]
37.Xiao W., Wang J., Fan L., Zhang J., Li X., Recent advances in Li_1+xAlxTi_2-x(PO₄)₃ solid-state electrolyte for safe lithium batteries. Energy Storage Mater. 19, 379–400 (2019). [Google Scholar]
38.Zhao P., Wen Y., Cheng J., Cao G., Jin Z., Ming H., Xu Y., Zhu X., A novel method for preparation of high dense tetragonal Li₇La₃Zr₂O₁₂. J. Power Sources 344, 56–61 (2017). [Google Scholar]
39.Zhao P., Xiang Y., Wen Y., Li M., Zhu X., Zhao S., Jin Z., Ming H., Cao G., Garnet-like Li_7-xLa₃Zr_2-xNbxO₁₂ (x = 0–0.7) solid state electrolytes enhanced by self-consolidation strategy. J. Eur. Ceram. Soc. 38, 5454–5462 (2018). [Google Scholar]
40.Pfenninger R., Struzik M., Garbayo I., Stilp E., Rupp J. L. M., A low ride on processing temperature for fast lithium conduction in garnet solid-state battery films. Nat. Energy 4, 475–483 (2019). [Google Scholar]
41.Hong H. Y.-P., Crystal structures and crystal chemistry in the system Na_1+xZr₂SixP_3−xO₁₂. Mater. Res. Bull. 11, 173–182 (1976). [Google Scholar]
42.Sharafi A., Kazyak E., Davis A. L., Yu S., Thompson T., Siegel D. J., Dasgupta N. P., Sakamoto J., Surface chemistry mechanism of ultra-low interfacial resistance in the solid-state electrolyte Li₇La₃Zr₂O₁₂. Chem. Mater. 29, 7961–7968 (2017). [Google Scholar]
43.Mauvy F., Siebert E., Fabry P., Reactivity of NASICON with water and interpretation of the detection limit of a NASICON based Na⁺ ion selective electrode. Talanta 48, 293–303 (1999). [DOI] [PubMed] [Google Scholar]
44.Guin M., Indris S., Kaus M., Ehrenberg H., Tietz F., Guillon O., Stability of NASICON materials against water and CO₂ uptake. Solid State Ion. 302, 102–106 (2017). [Google Scholar]
45.Lee W., Lyon C. K., Seo J.-H., Hallman R. L., Leng Y., Wang C.-Y., Hickner M. A., Randall C. A., Gomez E. D., Ceramic-salt composite electrolytes from cold sintering. Adv. Funct. Mater. 29, 1807872 (2019). [Google Scholar]
46.Liu Y. L., Liu J., Sun Q., Wang D., Adair K. R., Liang J., Zhang C., Zhang L., Lu S., Huang H., Song X., Sun X., Insight into the microstructure and ionic conductivity of cold sintered NASICON solid electrolyte for solid-state batteries. ACS Appl. Mater. Interfaces 11, 27890–27896 (2019). [DOI] [PubMed] [Google Scholar]
47.Andre D., Kim S.-J., Lamp P., Lux S. F., Maglia F., Paschosa O., Stiaszny B., Future generations of cathode materials: An automotive industry perspective. J. Mater. Chem. A 3, 6709–6732 (2015). [Google Scholar]
48.Chen S., Xie D., Liu G., Mwizerwa J. P., Zhang Q., Zhao Y., Xu X., Yao X., Sulfide solid electrolytes for all-solid-state lithium batteries: Structure, conductivity, stability and application. Energy Storage Mater. 14, 58–74 (2018). [Google Scholar]
49.Asano T., Sakai A., Ouchi S., Sakaida M., Miyazaki A., Hasegawa S., Solid halide electrolytes with high lithium-ion conductivity for application in 4 V class bulk-type all-solid-state batteries. Adv. Mater. 30, 1803075 (2018). [DOI] [PubMed] [Google Scholar]
50.Li X., Liang J., Chen N., Luo J., Adair K. R., Wang C., Banis M. N., Sham T.-K., Zhang L., Zhao S., Lu S., Huang H., Li R., Sun X., Water-mediated synthesis of a superionic halide solid electrolyte. Angew. Chem. Int. Ed. 131, 16579–16584 (2019). [DOI] [PubMed] [Google Scholar]
51.Liang J., Li X., Wang S., Adair K. R., Li W., Zhao Y., Wang C., Hu Y., Zhang L., Zhao S., Lu S., Huang H., Li R., Mo Y., Sun X., Site-occupation-tuned superionic LixScCl_3+x halide solid electrolytes for all-solid-state batteries. J. Am. Chem. Soc. 142, 7012–7022 (2020). [DOI] [PubMed] [Google Scholar]
52.Zahiri B., Patra A., Kiggins C., Yong A. X. B., Ertekin E., Cook J. B., Braun P. V., Revealing the role of the cathode–electrolyte interface on solid-state batteries. Nat. Mater. 20, 1392–1400 (2021). [DOI] [PubMed] [Google Scholar]
53.Li X., Liang J., Yang X., Adair K. R., Wang C., Zhao F., Sun X., Progress and perspectives on halide lithium conductors for all-solid-state lithium batteries. Energ. Environ. Sci. 13, 1429–1461 (2020). [Google Scholar]
54.Kresse G., Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996). [DOI] [PubMed] [Google Scholar]
55.Blochl P. E., Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994). [DOI] [PubMed] [Google Scholar]
56.Kresse G., Joubert D., From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999). [Google Scholar]
57.Monkhorst H. J., Pack J. D., Special points for brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976). [Google Scholar]
58.Perdew J. P., Burke K., Ernzerhof M., Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996). [DOI] [PubMed] [Google Scholar]
59.Nosé S., A unified formulation of the constant temperature molecular dynamics methods. J. Chem. Phys. 81, 511–519 (1984). [Google Scholar]
60.Udagawa T., Suzuki K., Tachikawa M., Multicomponent molecular orbital-climbing image-nudged elastic band method to analyze chemical reactions including nuclear quantum effect. ChemPhysChem 16, 3156–3160 (2015). [DOI] [PubMed] [Google Scholar]
61.M. H. Levitt, Chapter 7: NMR of other commonly studied nuclei, in Spin Dynamics: Basics of Nuclear Magnetic Resonance (John Wiley & Sons, 2002). [Google Scholar]
62.Chen J., Zhu L., Jia D., Jiang X., Wu Y., Hao Q., Xia X., Ouyang Y., Peng L., Tang W., Liu T., LiNi_0.8Co_0.15Al_0.05O₂ cathodes exhibiting improved capacity retention and thermal stability due to a lithium iron phosphate coating. Electrochim. Acta 312, 179–187 (2019). [Google Scholar]
63.Du M., Liao K., Lua Q., Shao Z., Recent advances in the interface engineering of solid-state Li-ion batteries with artificial buffer layers: Challenges, materials, construction, and characterization. Energ. Environ. Sci. 12, 1780–1804 (2019). [Google Scholar]
64.Zhang X., Liu T., Zhang S., Huang X., Xu B., Lin Y., Xu B., Li L., Nan C.-W., Shen Y., Synergistic coupling between Li_6.75La₃Zr_1.75Ta_0.25O₁₂ and poly(vinylidene fluoride) induces high ionic conductivity, mechanical strength, and thermal stability of solid composite electrolytes. J. Am. Chem. Soc. 139, 13779–13785 (2017). [DOI] [PubMed] [Google Scholar]
65.Nie K., Hong Y., Qiu J., Li Q., Yu X., Li H., Chen L., Interfaces between cathode and electrolyte in solid state lithium batteries: Challenges and perspectives. Front. Chem. 6, 616 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]
66.Ma X., Xu Y., Zhang B., Xue X., Wang C., He S., Lin J., Yang L., Garnet Si–Li₇La₃Zr₂O₁₂ electrolyte with a durable, low resistance interface layer for all-solid-state lithium metal batteries. J. Power Sources 453, 227881 (2020). [Google Scholar]
67.Pitawala H. M. J. C., Dissanayake M. A. K. L., Seneviratne V. A., Combined effect of Al₂O₃ nano-fillers and EC plasticizer on ionic conductivity enhancement in the solid polymer electrolyte (PEO)₉LiTf. Solid State Ion. 178, 885–888 (2007). [Google Scholar]
68.Nicotera I., Ranieri G. A., Terenzi M., Chadwick A. V., Webster M. I., A study of stability of plasticized PEO electrolytes. Solid State Ion. 146, 143–150 (2002). [Google Scholar]
69.Ratner M. A., Shriver D. F., Ion transport in solvent-Free polymers. Chem. Rev. 88, 109–124 (1988). [Google Scholar]
70.Liu Y., Li C., Li B., Song H., Cheng Z., Chen M., He P., Zhou H., Germanium thin film protected lithium aluminum germanium phosphate for solid-state Li batteries. Adv. Energy Mater. 8, 1702374 (2018). [Google Scholar]
71.Aono H., Sugimoto E., Sadaoka Y., Imanaka N., Adachi G., Ionic Conductivity of solid electrolytes based on lithium titanium phosphate. J. Electrochem. Soc. 137, 1023–1027 (1990). [Google Scholar]
72.Nairn K., Forsyth M., Every H., Greville M., MacFarlane D. R., Polymer-ceramic ion-conducting composites. Solid State Ion. 86-88, 589–593 (1996). [Google Scholar]
73.Birke P., Salam F., Doring S., Weppner W., A first approach to a monolithic all solid state inorganic lithium battery. Solid State Ion. 118, 149–157 (1999). [Google Scholar]
74.Yu J., Duan S., Huang B., Jin H., Xie S., Li J., Spatially resolved electrochemical strain of solid-state electrolytes via high resolution sequential excitation and its implication on grain boundary impedance. Small Methods 4, 2000308 (2020). [Google Scholar]
75.Li S.-C., Cai J.-Y., Lin Z.-X., Phase relationships and electrical conductivity of Li_1+xGe_2-xAlxP₃O₁₂ and Li_1+xGe_2-xGrxP₃O₁₂ systems. Solid State Ion. 28–30, 1265–1270 (1988). [Google Scholar]
76.Aono H., Sugimoto E., Sadaoka Y., Imanaka N., Adachi G., Electrical properties and sinterability for lithium germanium phosphate Li_1+xMxGe_2-x(PO₄)₃, M=Al, Cr, Ga, Fe, Sc, and in systems. Bull. Chem. Soc. Jpn. 65, 2200–2204 (1992). [Google Scholar]
77.Fu J., Fast Li ion conducting glass-ceramics in the system Li₂O-Al₂O₃-GeO₂-P₂O₅. Solid State Ion. 104, 191–194 (1997). [Google Scholar]
78.Xu X., Wen Z., Wu X., Yang X., Gu Z., Lithium ion-conducting glass-ceramics of Li_1.5Al_0.5Ge_1.5(PO₄)₃-xLi₂O (x = 0.0–0.20) with good electrical and electrochemical properties. J. Am. Ceram. Soc. 90, 2802–2806 (2007). [Google Scholar]
79.Nikodimos Y., Tsai M.-C., Abrha L. H., Weldeyohannis H. H., Chiu S.-F., Bezabh H. K., Shitaw K. N., Fenta F. W., Wu S.-H., Su W.-N., Yang C.-C., Hwang B. J., Al-Sc dual-doped LiGe₂(PO₄)₃—A NASICON-type solid electrolyte with improved ionic conductivity. J. Mater. Chem. A 8, 11302–11313 (2020). [Google Scholar]
80.Chang C.-M., Lee Y. I., Hong S.-H., Park H.-M., Spark plasma sintering of LiTi₂(PO₄)₃-based solid electrolytes. J. Am. Ceram. Soc. 88, 1803–1807 (2005). [Google Scholar]
81.Luo Z., Qin C., Xu W., Liang H., Lei W., Shen X., Lu A., Crystal structure refinement, microstructure and ionic conductivity of ATi₂(PO₄)₃ (A=Li, Na, K) solid electrolytes. Ceram. Int. 46, 15613–15620 (2020). [Google Scholar]
82.Yamamoto H., Tabuchi M., Takeuchi T., Kageyama H., Nakamura O., Ionic conductivity enhancement in LiGe₂(PO₄)₃ solid electrolyte. J. Power Sources 68, 397–401 (1997). [Google Scholar]
83.Feng J., Xia H., Lai M. O., Lu L., NASICON-structured LiGe₂(PO₄)₃ with improved cyclability for high-performance lithium batteries. J. Phys. Chem. C 113, 20514–20520 (2009). [Google Scholar]
84.Hu Y.-W., Raistrick I. D., Huggins R. A., Ionic conductivity of lithium phosphate-doped lithium orthosilicate. Mater. Res. Bull. 11, 1227–1230 (1976). [Google Scholar]
85.Khorassani A., Izquierdo G., West A. R., The solid electrolyte system Li₃PO₄-Li₄SiO₄. Mater. Res. Bull. 16, 1561–1567 (1981). [Google Scholar]
86.Wang D., Zhong G., Lia Y., Gong Z., McDonald M. J., Mi J.-X., Fu R., Shi Z., Yang Y., Enhanced ionic conductivity of Li_3.5Si_0.5P_0.5O₄ with addition of lithium borate. Solid State Ion. 283, 109–114 (2015). [Google Scholar]
87.Sudo R., Nakata Y., Ishiguro K., Matsui M., Hirano A., Takeda Y., Yamamoto O., Imanishi N., Interface behavior between garnet-type lithium-conducting solid electrolyte and lithium metal. Solid State Ion. 262, 151–154 (2014). [Google Scholar]
88.Ramakumar S., Janani N., Murugan R., Influence of lithium concentration on the structure and Li⁺ transport properties of cubic phase lithium garnets. Dalton Trans. 44, 539–552 (2015). [DOI] [PubMed] [Google Scholar]
89.Zhang Y., Luo D., Luo W., Du S., Deng Y., Deng J., High-purity and high-density cubic phase of Li₇La₃Zr₂O₁₂ solid electrolytes by controlling surface/volume ratio and sintering pressure. Electrochim. Acta 359, 136965 (2020). [Google Scholar]
90.Thangadurai V., Kaack H., Weppner W. J. F., Novel fast lithium ion conduction in garnet-type Li₅La₃M₂O₁₂ (M = Nb, Ta). J. Am. Ceram. Soc. 86, 437–440 (2003). [Google Scholar]
91.Nemori H., Matsuda Y., Matsui M., Yamamoto O., Takeda Y., Imanishi N., Relationship between lithium content and ionic conductivity in the Li_5+2xLa₃Nb_2-xScxO₁₂ system. Solid State Ion. 266, 9–12 (2014). [Google Scholar]
92.Wang W. G., Wang X. P., Gao Y. X., Fang Q. F., Lithium-ionic diffusion and electrical conduction in the Li₇La₃Ta₂O₁₃ compounds. Solid State Ion. 180, 1252–1256 (2009). [Google Scholar]
93.Wang W. G., Wang X. P., Gao Y. X., Hao G. L., Ma W. Q., Fang Q. F., Internal friction study on the lithium ion diffusion of Li₅La₃M₂O₁₂ (M = Ta, Nb) ionic conductors. Solid State Ion. 13, 1760–1764 (2011). [Google Scholar]
94.Wang Y., Lai W., High ionic conductivity lithium garnet oxides of Li_7-xLa₃Zr_2-xTaxO₁₂ compositions. Electrochem. Solid State 15, A68–A71 (2012). [Google Scholar]
95.Kotobuki M., Kanamura K., Fabrication of all-solid-state battery using Li₅La₃Ta₂O₁₂ ceramic electrolyte. Ceram. Int. 39, 6481–6487 (2013). [Google Scholar]
96.Inaguma Y., Chen L., Itoh M., Nakamura T., Uchida T., Ikuta H., Wakihara M., High ionic conductivity in lithium lanthanum titanate. Solid State Commun. 86, 689–693 (1993). [Google Scholar]
97.Tang H., Xu J., Enhanced electrochemical performance of LiFePO₄ coated with Li_0.34La_0.51TiO_2.94 by rheological phase reaction method. Mater. Sci. Eng. B 178, 1503–1508 (2013). [Google Scholar]
98.Le H. T. T., Kalubarme R. S., Ngo D. T., Jang S.-Y., Jung K.-N., Shin K.-H., Park C.-J., Citrate gel synthesis of aluminum-doped lithium lanthanum titanate solid electrolyte for application in organic-type lithium-oxygen batteries. J. Power Sources 274, 1188–1199 (2015). [Google Scholar]
99.Le H. T. T., Ngo D. T., Kim Y.-J., Park C.-N., Park C.-J., A perovskite-structured aluminium-substituted lithium lanthanum titanate as a potential artificial solid-electrolyte interface for aqueous rechargeable lithium-metal-based batteries. Electrochim. Acta 248, 232–242 (2017). [Google Scholar]
100.Itoh M., Inaguma Y., Jung W.-H., Chen L., Nakamura T., High lithium ion conductivity in the perovskite-type compounds Ln_1/2Li_1/2TiO₃ (Ln = La, Pr, Nd, Sm). Solid State Ion. 70-71, 203–207 (1994). [Google Scholar]
101.Stramare S., Thangadurai V., Weppner W., Lithium lanthanum titanates: A review. Chem. Mater. 15, 3974–3990 (2003). [Google Scholar]
102.Zhou Q., Xu B., Chien P.-H., Li Y., Huang B., Wu N., Xu H., Grundish N. S., Hu Y.-Y., Goodenough J. B., NASICON Li_1.2Mg_0.1Zr_1.9(PO₄)₃ solid electrolyte for an all-solid-state Li-metal battery. Small Methods 4, 2000764 (2020). [Google Scholar]
103.Kosova N. V., Devyatkina E. T., Stepanov A. P., Buzlukov A. L., Lithium conductivity and lithium diffusion in NASICON-type Li_1+xTi_2–xAlx(PO₄)₃ (x = 0;0.3) prepared by mechanical activation. Ionics 14, 303–311 (2008). [Google Scholar]
104.Zhu Y. Z., He X. F., Mo Y. F., Origin of outstanding stability in the lithium solid electrolyte materials: Insights from thermodynamic analyses based on first-principles calculations. ACS Appl. Mater. Interfaces 7, 23685–23693 (2015). [DOI] [PubMed] [Google Scholar]
105.Wu X. M., Li X. H., Zhang Y. H., Xu M. F., He Z. Q., Synthesis of Li_1.3Al_0.3Ti_1.7(PO₄)₃ by sol–gel technique. Mater. Lett. 58, 1227–1230 (2004). [Google Scholar]
106.Kotobuki M., Koishi M., Preparation of Li_1.5Al_0.5Ti_1.5(PO₄)₃ solid electrolyte via a sol-gel route using various Al sources. Ceram. Int. 39, 4645–4649 (2013). [Google Scholar]
107.Breuer S., Prutsch D., Ma Q., Epp V., Preishuber-Pflugl F., Tietz F., Wilkening M., Separating bulk from grain boundary Li ion conductivity in the sol-gel prepared solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃. J. Mater. Chem. A 3, 21343–21350 (2015). [Google Scholar]
108.Feng J. K., Lu L., Lai M. O., Lithium storage capability of lithium ion conductor Li_1.5Al_0.5Ge_1.5(PO₄)₃. J. Alloys Compd. 501, 255–258 (2010). [Google Scholar]
109.Illbeigi M., Fazlali A., Kazazi M., Mohammadi A. H., Effect of simultaneous addition of aluminum and chromium on the lithium ionic conductivity of LiGe₂(PO₄)₃ NASICON-type glass-ceramics. Solid State Ion. 289, 180–187 (2016). [Google Scholar]
110.Thompson T., Yu S., Williams L., Schmidt R. D., Garcia-Mendez R., Wolfenstine J., Allen J. L., Kioupakis E., Siegel D. J., Sakamoto J., Electrochemical window of the Li-ion solid electrolyte Li₇La₃Zr₂O₁₂. ACS Energy Lett. 2, 462–468 (2017). [Google Scholar]
111.Ohta S., Kobayashi T., Asaoka T., High lithium ionic conductivity in the garnet-type oxide Li_7−xLa₃(Zr_2−x, Nbx)O₁₂ (x = 0–2). J. Power Sources 196, 3342–3345 (2011). [Google Scholar]
112.Wei J., Ogawa D., Fukumura T., Hirose Y., Hasegawa T., Epitaxial strain-controlled ionic conductivity in Li-ion solid electrolyte Li_0.33La_0.56TiO₃ thin films. Cryst. Growth Des. 15, 2187–2191 (2015). [Google Scholar]
113.Chen C. H., Amine K., Ionic conductivity, lithium insertion and extraction of lanthanum lithium titanate. Solid State Ion. 144, 51–57 (2001). [Google Scholar]
114.Yamaki J., Ohtsuka H., Shodai T., Rechargeable lithium thin film cells with inorganic electrolytes. Solid State Ion. 86-88, 1279–1284 (1996). [Google Scholar]
115.Bruce P. G., West A. R., Ionic conductivity of LISICON solid solutions, Li_2+2xZn_1-xGeO₄. J. Solid State Chem. 44, 354–365 (1982). [Google Scholar]
116.Gao J., Zhao Y. S., Shi S. Q., Li H., Lithium-ion transport in inorganic solid state electrolyte. Chin. Phys. B 25, 018211 (2016). [Google Scholar]
117.Li W., Wu G., Araújo C. M., Scheicher R. H., Blomqvist A., Ahuja R., Xiong Z., Feng Y., Chen P., Li⁺ ion conductivity and diffusion mechanism in α-Li₃N and β-Li₃N. Energ. Environ. Sci. 3, 1524–1530 (2010). [Google Scholar]
118.Rabenau A., Lithium nitride and related materials case study of the use of modern solid state research techniques. Solid State Ion. 6, 277–293 (1982). [Google Scholar]
119.Rea J. R., Foster D. L., Mallory P. R., Inc C., High ionic conductivity in densified polycrystalline lithium nitride. Mater. Res. Bull. 14, 841–846 (1979). [Google Scholar]
120.Xu R., Wu Z., Zhang S., Wang X., Xia Y., Xia X., Huang X., Tu J., Construction of all-solid-state batteries based on a sulfur-graphene composite and Li_9.54Si_1.74P_1.44S_11.7Cl_0.3 solid electrolyte. Chem. Eur. J. 23, 13950–13956 (2017). [DOI] [PubMed] [Google Scholar]
121.Seino Y., Ota T., Takada K., Hayashi A., Tatsumisago M., A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries. Energ. Environ. Sci. 7, 627–631 (2014). [Google Scholar]
122.Boulineau S., Courty M., Tarascon J. M., Viallet V., Mechanochemical synthesis of li-argyrodite Li₆PS₅X (X=Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application. Solid State Ion. 221, 1–5 (2012). [Google Scholar]
123.Rangasamy E., Liu Z., Gobet M., Pilar K., Sahu G., Zhou W., Wu H., Greenbaum S., Liang C., An iodide-based Li₇P₂S₈I superionic conductor. J. Am. Chem. Soc. 137, 1384–1387 (2015). [DOI] [PubMed] [Google Scholar]
124.Zhou D., Shanmukaraj D., Tkacheva A., Armand M., Wang G. X., Polymer electrolytes for lithium-based batteries: Advances and Prospects. Chem 5, 2326–2352 (2019). [Google Scholar]
125.Zhang J., Zhao J., Yue L., Wang Q., Chai J., Liu Z., Zhou X., Li H., Guo Y., Cui G., Chen L., Safety-reinforced poly(propylene carbonate)-based all-solid-state polymer electrolyte for ambient-temperature solid polymer lithium batteries. Adv. Energy Mater. 5, 1501082 (2015). [Google Scholar]
126.Chen K., Shen Y., Jiang J., Zhang Y., Lin Y., Nan C.-W., High capacity and rate performance of LiNi_0.5Co_0.2Mn_0.3O₂ composite cathode for bulk-type all-solid-state lithium battery. J. Mater. Chem. A 2, 13332–13337 (2014). [Google Scholar]
127.Shao Y., Wang H., Gong Z., Wang D., Zheng B., Zhu J., Lu Y., Hu Y.-S., Guo X., Li H., Huang X., Yang Y., Nan C.-W., Chen L., Drawing a soft interface: An effective interfacial modification strategy for garnet-type solid-state Li batteries. ACS Energy Lett. 3, 1212–1218 (2018). [Google Scholar]
128.Liu B., Zhang L., Xu S., McOwen D. W., Gong Y., Yang C., Pastel G. R., Xie H., Fu K., Dai J., Chen C., Wachsman E. D., Hu L., 3D lithium metal anodes hosted in asymmetric garnet frameworks toward high energy density batteries. Energy Storage Mater. 14, 376–382 (2018). [Google Scholar]
129.Liu T., Zhang Y., Zhang X., Wang L., Zhao S.-X., Lin Y.-H., Shen Y., Luo J., Li L., Nan C.-W., Enhanced electrochemical performance of bulk type oxide ceramic lithium batteries enabled by interface modification. J. Mater. Chem. A 6, 4649–4657 (2018). [Google Scholar]
130.Chen L., Li W. X., Fan L. Z., Nan C.-W., Zhang Q., Intercalated electrolyte with high transference number for dendrite-free solid-state lithium batteries. Adv. Funct. Mater. 29, 1901047 (2019). [Google Scholar]
131.Jiang T., He P., Wang G., Shen Y., Nan C.-W., Fan L.-Z., Solvent-free synthesis of thin, flexible, nonflammable garnet-based composite solid electrolyte for all-solid-state lithium batteries. Adv. Energy Mater. 10, 1903376 (2020). [Google Scholar]
132.Zhang B., Chen L., Hu J., Liu Y., Liu Y., Feng Q., Zhu G., Fan L.-Z., Solid-state lithium metal batteries enabled with high loading composite cathode materials and ceramic-based composite electrolytes. J. Power Sources 442, 227230 (2019). [Google Scholar]
133.Huang S., Yang H., Hu J., Liu Y., Wang K., Peng H., Zhang H., Fan L.-Z., Early lithium plating behavior in confined nanospace of 3D lithiophilic carbon matrix for stable solid-state lithium metal batteries. Small 15, 1904216 (2019). [DOI] [PubMed] [Google Scholar]
134.Ruan Y., Lu Y., Huang X., Su J., Sun C., Jin J., Wen Z., Acid induced conversion towards a robust and lithiophilic interface for Li-Li₇La₃Zr₂O₁₂ solid-state batteries. J. Mater. Chem. A 7, 14565–14574 (2019). [Google Scholar]
135.Wang G. X., He P. G., Fan L. Z., Asymmetric polymer electrolyte constructed by metal-organic framework for solid-state, dendrite-free lithium metal battery. Adv. Funct. Mater. 31, 2007198 (2021). [Google Scholar]
136.Zhuang Z., Yang L., Ju B., Lei G., Zhou Q., Liao H., Yin A., Deng Z., Tang Y., Qin S., Tu F., Ameliorating interfacial issues of LiNi_0.5Co_0.2Mn_0.3O₂/poly (propylene carbonate) by introducing graphene interlayer for all-solid-state lithium batteries. ChemistrySelect 5, 2291–2299 (2020). [Google Scholar]
137.Zhao L., Fu J., Du Z., Jia X., Qu Y., Yu F., Du J., Chen Y., High-strength and flexible cellulose/PEG based gel polymer electrolyte with high performance for lithium ion batteries. J. Membr. Sci. 593, 117428 (2020). [Google Scholar]
138.Zha W. P., Li W. W., Ruan Y. D., Wang J. C., Wen Z. Y., In situ fabricated ceramic/polymer hybrid electrolyte with vertically aligned structure for solid-state lithium batteries. Energ. Storage Mater. 36, 171–178 (2021). [Google Scholar]

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Supplementary Materials

Figs. S1 to S32

Tables S1 to S9

Texts S1 to S3

References

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[R1] 1.Manthiram A., Yu X., Wang S., Lithium battery chemistries enabled by solid-state electrolytes. Nat. Rev. Mater. 2, 16103 (2017). [Google Scholar]

[R2] 2.Gao Z., Sun H., Fu L., Ye F., Zhang Y., Luo W., Huang Y., Promises, challenges, and recent progress of inorganic solid-state electrolytes for all-solid-state lithium batteries. Adv. Mater. 30, 1705702 (2018). [DOI] [PubMed] [Google Scholar]

[R3] 3.Chen R., Li Q., Yu X., Chen L., Li H., Approaching practically accessible solid-state batteries: Stability issues related to solid electrolytes and interfaces. Chem. Rev. 120, 6820–6877 (2019). [DOI] [PubMed] [Google Scholar]

[R4] 4.Schwietert T. K., Arszelewska V. A., Wang C., Yu C., Vasileiadis A., de Klerk N. J. J., Hageman J., Hupfer T., Kerkamm I., Xu Y., van der Maas E., Kelder E. M., Ganapathy S., Wagemaker M., Clarifying the relationship between redox activity and electrochemical stability in solid electrolytes. Nat. Mater. 19, 428–435 (2020). [DOI] [PubMed] [Google Scholar]

[R5] 5.Han F., Zhu Y., He X., Mo Y., Wang C., Electrochemical stability of Li₁₀GeP₂S₁₂ and Li₇La₃Zr₂O₁₂ solid electrolytes. Adv. Energy Mater. 6, 1501590 (2016). [Google Scholar]

[R6] 6.Kamaya N., Homma K., Yamakawa Y., Hirayama M., Kanno R., Yonemura M., Kamiyama T., Kato Y., Hama S., Kawamoto K., Mitsui A., A lithium superionic conductor. Nat. Mater. 10, 682–686 (2011). [DOI] [PubMed] [Google Scholar]

[R7] 7.Zhao Y., Daemen L. L., Superionic conductivity in lithium-rich anti-perovskites. J. Am. Chem. Soc. 134, 15042–15047 (2012). [DOI] [PubMed] [Google Scholar]

[R8] 8.Lü X., Howard J. W., Chen A., Zhu J., Li S., Wu G., Dowden P., Xu H., Zhao Y., Jia Q., Antiperovskite Li₃OCl superionic conductor films for solid-state Li-ion batteries. Adv. Sci. 3, 1500359 (2016). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R9] 9.Wenzel S., Randau S., Leichtweiß T., Weber D. A., Sann J., Zeier W. G., Janek J., Direct observation of the interfacial instability of the fast ionic conductor Li₁₀GeP₂S₁₂ at the lithium metal anode. Chem. Mater. 28, 2400–2407 (2016). [Google Scholar]

[R10] 10.Murugan R., Thangadurai V., Weppner W., Fast lithium ion conduction in garnet-type Li₇La₃Zr₂O₁₂. Angew. Chem. Int. Ed. 46, 7778–7781 (2007). [DOI] [PubMed] [Google Scholar]

[R11] 11.Suzuki N., Inaba T., Shiga T., Electrochemical properties of LiPON films made from a mixed powder target of Li₃PO₄ and Li₂O. Thin Solid Films 520, 1821–1825 (2012). [Google Scholar]

[R12] 12.Li Y., Zhou W., Chen X., Lü X., Cui Z., Xin S., Xue L., Jia Q., Goodenough J. B., Mastering the interface for advanced all-solid-state lithium rechargeable batteries. Proc. Natl. Acad. Sci. U.S.A. 113, 13313–13317 (2016). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R13] 13.Kim K. J., Balaish M., Wadaguchi M., Kong L. P., Rupp J., Solid-state Li–metal batteries: Challenges and horizons of oxide and sulfide solid electrolytes and their interfaces. Adv. Energy Mater. 11, 2002689 (2020). [Google Scholar]

[R14] 14.Deng Y., Eames C., Fleutot B., David R., Chotard J., Suard E., Masquelier C., Islam M. S., Enhancing the lithium ion conductivity in lithium superionic conductor (LISICON) solid electrolytes through a mixed polyanion effect. ACS Appl. Mater. Interfaces 9, 7050–7058 (2017). [DOI] [PubMed] [Google Scholar]

[R15] 15.Hou M., Liang F., Chen K., Dai Y., Xue D., Challenges and perspectives of NASICON-type solid electrolytes for all-solid-state lithium batteries. Nanotechnology 31, 132003 (2020). [DOI] [PubMed] [Google Scholar]

[R16] 16.Jian Z., Hu Y.-S., Ji X., Chen W., NASICON-structured materials for energy storage. Adv. Mater. 29, 1601925 (2017). [DOI] [PubMed] [Google Scholar]

[R17] 17.Ladenstein L., Simic S., Kothleitner G., Rettenwander D., Wilkening H. M. R., Anomalies in bulk ion transport in the solid solutions of Li₇La₃M₂O₁₂ (M = Hf, Sn) and Li₅La₃Ta₂O₁₂. J. Phys. Chem. C 124, 16796–16805 (2020). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R18] 18.Mei A., Jiang Q.-H., Lin Y.-H., Nan C.-W., Lithium lanthanum titanium oxide solid-state electrolyte by spark plasma sintering. J. Alloys Compd. 486, 16796–16805 (2009). [Google Scholar]

[R19] 19.Wang C., Fu K., Kammampata S. P., McOwen D. W., Samson A. J., Zhang L., Hitz G. T., Nolan A. M., Wachsman E. D., Mo Y., Thangadurai V., Hu L., Garnet-type solid-state electrolytes: Materials, interfaces, and batteries. Chem. Rev. 120, 4257–4300 (2020). [DOI] [PubMed] [Google Scholar]

[R20] 20.Lacivita V., Westover A. S., Kercher A., Phillip N. D., Yang G., Veith G., Ceder G., Dudney N. J., Resolving the amorphous structure of lithium phosphorus oxynitride (Lipon). J. Am. Chem. Soc. 140, 11029–11038 (2018). [DOI] [PubMed] [Google Scholar]

[R21] 21.Wang Y., Richards W. D., Ong S. P., Miara L. J., Kim J. C., Mo Y., Ceder G., Design principles for solid-state lithium superionic conductors. Nat. Mater. 14, 1026–1031 (2015). [DOI] [PubMed] [Google Scholar]

[R22] 22.Bachman J. C., Muy S., Grimaud A., Chang H.-H., Pour N., Lux S. F., Paschos O., Maglia F., Lupart S., Lamp P., Giordano L., Shao-Horn Y., Inorganic solid-state electrolytes for lithium batteries: Mechanisms and properties governing ion conduction. Chem. Rev. 116, 140–162 (2016). [DOI] [PubMed] [Google Scholar]

[R23] 23.Gao J., Wu J., Han S., Zhang J., Zhu L., Wu Y., Zhao J., Tang W., A novel solid electrolyte formed by NASICON-type Li₃Zr₂Si₂PO₁₂ and poly(vinylidene fluoride) for solid state batteries. Funct. Mater. Lett. 14, 2140001 (2021). [Google Scholar]

[R24] 24.Belam W., Sol-gel chemistry synthesis and DTA-TGA, XRPD, SIC and ⁷Li, ³¹P, ²⁹Si MAS-NMR studies on the Li-NASICON Li₃Zr_2-ySi_2-4yP_1+4yO₁₂ (0⩽y⩽0.5) system. J. Alloys Compd. 551, 267–273 (2013). [Google Scholar]

[R25] 25.Shannon R. D., Revised effective ionic radii and systematic studies of interatomic distances in halides and chalcogenides. Acta Crystallogr. 32, 751–767 (1976). [Google Scholar]

[R26] 26.Yang K., Chen L., Ma J., He Y.-B., Kang F., Progress and perspective of Li_1+xAl_xTi_2-x(PO₄)₃ ceramic electrolyte in lithium batteries. InfoMat. 3, 1195–1217 (2021). [Google Scholar]

[R27] 27.Zhang Z., Zou Z., Kaup K., Xiao R., Shi S., Avdeev M., Hu Y.-S., Wang D., He B., Li H., Huang X., Nazar L. F., Chen L., Correlated migration invokes higher Na⁺-ion conductivity in NaSICON-type solid electrolytes. Adv. Energy Mater. 9, 1902373 (2019). [Google Scholar]

[R28] 28.Vera V. B., Igor L. S., Ion exchange conversion of solid electrolyte, potassium sodiostannate, into isomorphous metastable sodium stannate. Mendeleev Commun. 26, 246–247 (2016). [Google Scholar]

[R29] 29.Malavasi L., Fisher C. A. J., Islam M. S., Oxide-ion and proton conducting electrolyte materials for clean energy applications: Structural and mechanistic features. Chem. Soc. Rev. 39, 4370–4387 (2010). [DOI] [PubMed] [Google Scholar]

[R30] 30.Zhang Z., Shao Y., Lotsch B., Hu Y.-S., Li H., Janek J., Nazar L. F., Nan C.-W., Maier J., Armand M., Chen L., New horizons for inorganic solid state ion conductors. Energ. Environ. Sci. 11, 1945–1976 (2018). [Google Scholar]

[R31] 31.Chen J., Wu X.-P., Hope M. A., Qian K., Halat D. M., Liu T., Li Y., Shen L., Ke X., Wen Y., Du J.-H., Magusin P. C. M. M., Paul S., Ding W., Gong X.-Q., Grey C. P., Peng L., Polar surface structure of oxide nanocrystals revealed with solid-state NMR spectroscopy. Nat. Commun. 10, 5420 (2019). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R32] 32.Chen J., Hope M. A., Lin Z., Wang M., Liu T., Halat D. M., Wen Y., Chen T., Ke X., Magusin P. C. M. M., Ding W., Xia X., Wu X.-P., Gong X.-Q., Grey C. P., Peng L., Interactions of oxide surfaces with water revealed with solid-state NMR spectroscopy. J. Am. Chem. Soc. 142, 11173–11182 (2020). [DOI] [PubMed] [Google Scholar]

[R33] 33.Van Den Broek J., Afyon S., Rupp J. L. M., Interface-engineered all-solid-state Li-ion batteries based on garnet-type fast Li⁺ conductors. Adv. Energy Mater. 6, 1600736 (2016). [Google Scholar]

[R34] 34.Han X., Gong Y., Fu K. K., He X., Hitz G. T., Dai J., Pearse A., Liu B., Wang H., Rubloff G., Mo Y., Thangadurai V., Wachsman E. D., Hu L., Negating interfacial impedance in garnet-based solid-state Li metal batteries. Nat. Mater. 16, 572–579 (2017). [DOI] [PubMed] [Google Scholar]

[R35] 35.DeWees R., Wang H., Synthesis and properties of NaSICON-type LATP and LAGP solid electrolytes. ChemSusChem 12, 3713–3725 (2019). [DOI] [PubMed] [Google Scholar]

[R36] 36.MacNeil D. D., Lu Z., Chen Z., Dahn J. R., A comparison of the electrode/electrolyte reaction at elevated temperatures for various Li-ion battery cathodes. J. Power Sources 108, 8–14 (2002). [Google Scholar]

[R37] 37.Xiao W., Wang J., Fan L., Zhang J., Li X., Recent advances in Li_1+xAlxTi_2-x(PO₄)₃ solid-state electrolyte for safe lithium batteries. Energy Storage Mater. 19, 379–400 (2019). [Google Scholar]

[R38] 38.Zhao P., Wen Y., Cheng J., Cao G., Jin Z., Ming H., Xu Y., Zhu X., A novel method for preparation of high dense tetragonal Li₇La₃Zr₂O₁₂. J. Power Sources 344, 56–61 (2017). [Google Scholar]

[R39] 39.Zhao P., Xiang Y., Wen Y., Li M., Zhu X., Zhao S., Jin Z., Ming H., Cao G., Garnet-like Li_7-xLa₃Zr_2-xNbxO₁₂ (x = 0–0.7) solid state electrolytes enhanced by self-consolidation strategy. J. Eur. Ceram. Soc. 38, 5454–5462 (2018). [Google Scholar]

[R40] 40.Pfenninger R., Struzik M., Garbayo I., Stilp E., Rupp J. L. M., A low ride on processing temperature for fast lithium conduction in garnet solid-state battery films. Nat. Energy 4, 475–483 (2019). [Google Scholar]

[R41] 41.Hong H. Y.-P., Crystal structures and crystal chemistry in the system Na_1+xZr₂SixP_3−xO₁₂. Mater. Res. Bull. 11, 173–182 (1976). [Google Scholar]

[R42] 42.Sharafi A., Kazyak E., Davis A. L., Yu S., Thompson T., Siegel D. J., Dasgupta N. P., Sakamoto J., Surface chemistry mechanism of ultra-low interfacial resistance in the solid-state electrolyte Li₇La₃Zr₂O₁₂. Chem. Mater. 29, 7961–7968 (2017). [Google Scholar]

[R43] 43.Mauvy F., Siebert E., Fabry P., Reactivity of NASICON with water and interpretation of the detection limit of a NASICON based Na⁺ ion selective electrode. Talanta 48, 293–303 (1999). [DOI] [PubMed] [Google Scholar]

[R44] 44.Guin M., Indris S., Kaus M., Ehrenberg H., Tietz F., Guillon O., Stability of NASICON materials against water and CO₂ uptake. Solid State Ion. 302, 102–106 (2017). [Google Scholar]

[R45] 45.Lee W., Lyon C. K., Seo J.-H., Hallman R. L., Leng Y., Wang C.-Y., Hickner M. A., Randall C. A., Gomez E. D., Ceramic-salt composite electrolytes from cold sintering. Adv. Funct. Mater. 29, 1807872 (2019). [Google Scholar]

[R46] 46.Liu Y. L., Liu J., Sun Q., Wang D., Adair K. R., Liang J., Zhang C., Zhang L., Lu S., Huang H., Song X., Sun X., Insight into the microstructure and ionic conductivity of cold sintered NASICON solid electrolyte for solid-state batteries. ACS Appl. Mater. Interfaces 11, 27890–27896 (2019). [DOI] [PubMed] [Google Scholar]

[R47] 47.Andre D., Kim S.-J., Lamp P., Lux S. F., Maglia F., Paschosa O., Stiaszny B., Future generations of cathode materials: An automotive industry perspective. J. Mater. Chem. A 3, 6709–6732 (2015). [Google Scholar]

[R48] 48.Chen S., Xie D., Liu G., Mwizerwa J. P., Zhang Q., Zhao Y., Xu X., Yao X., Sulfide solid electrolytes for all-solid-state lithium batteries: Structure, conductivity, stability and application. Energy Storage Mater. 14, 58–74 (2018). [Google Scholar]

[R49] 49.Asano T., Sakai A., Ouchi S., Sakaida M., Miyazaki A., Hasegawa S., Solid halide electrolytes with high lithium-ion conductivity for application in 4 V class bulk-type all-solid-state batteries. Adv. Mater. 30, 1803075 (2018). [DOI] [PubMed] [Google Scholar]

[R50] 50.Li X., Liang J., Chen N., Luo J., Adair K. R., Wang C., Banis M. N., Sham T.-K., Zhang L., Zhao S., Lu S., Huang H., Li R., Sun X., Water-mediated synthesis of a superionic halide solid electrolyte. Angew. Chem. Int. Ed. 131, 16579–16584 (2019). [DOI] [PubMed] [Google Scholar]

[R51] 51.Liang J., Li X., Wang S., Adair K. R., Li W., Zhao Y., Wang C., Hu Y., Zhang L., Zhao S., Lu S., Huang H., Li R., Mo Y., Sun X., Site-occupation-tuned superionic LixScCl_3+x halide solid electrolytes for all-solid-state batteries. J. Am. Chem. Soc. 142, 7012–7022 (2020). [DOI] [PubMed] [Google Scholar]

[R52] 52.Zahiri B., Patra A., Kiggins C., Yong A. X. B., Ertekin E., Cook J. B., Braun P. V., Revealing the role of the cathode–electrolyte interface on solid-state batteries. Nat. Mater. 20, 1392–1400 (2021). [DOI] [PubMed] [Google Scholar]

[R53] 53.Li X., Liang J., Yang X., Adair K. R., Wang C., Zhao F., Sun X., Progress and perspectives on halide lithium conductors for all-solid-state lithium batteries. Energ. Environ. Sci. 13, 1429–1461 (2020). [Google Scholar]

[R54] 54.Kresse G., Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996). [DOI] [PubMed] [Google Scholar]

[R55] 55.Blochl P. E., Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994). [DOI] [PubMed] [Google Scholar]

[R56] 56.Kresse G., Joubert D., From ultrasoft pseudopotentials to the projector augmented-wave method. Phys. Rev. B 59, 1758–1775 (1999). [Google Scholar]

[R57] 57.Monkhorst H. J., Pack J. D., Special points for brillouin-zone integrations. Phys. Rev. B 13, 5188–5192 (1976). [Google Scholar]

[R58] 58.Perdew J. P., Burke K., Ernzerhof M., Generalized gradient approximation made simple. Phys. Rev. Lett. 77, 3865–3868 (1996). [DOI] [PubMed] [Google Scholar]

[R59] 59.Nosé S., A unified formulation of the constant temperature molecular dynamics methods. J. Chem. Phys. 81, 511–519 (1984). [Google Scholar]

[R60] 60.Udagawa T., Suzuki K., Tachikawa M., Multicomponent molecular orbital-climbing image-nudged elastic band method to analyze chemical reactions including nuclear quantum effect. ChemPhysChem 16, 3156–3160 (2015). [DOI] [PubMed] [Google Scholar]

[R61] 61.M. H. Levitt, Chapter 7: NMR of other commonly studied nuclei, in Spin Dynamics: Basics of Nuclear Magnetic Resonance (John Wiley & Sons, 2002). [Google Scholar]

[R62] 62.Chen J., Zhu L., Jia D., Jiang X., Wu Y., Hao Q., Xia X., Ouyang Y., Peng L., Tang W., Liu T., LiNi_0.8Co_0.15Al_0.05O₂ cathodes exhibiting improved capacity retention and thermal stability due to a lithium iron phosphate coating. Electrochim. Acta 312, 179–187 (2019). [Google Scholar]

[R63] 63.Du M., Liao K., Lua Q., Shao Z., Recent advances in the interface engineering of solid-state Li-ion batteries with artificial buffer layers: Challenges, materials, construction, and characterization. Energ. Environ. Sci. 12, 1780–1804 (2019). [Google Scholar]

[R64] 64.Zhang X., Liu T., Zhang S., Huang X., Xu B., Lin Y., Xu B., Li L., Nan C.-W., Shen Y., Synergistic coupling between Li_6.75La₃Zr_1.75Ta_0.25O₁₂ and poly(vinylidene fluoride) induces high ionic conductivity, mechanical strength, and thermal stability of solid composite electrolytes. J. Am. Chem. Soc. 139, 13779–13785 (2017). [DOI] [PubMed] [Google Scholar]

[R65] 65.Nie K., Hong Y., Qiu J., Li Q., Yu X., Li H., Chen L., Interfaces between cathode and electrolyte in solid state lithium batteries: Challenges and perspectives. Front. Chem. 6, 616 (2018). [DOI] [PMC free article] [PubMed] [Google Scholar]

[R66] 66.Ma X., Xu Y., Zhang B., Xue X., Wang C., He S., Lin J., Yang L., Garnet Si–Li₇La₃Zr₂O₁₂ electrolyte with a durable, low resistance interface layer for all-solid-state lithium metal batteries. J. Power Sources 453, 227881 (2020). [Google Scholar]

[R67] 67.Pitawala H. M. J. C., Dissanayake M. A. K. L., Seneviratne V. A., Combined effect of Al₂O₃ nano-fillers and EC plasticizer on ionic conductivity enhancement in the solid polymer electrolyte (PEO)₉LiTf. Solid State Ion. 178, 885–888 (2007). [Google Scholar]

[R68] 68.Nicotera I., Ranieri G. A., Terenzi M., Chadwick A. V., Webster M. I., A study of stability of plasticized PEO electrolytes. Solid State Ion. 146, 143–150 (2002). [Google Scholar]

[R69] 69.Ratner M. A., Shriver D. F., Ion transport in solvent-Free polymers. Chem. Rev. 88, 109–124 (1988). [Google Scholar]

[R70] 70.Liu Y., Li C., Li B., Song H., Cheng Z., Chen M., He P., Zhou H., Germanium thin film protected lithium aluminum germanium phosphate for solid-state Li batteries. Adv. Energy Mater. 8, 1702374 (2018). [Google Scholar]

[R71] 71.Aono H., Sugimoto E., Sadaoka Y., Imanaka N., Adachi G., Ionic Conductivity of solid electrolytes based on lithium titanium phosphate. J. Electrochem. Soc. 137, 1023–1027 (1990). [Google Scholar]

[R72] 72.Nairn K., Forsyth M., Every H., Greville M., MacFarlane D. R., Polymer-ceramic ion-conducting composites. Solid State Ion. 86-88, 589–593 (1996). [Google Scholar]

[R73] 73.Birke P., Salam F., Doring S., Weppner W., A first approach to a monolithic all solid state inorganic lithium battery. Solid State Ion. 118, 149–157 (1999). [Google Scholar]

[R74] 74.Yu J., Duan S., Huang B., Jin H., Xie S., Li J., Spatially resolved electrochemical strain of solid-state electrolytes via high resolution sequential excitation and its implication on grain boundary impedance. Small Methods 4, 2000308 (2020). [Google Scholar]

[R75] 75.Li S.-C., Cai J.-Y., Lin Z.-X., Phase relationships and electrical conductivity of Li_1+xGe_2-xAlxP₃O₁₂ and Li_1+xGe_2-xGrxP₃O₁₂ systems. Solid State Ion. 28–30, 1265–1270 (1988). [Google Scholar]

[R76] 76.Aono H., Sugimoto E., Sadaoka Y., Imanaka N., Adachi G., Electrical properties and sinterability for lithium germanium phosphate Li_1+xMxGe_2-x(PO₄)₃, M=Al, Cr, Ga, Fe, Sc, and in systems. Bull. Chem. Soc. Jpn. 65, 2200–2204 (1992). [Google Scholar]

[R77] 77.Fu J., Fast Li ion conducting glass-ceramics in the system Li₂O-Al₂O₃-GeO₂-P₂O₅. Solid State Ion. 104, 191–194 (1997). [Google Scholar]

[R78] 78.Xu X., Wen Z., Wu X., Yang X., Gu Z., Lithium ion-conducting glass-ceramics of Li_1.5Al_0.5Ge_1.5(PO₄)₃-xLi₂O (x = 0.0–0.20) with good electrical and electrochemical properties. J. Am. Ceram. Soc. 90, 2802–2806 (2007). [Google Scholar]

[R79] 79.Nikodimos Y., Tsai M.-C., Abrha L. H., Weldeyohannis H. H., Chiu S.-F., Bezabh H. K., Shitaw K. N., Fenta F. W., Wu S.-H., Su W.-N., Yang C.-C., Hwang B. J., Al-Sc dual-doped LiGe₂(PO₄)₃—A NASICON-type solid electrolyte with improved ionic conductivity. J. Mater. Chem. A 8, 11302–11313 (2020). [Google Scholar]

[R80] 80.Chang C.-M., Lee Y. I., Hong S.-H., Park H.-M., Spark plasma sintering of LiTi₂(PO₄)₃-based solid electrolytes. J. Am. Ceram. Soc. 88, 1803–1807 (2005). [Google Scholar]

[R81] 81.Luo Z., Qin C., Xu W., Liang H., Lei W., Shen X., Lu A., Crystal structure refinement, microstructure and ionic conductivity of ATi₂(PO₄)₃ (A=Li, Na, K) solid electrolytes. Ceram. Int. 46, 15613–15620 (2020). [Google Scholar]

[R82] 82.Yamamoto H., Tabuchi M., Takeuchi T., Kageyama H., Nakamura O., Ionic conductivity enhancement in LiGe₂(PO₄)₃ solid electrolyte. J. Power Sources 68, 397–401 (1997). [Google Scholar]

[R83] 83.Feng J., Xia H., Lai M. O., Lu L., NASICON-structured LiGe₂(PO₄)₃ with improved cyclability for high-performance lithium batteries. J. Phys. Chem. C 113, 20514–20520 (2009). [Google Scholar]

[R84] 84.Hu Y.-W., Raistrick I. D., Huggins R. A., Ionic conductivity of lithium phosphate-doped lithium orthosilicate. Mater. Res. Bull. 11, 1227–1230 (1976). [Google Scholar]

[R85] 85.Khorassani A., Izquierdo G., West A. R., The solid electrolyte system Li₃PO₄-Li₄SiO₄. Mater. Res. Bull. 16, 1561–1567 (1981). [Google Scholar]

[R86] 86.Wang D., Zhong G., Lia Y., Gong Z., McDonald M. J., Mi J.-X., Fu R., Shi Z., Yang Y., Enhanced ionic conductivity of Li_3.5Si_0.5P_0.5O₄ with addition of lithium borate. Solid State Ion. 283, 109–114 (2015). [Google Scholar]

[R87] 87.Sudo R., Nakata Y., Ishiguro K., Matsui M., Hirano A., Takeda Y., Yamamoto O., Imanishi N., Interface behavior between garnet-type lithium-conducting solid electrolyte and lithium metal. Solid State Ion. 262, 151–154 (2014). [Google Scholar]

[R88] 88.Ramakumar S., Janani N., Murugan R., Influence of lithium concentration on the structure and Li⁺ transport properties of cubic phase lithium garnets. Dalton Trans. 44, 539–552 (2015). [DOI] [PubMed] [Google Scholar]

[R89] 89.Zhang Y., Luo D., Luo W., Du S., Deng Y., Deng J., High-purity and high-density cubic phase of Li₇La₃Zr₂O₁₂ solid electrolytes by controlling surface/volume ratio and sintering pressure. Electrochim. Acta 359, 136965 (2020). [Google Scholar]

[R90] 90.Thangadurai V., Kaack H., Weppner W. J. F., Novel fast lithium ion conduction in garnet-type Li₅La₃M₂O₁₂ (M = Nb, Ta). J. Am. Ceram. Soc. 86, 437–440 (2003). [Google Scholar]

[R91] 91.Nemori H., Matsuda Y., Matsui M., Yamamoto O., Takeda Y., Imanishi N., Relationship between lithium content and ionic conductivity in the Li_5+2xLa₃Nb_2-xScxO₁₂ system. Solid State Ion. 266, 9–12 (2014). [Google Scholar]

[R92] 92.Wang W. G., Wang X. P., Gao Y. X., Fang Q. F., Lithium-ionic diffusion and electrical conduction in the Li₇La₃Ta₂O₁₃ compounds. Solid State Ion. 180, 1252–1256 (2009). [Google Scholar]

[R93] 93.Wang W. G., Wang X. P., Gao Y. X., Hao G. L., Ma W. Q., Fang Q. F., Internal friction study on the lithium ion diffusion of Li₅La₃M₂O₁₂ (M = Ta, Nb) ionic conductors. Solid State Ion. 13, 1760–1764 (2011). [Google Scholar]

[R94] 94.Wang Y., Lai W., High ionic conductivity lithium garnet oxides of Li_7-xLa₃Zr_2-xTaxO₁₂ compositions. Electrochem. Solid State 15, A68–A71 (2012). [Google Scholar]

[R95] 95.Kotobuki M., Kanamura K., Fabrication of all-solid-state battery using Li₅La₃Ta₂O₁₂ ceramic electrolyte. Ceram. Int. 39, 6481–6487 (2013). [Google Scholar]

[R96] 96.Inaguma Y., Chen L., Itoh M., Nakamura T., Uchida T., Ikuta H., Wakihara M., High ionic conductivity in lithium lanthanum titanate. Solid State Commun. 86, 689–693 (1993). [Google Scholar]

[R97] 97.Tang H., Xu J., Enhanced electrochemical performance of LiFePO₄ coated with Li_0.34La_0.51TiO_2.94 by rheological phase reaction method. Mater. Sci. Eng. B 178, 1503–1508 (2013). [Google Scholar]

[R98] 98.Le H. T. T., Kalubarme R. S., Ngo D. T., Jang S.-Y., Jung K.-N., Shin K.-H., Park C.-J., Citrate gel synthesis of aluminum-doped lithium lanthanum titanate solid electrolyte for application in organic-type lithium-oxygen batteries. J. Power Sources 274, 1188–1199 (2015). [Google Scholar]

[R99] 99.Le H. T. T., Ngo D. T., Kim Y.-J., Park C.-N., Park C.-J., A perovskite-structured aluminium-substituted lithium lanthanum titanate as a potential artificial solid-electrolyte interface for aqueous rechargeable lithium-metal-based batteries. Electrochim. Acta 248, 232–242 (2017). [Google Scholar]

[R100] 100.Itoh M., Inaguma Y., Jung W.-H., Chen L., Nakamura T., High lithium ion conductivity in the perovskite-type compounds Ln_1/2Li_1/2TiO₃ (Ln = La, Pr, Nd, Sm). Solid State Ion. 70-71, 203–207 (1994). [Google Scholar]

[R101] 101.Stramare S., Thangadurai V., Weppner W., Lithium lanthanum titanates: A review. Chem. Mater. 15, 3974–3990 (2003). [Google Scholar]

[R102] 102.Zhou Q., Xu B., Chien P.-H., Li Y., Huang B., Wu N., Xu H., Grundish N. S., Hu Y.-Y., Goodenough J. B., NASICON Li_1.2Mg_0.1Zr_1.9(PO₄)₃ solid electrolyte for an all-solid-state Li-metal battery. Small Methods 4, 2000764 (2020). [Google Scholar]

[R103] 103.Kosova N. V., Devyatkina E. T., Stepanov A. P., Buzlukov A. L., Lithium conductivity and lithium diffusion in NASICON-type Li_1+xTi_2–xAlx(PO₄)₃ (x = 0;0.3) prepared by mechanical activation. Ionics 14, 303–311 (2008). [Google Scholar]

[R104] 104.Zhu Y. Z., He X. F., Mo Y. F., Origin of outstanding stability in the lithium solid electrolyte materials: Insights from thermodynamic analyses based on first-principles calculations. ACS Appl. Mater. Interfaces 7, 23685–23693 (2015). [DOI] [PubMed] [Google Scholar]

[R105] 105.Wu X. M., Li X. H., Zhang Y. H., Xu M. F., He Z. Q., Synthesis of Li_1.3Al_0.3Ti_1.7(PO₄)₃ by sol–gel technique. Mater. Lett. 58, 1227–1230 (2004). [Google Scholar]

[R106] 106.Kotobuki M., Koishi M., Preparation of Li_1.5Al_0.5Ti_1.5(PO₄)₃ solid electrolyte via a sol-gel route using various Al sources. Ceram. Int. 39, 4645–4649 (2013). [Google Scholar]

[R107] 107.Breuer S., Prutsch D., Ma Q., Epp V., Preishuber-Pflugl F., Tietz F., Wilkening M., Separating bulk from grain boundary Li ion conductivity in the sol-gel prepared solid electrolyte Li_1.5Al_0.5Ti_1.5(PO₄)₃. J. Mater. Chem. A 3, 21343–21350 (2015). [Google Scholar]

[R108] 108.Feng J. K., Lu L., Lai M. O., Lithium storage capability of lithium ion conductor Li_1.5Al_0.5Ge_1.5(PO₄)₃. J. Alloys Compd. 501, 255–258 (2010). [Google Scholar]

[R109] 109.Illbeigi M., Fazlali A., Kazazi M., Mohammadi A. H., Effect of simultaneous addition of aluminum and chromium on the lithium ionic conductivity of LiGe₂(PO₄)₃ NASICON-type glass-ceramics. Solid State Ion. 289, 180–187 (2016). [Google Scholar]

[R110] 110.Thompson T., Yu S., Williams L., Schmidt R. D., Garcia-Mendez R., Wolfenstine J., Allen J. L., Kioupakis E., Siegel D. J., Sakamoto J., Electrochemical window of the Li-ion solid electrolyte Li₇La₃Zr₂O₁₂. ACS Energy Lett. 2, 462–468 (2017). [Google Scholar]

[R111] 111.Ohta S., Kobayashi T., Asaoka T., High lithium ionic conductivity in the garnet-type oxide Li_7−xLa₃(Zr_2−x, Nbx)O₁₂ (x = 0–2). J. Power Sources 196, 3342–3345 (2011). [Google Scholar]

[R112] 112.Wei J., Ogawa D., Fukumura T., Hirose Y., Hasegawa T., Epitaxial strain-controlled ionic conductivity in Li-ion solid electrolyte Li_0.33La_0.56TiO₃ thin films. Cryst. Growth Des. 15, 2187–2191 (2015). [Google Scholar]

[R113] 113.Chen C. H., Amine K., Ionic conductivity, lithium insertion and extraction of lanthanum lithium titanate. Solid State Ion. 144, 51–57 (2001). [Google Scholar]

[R114] 114.Yamaki J., Ohtsuka H., Shodai T., Rechargeable lithium thin film cells with inorganic electrolytes. Solid State Ion. 86-88, 1279–1284 (1996). [Google Scholar]

[R115] 115.Bruce P. G., West A. R., Ionic conductivity of LISICON solid solutions, Li_2+2xZn_1-xGeO₄. J. Solid State Chem. 44, 354–365 (1982). [Google Scholar]

[R116] 116.Gao J., Zhao Y. S., Shi S. Q., Li H., Lithium-ion transport in inorganic solid state electrolyte. Chin. Phys. B 25, 018211 (2016). [Google Scholar]

[R117] 117.Li W., Wu G., Araújo C. M., Scheicher R. H., Blomqvist A., Ahuja R., Xiong Z., Feng Y., Chen P., Li⁺ ion conductivity and diffusion mechanism in α-Li₃N and β-Li₃N. Energ. Environ. Sci. 3, 1524–1530 (2010). [Google Scholar]

[R118] 118.Rabenau A., Lithium nitride and related materials case study of the use of modern solid state research techniques. Solid State Ion. 6, 277–293 (1982). [Google Scholar]

[R119] 119.Rea J. R., Foster D. L., Mallory P. R., Inc C., High ionic conductivity in densified polycrystalline lithium nitride. Mater. Res. Bull. 14, 841–846 (1979). [Google Scholar]

[R120] 120.Xu R., Wu Z., Zhang S., Wang X., Xia Y., Xia X., Huang X., Tu J., Construction of all-solid-state batteries based on a sulfur-graphene composite and Li_9.54Si_1.74P_1.44S_11.7Cl_0.3 solid electrolyte. Chem. Eur. J. 23, 13950–13956 (2017). [DOI] [PubMed] [Google Scholar]

[R121] 121.Seino Y., Ota T., Takada K., Hayashi A., Tatsumisago M., A sulphide lithium super ion conductor is superior to liquid ion conductors for use in rechargeable batteries. Energ. Environ. Sci. 7, 627–631 (2014). [Google Scholar]

[R122] 122.Boulineau S., Courty M., Tarascon J. M., Viallet V., Mechanochemical synthesis of li-argyrodite Li₆PS₅X (X=Cl, Br, I) as sulfur-based solid electrolytes for all solid state batteries application. Solid State Ion. 221, 1–5 (2012). [Google Scholar]

[R123] 123.Rangasamy E., Liu Z., Gobet M., Pilar K., Sahu G., Zhou W., Wu H., Greenbaum S., Liang C., An iodide-based Li₇P₂S₈I superionic conductor. J. Am. Chem. Soc. 137, 1384–1387 (2015). [DOI] [PubMed] [Google Scholar]

[R124] 124.Zhou D., Shanmukaraj D., Tkacheva A., Armand M., Wang G. X., Polymer electrolytes for lithium-based batteries: Advances and Prospects. Chem 5, 2326–2352 (2019). [Google Scholar]

[R125] 125.Zhang J., Zhao J., Yue L., Wang Q., Chai J., Liu Z., Zhou X., Li H., Guo Y., Cui G., Chen L., Safety-reinforced poly(propylene carbonate)-based all-solid-state polymer electrolyte for ambient-temperature solid polymer lithium batteries. Adv. Energy Mater. 5, 1501082 (2015). [Google Scholar]

[R126] 126.Chen K., Shen Y., Jiang J., Zhang Y., Lin Y., Nan C.-W., High capacity and rate performance of LiNi_0.5Co_0.2Mn_0.3O₂ composite cathode for bulk-type all-solid-state lithium battery. J. Mater. Chem. A 2, 13332–13337 (2014). [Google Scholar]

[R127] 127.Shao Y., Wang H., Gong Z., Wang D., Zheng B., Zhu J., Lu Y., Hu Y.-S., Guo X., Li H., Huang X., Yang Y., Nan C.-W., Chen L., Drawing a soft interface: An effective interfacial modification strategy for garnet-type solid-state Li batteries. ACS Energy Lett. 3, 1212–1218 (2018). [Google Scholar]

[R128] 128.Liu B., Zhang L., Xu S., McOwen D. W., Gong Y., Yang C., Pastel G. R., Xie H., Fu K., Dai J., Chen C., Wachsman E. D., Hu L., 3D lithium metal anodes hosted in asymmetric garnet frameworks toward high energy density batteries. Energy Storage Mater. 14, 376–382 (2018). [Google Scholar]

[R129] 129.Liu T., Zhang Y., Zhang X., Wang L., Zhao S.-X., Lin Y.-H., Shen Y., Luo J., Li L., Nan C.-W., Enhanced electrochemical performance of bulk type oxide ceramic lithium batteries enabled by interface modification. J. Mater. Chem. A 6, 4649–4657 (2018). [Google Scholar]

[R130] 130.Chen L., Li W. X., Fan L. Z., Nan C.-W., Zhang Q., Intercalated electrolyte with high transference number for dendrite-free solid-state lithium batteries. Adv. Funct. Mater. 29, 1901047 (2019). [Google Scholar]

[R131] 131.Jiang T., He P., Wang G., Shen Y., Nan C.-W., Fan L.-Z., Solvent-free synthesis of thin, flexible, nonflammable garnet-based composite solid electrolyte for all-solid-state lithium batteries. Adv. Energy Mater. 10, 1903376 (2020). [Google Scholar]

[R132] 132.Zhang B., Chen L., Hu J., Liu Y., Liu Y., Feng Q., Zhu G., Fan L.-Z., Solid-state lithium metal batteries enabled with high loading composite cathode materials and ceramic-based composite electrolytes. J. Power Sources 442, 227230 (2019). [Google Scholar]

[R133] 133.Huang S., Yang H., Hu J., Liu Y., Wang K., Peng H., Zhang H., Fan L.-Z., Early lithium plating behavior in confined nanospace of 3D lithiophilic carbon matrix for stable solid-state lithium metal batteries. Small 15, 1904216 (2019). [DOI] [PubMed] [Google Scholar]

[R134] 134.Ruan Y., Lu Y., Huang X., Su J., Sun C., Jin J., Wen Z., Acid induced conversion towards a robust and lithiophilic interface for Li-Li₇La₃Zr₂O₁₂ solid-state batteries. J. Mater. Chem. A 7, 14565–14574 (2019). [Google Scholar]

[R135] 135.Wang G. X., He P. G., Fan L. Z., Asymmetric polymer electrolyte constructed by metal-organic framework for solid-state, dendrite-free lithium metal battery. Adv. Funct. Mater. 31, 2007198 (2021). [Google Scholar]

[R136] 136.Zhuang Z., Yang L., Ju B., Lei G., Zhou Q., Liao H., Yin A., Deng Z., Tang Y., Qin S., Tu F., Ameliorating interfacial issues of LiNi_0.5Co_0.2Mn_0.3O₂/poly (propylene carbonate) by introducing graphene interlayer for all-solid-state lithium batteries. ChemistrySelect 5, 2291–2299 (2020). [Google Scholar]

[R137] 137.Zhao L., Fu J., Du Z., Jia X., Qu Y., Yu F., Du J., Chen Y., High-strength and flexible cellulose/PEG based gel polymer electrolyte with high performance for lithium ion batteries. J. Membr. Sci. 593, 117428 (2020). [Google Scholar]

[R138] 138.Zha W. P., Li W. W., Ruan Y. D., Wang J. C., Wen Z. Y., In situ fabricated ceramic/polymer hybrid electrolyte with vertically aligned structure for solid-state lithium batteries. Energ. Storage Mater. 36, 171–178 (2021). [Google Scholar]

PERMALINK

Enhancing ionic conductivity in solid electrolyte by relocating diffusion ions to under-coordination sites

Lei Zhu

Youwei Wang

Junchao Chen

Wenlei Li

Tiantian Wang

Jie Wu

Songyi Han

Yuanhua Xia

Yongmin Wu

Mengqiang Wu

Fangwei Wang

Yi Zheng

Luming Peng

Jianjun Liu

Liquan Chen

Weiping Tang

Roles

Abstract

INTRODUCTION

Fig. 1. Relationships among coordination modulation, bottleneck, and migration energy barrier.

RESULTS

Synthesis and local coordination of Li+ ions

Fig. 2. Crystal structures of NZSP and LZSP.

Ionic conductivity of the LZSP solid electrolyte

Fig. 3. Comparison of LZSP with other undoped oxide solid electrolytes on ionic conductivities.

Diffusion mechanism and kinetics

Fig. 4. Single-ion migration mechanisms of Na+ ion and Li+ ion from CI-NEB.

Fig. 5. Diffusion kinetics of NZSP and LZSP from AIMD simulations.

Electrochemical test of solid-state batteries

Fig. 6. The electrochemical performance of battery devices based on the LZSP solid electrolyte.

DISCUSSION

MATERIALS AND METHODS

Preparation of NZSP

Process of skeleton-retained cation exchange

Process of 17O isotopic labeling

Characterization

Computational methods

Fabrication of LZSP pellets

Electrochemical tests

Acknowledgments

Supplementary Materials

This PDF file includes:

REFERENCES AND NOTES

Associated Data

Supplementary Materials

ACTIONS

PERMALINK

RESOURCES

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Synthesis and local coordination of Li⁺ ions

Fig. 4. Single-ion migration mechanisms of Na⁺ ion and Li⁺ ion from CI-NEB.

Process of ¹⁷O isotopic labeling