Weidong Zhou

Plating a Dendrite-Free Lithium Anode with a Polymer/Ceramic/Polymer Sandwich Electrolyte

A cross-linked polymer containing pendant molecules attached to the polymer framework is shown to form flexible and low-cost membranes, to be a solid Li(+) electrolyte up to 270 °C, much higher than those based on poly(ethylene oxide), to be wetted by a metallic lithium anode, and to be not decomposed by the metallic anode if the anions of the salt are blocked by a ceramic electrolyte in a polymer/ceramic membrane/polymer sandwich electrolyte (PCPSE). In this sandwich architecture, the double-layer electric field at the Li/polymer interface is reduced due to the blocked salt anion transfer. The polymer layer adheres/wets the lithium metal surface and makes the Li-ion flux at the interface more homogeneous. This structure integrates the advantages of the ceramic and polymer. With the PCPSE, all-solid-state Li/LiFePO4 cells showed a notably high Coulombic efficiency of 99.8-100% over 640 cycles.

Mesoporous Titanium Nitride‐Enabled Highly Stable Lithium‐Sulfur Batteries

The TiN-S composite cathode exhibits superior performance because of higher electrical conductivity and the capture of the soluble intermediate species of the electrode reactions by 2-5 nm mesopores and strong N-S surface bonding.

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.

Fluorine-Doped Antiperovskite Electrolyte for All-Solid-State Lithium-Ion Batteries

A fluorine-doped antiperovskite Li-ion conductor Li2 (OH)X (X=Cl, Br) is shown to be a promising candidate for a solid electrolyte in an all-solid-state Li-ion rechargeable battery. Substitution of F(-) for OH(-) transforms orthorhombic Li2 OHCl to a room-temperature cubic phase, which shows electrochemical stability to 9 V versus Li(+) /Li and two orders of magnitude higher Li-ion conductivity than that of orthorhombic Li2 OHCl. An all-solid-state Li/LiFePO4 with F-doped Li2 OHCl as the solid electrolyte showed good cyclability and a high coulombic efficiency over 40 charge/discharge cycles.

Rechargeable Sodium All-Solid-State Battery

A reversible plating/stripping of a dendrite-free metallic-sodium anode with a reduced anode/ceramic interfacial resistance is created by a thin interfacial interlayer formed in situ or by the introduction of a dry polymer film. Wetting of the sodium on the interfacial interlayer suppresses dendrite formation and growth at different discharge/charge C-rates. All-solid-state batteries were obtained with a high cycling stability and Coulombic efficiency at 65 °C.

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.

NaFe2PO4(SO4)2: a potential cathode for a Na-ion battery

Hexagonal Na3Zr2PO4(SiO4)2 is a well-known fast Na+ conductor commonly referred to as NASICON. The low cost and wide availability of sodium invites exploration of Na+-insertion cathodes with the hexagonal NASICON framework structure. Here we report a low-temperature synthesis of NaFe2PO4(SO4)2 with the same host framework as NASICON and its performance as the cathode of a Na/Na1+xFe2PO4(SO4)2 cell operating on the Fe3+/Fe2+ redox couple. The cell provides a single-phase reaction having a capacity approaching 100 mA h g−1 at 0.1C after 50 cycles over the voltage range 2 ≤ V ≤ 4 V with a coulomb efficiency approaching 100%. An increase in capacity with cycling is the result of aging of an unoptimized electrode morphology.

Li-Ion Conduction and Stability of Perovskite Li3/8Sr7/16Hf1/4Ta3/4O3.

A solid Li-ion conductor with a high room temperature Li-ion conductivity and small interfacial resistance is required for its application in next-generation Li-ion batteries. Here, we prepared a cubic perovskite-related oxide with the general formula Li3/8Sr7/16Hf1/4Ta3/4O3 (LSHT) by a conventional solid-state reaction method, which was studied by X-ray diffraction, electrochemical impedance spectroscopy, and (7)Li MAS NMR. Li3/8Sr7/16Hf1/4Ta3/4O3 has a high Li-ion conductivity of 3.8 × 10(-4) S cm(-1) at 25 °C and a low activation energy of 0.36 eV in the temperature range 298-430 K. It exhibits both high stability and small interfacial resistance with commercial organic liquid electrolytes, which makes it promising as a separator in Li-ion batteries.