Solid-state batteries with desirable advantages, including high-energy density, wide temperature tolerance, and fewer safety-concerns, have been considered as a promising energy storage technology to replace organic liquid electrolyte-dominated Li-ion batteries. Solid-state electrolytes (SSEs) as the most critical component in solid-state batteries largely lead the future battery development. Among different types of solid-state electrolytes, garnet-type Li7La3Zr2O12 (LLZO) solid-state electrolytes have particularly high ionic conductivity (10–3 to 10–4 S/cm) and good chemical stability against Li metal, offering a great opportunity for solid-state Li-metal batteries. Since the discovery of garnet-type LLZO in 2007, there has been an increasing interest in the development of garnet-type solid-state electrolytes and all solid-state batteries. Garnet-type electrolyte has been considered one of the most promising and important solid-state electrolytes for batteries with potential benefits in energy density, electrochemical stability, high temperature stability, and safety. In this Review, we will survey recent development of garnet-type LLZO electrolytes with discussions of experimental studies and theoretical results in parallel, LLZO electrolyte synthesis strategies and modifications, stability of garnet solid electrolytes/electrodes, emerging nanostructure designs, degradation mechanisms and mitigations, and battery architectures and integrations. We will also provide a target-oriented research overview of garnet-type LLZO electrolyte and its application in various types of solid-state battery concepts (e.g., Li-ion, Li–S, and Li–air), and we will show opportunities and perspectives as guides for future development of solid electrolytes and solid-state batteries.

Beyond state-of-the-art lithium-ion battery (LIB) technology with metallic lithium anodes to replace conventional ion intercalation anode materials is highly desirable because of lithium's highest specific capacity (3,860 mA/g) and lowest negative electrochemical potential (∼3.040 V vs. the standard hydrogen electrode). In this work, we report for the first time, to our knowledge, a 3D lithium-ion-conducting ceramic network based on garnet-type Li 6.4 La 3 Zr 2 Al 0.2 O 12 (LLZO) lithium-ion conductor to provide continuous Li + transfer channels in a polyethylene oxide (PEO)-based composite. This composite structure further provides structural reinforcement to enhance the mechanical properties of the polymer matrix. The flexible solid-state electrolyte composite membrane exhibited an ionic conductivity of 2.5 × 10 −4 S/cm at room temperature. The membrane can effectively block dendrites in a symmetric Li j electrolyte j Li cell during repeated lithium stripping/plating at room temperature, with a current density of 0.2 mA/cm 2 for around 500 h and a current density of 0.5 mA/cm 2 for over 300 h. These results provide an all solid ion-conducting membrane that can be applied to flexible LIBs and other electrochemical energy storage systems, such as lithium-sulfur batteries.solid-state electrolyte | 3D garnet nanofibers | polyethylene oxide | ionic conductor | flexible membrane H igh capacity, high safety, and long lifespan are three of the most important key factors to developing rechargeable lithium batteries for applications in portable electronics, transportation (e.g., electrical vehicles), and large-scale energy storage systems (1-5). Based on state-of-the-art lithium-ion battery (LIB) technology, metallic lithium anode is preferable to replace conventional ion intercalation anode materials because of the highest specific capacity (3,860 mAh/g) of lithium and the lowest negative electrochemical potential (∼3.040 V vs. the standard hydrogen electrode), which can maximize the capacity density and voltage window for increased battery energy density (1). Moreover, the success of beyond LIBs, such as lithium-sulfur and lithium-oxygen, will strongly rely on lithium metal anode designs with good stability to achieve their targeted goals of high energy density and long cycle life.Using lithium metal in organic liquid electrolyte systems faces many challenges in terms of battery performance and safety. For example, lithium-sulfur batteries suffer from the dissolution of intermediate polysulfides in the organic electrolyte that causes severe parasitic reactions on lithium metal surfaces, leading to lithium metal degradation and low lithium cycling efficiency (6). Lithium-oxygen batteries have the challenge of chemically instable liquid electrolytes on the oxygen electrode that cause limited battery cycling (7). All of these challenges are associated with the use of lithium metal in liquid electrolyte battery systems. Another major associated challenge is lithium dendrite growth on lithium metal anodes, which causes int...

Strategy to change the wettability of the solid-state electrolyte against Li and reduce interface resistance.

Solid-state electrolytes are known for nonflammability, dendrite blocking, and stability over large potential windows. Garnet-based solid-state electrolytes have attracted much attention for their high ionic conductivities and stability with lithium metal anodes. However, high-interface resistance with lithium anodes hinders their application to lithium metal batteries. Here, we demonstrate an ultrathin, conformal ZnO surface coating by atomic layer deposition for improved wettability of garnet solid-state electrolytes to molten lithium that significantly decreases the interface resistance to as low as ∼20 Ω·cm. The ZnO coating demonstrates a high reactivity with lithium metal, which is systematically characterized. As a proof-of-concept, we successfully infiltrated lithium metal into porous garnet electrolyte, which can potentially serve as a self-supported lithium metal composite anode having both high ionic and electrical conductivity for solid-state lithium metal batteries. The facile surface treatment method offers a simple strategy to solve the interface problem in solid-state lithium metal batteries with garnet solid electrolytes.

All-solid-state Li-batteries using solid-state electrolytes (SSEs) offer enhanced safety over conventional Li-ion batteries with organic liquid electrolytes due to the nonflammable nature of SSEs. The superior mechanical strength of SSEs can also protect against Li dendrite penetration, which enables the use of the highest specific capacity (3861 mAh/g) and lowest redox potential (-3.04 V vs standard hydrogen electrode) anode: Li metal. However, contact between the Li metal and SSEs presents a major challenge, where a large polarization occurs at the Li metal/SSE interface. Here, the chemical properties of a promising oxide-based SSE (garnet) changed from "super-lithiophobicity" to "super-lithiophilicity" through an ultrathin coating of amorphous Si deposited by plasma-enhanced chemical vapor deposition (PECVD). The wettability transition is due to the reaction between Li and Si and the in situ formation of lithiated Si. As a result, symmetric cells composed of a Si-coated garnet-structured SSE and Li metal electrodes exhibited much smaller impedance and excellent stability upon plating/stripping cycles compared to cells using bare garnet SSE. Specifically, the interfacial resistance between Li and garnet dramatically decreased from 925 to 127 Ω cm(2) when lithiated Si was formed on the garnet. Our discovery of switchable lithiophobic-lithiophilic surfaces to improve the Li metal/SSE interface opens opportunities for improving many other SSEs.