Leigang Xue

Low-Cost High-Energy Potassium Cathode

Potassium has as rich an abundance as sodium in the earth, but the development of a K-ion battery is lagging behind because of the higher mass and larger ionic size of K+ than that of Li+ and Na+, which makes it difficult to identify a high-voltage and high-capacity intercalation cathode host. Here we propose a cyanoperovskite KxMnFe(CN)6 (0 ≤ x ≤ 2) as a potassium cathode: high-spin MnIII/MnII and low-spin FeIII/FeII couples have similar energies and exhibit two close plateaus centered at 3.6 V; two active K+ per formula unit enable a theoretical specific capacity of 156 mAh g-1; Mn and Fe are the two most-desired transition metals for electrodes because they are cheap and environmental friendly. As a powder prepared by an inexpensive precipitation method, the cathode delivers a specific capacity of 142 mAh g-1. The observed voltage, capacity, and its low cost make it competitive in large-scale electricity storage applications.

Hybrid Polymer/Garnet Electrolyte with a Small Interfacial Resistance for Lithium-Ion Batteries

Li7 La3 Zr2 O12 -based Li-rich garnets react with water and carbon dioxide in air to form a Li-ion insulating Li2 CO3 layer on the surface of the garnet particles, which results in a large interfacial resistance for Li-ion transfer. Here, we introduce LiF to garnet Li6.5 La3 Zr1.5 Ta0.5 O12 (LLZT) to increase the stability of the garnet electrolyte against moist air; the garnet LLZT-2 wt % LiF (LLZT-2LiF) has less Li2 CO3 on the surface and shows a small interfacial resistance with Li metal, a solid polymer electrolyte, and organic-liquid electrolytes. An all-solid-state Li/polymer/LLZT-2LiF/LiFePO4 battery has a high Coulombic efficiency and long cycle life; a Li-S cell with the LLZT-2LiF electrolyte as a separator, which blocks the polysulfide transport towards the Li-metal, also has high Coulombic efficiency and kept 93 % of its capacity after 100 cycles.

Mastering the interface for advanced all-solid-state lithium rechargeable batteries

Significance Realization of a safe, low-cost rechargeable lithium battery of high energy density and long cycle life is needed for powering an electric road vehicle and for storing electric power generated by solar or wind energy. This urgent need has prompted efforts to develop a solid electrolyte with an alkali metal anode. Only now is it recognized that the key requirement is wetting of the electrolyte surface by the alkali-metal anode. We report a full rechargeable cell with a solid electrolyte that, although it is reduced by metallic lithium, forms a thin lithium–electrolyte interface that is wet by the anode and wets the electrolyte to give a small Li+ transfer resistance across the interface. A solid electrolyte with a high Li-ion conductivity and a small interfacial resistance against a Li metal anode is a key component in all-solid-state Li metal batteries, but there is no ceramic oxide electrolyte available for this application except the thin-film Li-P oxynitride electrolyte; ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites in a short time. Here, we introduce a solid electrolyte LiZr2(PO4)3 with rhombohedral structure at room temperature that has a bulk Li-ion conductivity σLi = 2 × 10−4 S⋅cm−1 at 25 °C, a high electrochemical stability up to 5.5 V versus Li+/Li, and a small interfacial resistance for Li+ transfer. It reacts with a metallic lithium anode to form a Li+-conducting passivation layer (solid-electrolyte interphase) containing Li3P and Li8ZrO6 that is wet by the lithium anode and also wets the LiZr2(PO4)3 electrolyte. An all-solid-state Li/LiFePO4 cell with a polymer catholyte shows good cyclability and a long cycle life.

Liquid K-Na Alloy Anode Enables Dendrite-Free Potassium Batteries.

A K-Na liquid alloy allows a dendrite-free high-capacity anode; its immiscibility with an organic liquid electrolyte offers a liquid-liquid anode-electrolyte interface. Working with a sodiated Na2 MnFe(CN)6 cathode, the working cation becomes K+ to give a potassium battery of long cycle life with an acceptable capacity at high charge/discharge rates.

Garnet Electrolyte with an Ultralow Interfacial Resistance for Li-Metal Batteries

Garnet-structured Li7La3Zr2O12 is a promising solid Li-ion electrolyte for all-solid-state Li-metal batteries and Li-redox-flow batteries owing to its high Li-ion conductivity at room temperature and good electrochemical stability with Li metal. However, there are still three major challenges unsolved: (1) the controversial electrochemical window of garnet, (2) the impractically large resistance at a garnet/electrode interface and the fast lithium-dendrite growth along the grain boundaries of the garnet pellet, and (3) the fast degradation during storage. We have found that these challenges are closely related to a thick Li2CO3 layer and the Li-Al-O glass phase on the surface of garnet materials. Here we introduce a simple method to remove Li2CO3 and the protons in the garnet framework by reacting garnet with carbon at 700 °C; moreover, the amount of the Li-Al-O glass phase with a low Li-ion conductivity in the grain boundary on the garnet surface was also reduced. The surface of the carbon-treated garnet pellets is free of Li2CO3 and is wet by a metallic lithium anode, an organic electrolyte, and a solid composite cathode. The carbon post-treatment has reduced significantly the interfacial resistances to 28, 92 (at 65 °C), and 45 Ω cm2 at Li/garnet, garnet/LiFePO4, and garnet/organic-liquid interfaces, respectively. A symmetric Li/garnet/Li, an all-solid-state Li/garnet/LiFePO4, and a hybrid Li-S cell show small overpotentials, high Coulombic efficiencies, and stable cycling performance.

Cathode Dependence of Liquid-Alloy Na–K Anodes

Alkali ions can be plated dendrite-free into a liquid alkali-metal anode. Commercialized Na-S battery technology operates above 300 °C. A low-cost Na-K alloy is liquid at 25 °C from 9.2 to 58.2 wt% of sodium; sodium and/or potassium can be plated dendrite-free in the liquid range at room temperature. The co-existence of two alkali metals in an anode raises a question: whether the liquid Na-K alloy acts as a Na or a K anode. Here we show the alkali-metal that is stripped from the liquid Na-K anode is dependent on the preference of the cathode host. It acts as the anode of a sodium rechargeable cell if the cathode host structure selectively accepts only Na+ ions; as the anode of a potassium rechargeable cell if the cathode accepts K+ ions in preference to Na+ ions. This dual-anode behavior means the liquid Na-K alkali-alloy can be applied as a dendrite-free anode in Na-metal batteries as well as K-metal batteries.

A Perovskite Electrolyte That Is Stable in Moist Air for Lithium‐Ion Batteries

Solid-oxide Li+ electrolytes of a rechargeable cell are generally sensitive to moisture in the air as H+ exchanges for the mobile Li+ of the electrolyte and forms insulating surface phases at the electrolyte interfaces and in the grain boundaries of a polycrystalline membrane. These surface phases dominate the total interfacial resistance of a conventional rechargeable cell with a solid-electrolyte separator. We report a new perovskite Li+ solid electrolyte, Li0.38 Sr0.44 Ta0.7 Hf0.3 O2.95 F0.05 , with a lithium-ion conductivity of σLi =4.8×10-4  S cm-1 at 25 °C that does not react with water having 3≤pH≤14. The solid electrolyte with a thin Li+ -conducting polymer on its surface to prevent reduction of Ta5+ is wet by metallic lithium and provides low-impedance dendrite-free plating/stripping of a lithium anode. It is also stable upon contact with a composite polymer cathode. With this solid electrolyte, we demonstrate excellent cycling performance of an all-solid-state Li/LiFePO4 cell, a Li-S cell with a polymer-gel cathode, and a supercapacitor.