Yonggang Yao

Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries

Significance This work describes a flexible, solid-state, lithium-ion–conducting membrane based on a 3D ion-conducting network and polymer electrolyte for lithium batteries. The 3D ion-conducting network is based on percolative garnet-type Li6.4La3Zr2Al0.2O12 solid-state electrolyte nanofibers, which enhance the ionic conductivity of the solid-state electrolyte membrane at room temperature and improve the mechanical strength of the polymer electrolyte. The membrane has shown superior electrochemical stability to high voltage and high mechanical stability to effectively block lithium dendrites. This work represents a significant breakthrough to enable high performance of lithium 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 Li6.4La3Zr2Al0.2O12 (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 | electrolyte | Li cell during repeated lithium stripping/plating at room temperature, with a current density of 0.2 mA/cm2 for around 500 h and a current density of 0.5 mA/cm2 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.

Graphene Oxide‐Based Electrode Inks for 3D‐Printed Lithium‐Ion Batteries

All-component 3D-printed lithium-ion batteries are fabricated by printing graphene-oxide-based composite inks and solid-state gel polymer electrolyte. An entirely 3D-printed full cell features a high electrode mass loading of 18 mg cm(-2) , which is normalized to the overall area of the battery. This all-component printing can be extended to the fabrication of multidimensional/multiscale complex-structures of more energy-storage devices.

All-wood, low tortuosity, aqueous, biodegradable supercapacitors with ultra-high capacitance

In energy storage devices, the critical demands for high energy/power density, low cost, long cycle lives and environmental friendliness have highlighted an urgent need for developing storage electrodes with low cost, large thickness, high mass loading, low tortuosity and high energy/power density. Here we demonstrate the design and construction of an all-wood-structured asymmetric supercapacitor (ASC) based on an activated wood carbon (AWC) anode, a wood membrane separator and a MnO2/wood carbon (MnO2@WC) cathode. The structural virtues of the all-wood-structured ASC device – desirable thickness (up to ∼1 mm), direct channels with low tortuosity, high electronic and ionic conductivity – enable ASC high areal mass loadings (up to 30 mg cm−2 for the anode and 75 mg cm−2 for the wood carbon/MnO2 composite cathode), a high energy density of 1.6 mW h cm−2 and a maximum power density of 24 W cm−2, representing the highest mass loading and areal energy/power densities among all reported MnO2-based supercapacitors. Moreover, all components in the all-wood-structured ASC are low-cost, environmentally friendly and biocompatible. With these unique features, the all-wood-structured ASC represents a promising energy storage device to realize high mass loading, high energy/power density, and biocompatibility for green and renewable energy storage.

A Thermally Conductive Separator for Stable Li Metal Anodes.

Li metal anodes have attracted considerable research interest due to their low redox potential (-3.04 V vs standard hydrogen electrode) and high theoretical gravimetric capacity of 3861 mAh/g. Battery technologies using Li metal anodes have shown much higher energy density than current Li-ion batteries (LIBs) such as Li-O2 and Li-S systems. However, issues related to dendritic Li formation and low Coulombic efficiency have prevented the use of Li metal anode technology in many practical applications. In this paper, a thermally conductive separator coated with boron-nitride (BN) nanosheets has been developed to improve the stability of the Li metal anodes. It is found that using the BN-coated separator in a conventional organic carbonate-based electrolyte results in the Coulombic efficiency stabilizing at 92% over 100 cycles at a current rate of 0.5 mA/cm(2) and 88% at 1.0 mA/cm(2). The improved Coulombic efficiency and reliability of the Li metal anodes is due to the more homogeneous thermal distribution resulting from the thermally conductive BN coating and to the smaller surface area of initial Li deposition.

Conformal, Nanoscale ZnO Surface Modification of Garnet-Based Solid-State Electrolyte for Lithium Metal Anodes

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·cm2. 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.

Highly Anisotropic, Highly Transparent Wood Composites

For the first time, two types of highly anisotropic, highly transparent wood composites are demonstrated by taking advantage of the macro-structures in original wood. These wood composites are highly transparent with a total transmittance up to 90% but exhibit dramatically different optical and mechanical properties.

Reducing Interfacial Resistance between Garnet‐Structured Solid‐State Electrolyte and Li‐Metal Anode by a Germanium Layer

Substantial efforts are underway to develop all-solid-state Li batteries (SSLiBs) toward high safety, high power density, and high energy density. Garnet-structured solid-state electrolyte exhibits great promise for SSLiBs owing to its high Li-ion conductivity, wide potential window, and sufficient thermal/chemical stability. A major challenge of garnet is that the contact between the garnet and the Li-metal anodes is poor due to the rigidity of the garnet, which leads to limited active sites and large interfacial resistance. This study proposes a new methodology for reducing the garnet/Li-metal interfacial resistance by depositing a thin germanium (Ge) (20 nm) layer on garnet. By applying this approach, the garnet/Li-metal interfacial resistance decreases from ≈900 to ≈115 Ω cm2 due to an alloying reaction between the Li metal and the Ge. In agreement with experiments, first-principles calculation confirms the good stability and improved wetting at the interface between the lithiated Ge layer and garnet. In this way, this unique Ge modification technique enables a stable cycling performance of a full cell of lithium metal, garnet electrolyte, and LiFePO4 cathode at room temperature.

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

Strategy to change the wettability of the solid-state electrolyte against Li and reduce interface resistance. Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li7La3Zr2O12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10−3 to 10−4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnet solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm2 for the surface-engineered garnet/Li. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.

Three-dimensional bilayer garnet solid electrolyte based high energy density lithium metal–sulfur batteries

To simultaneously address the challenges of chemical/physical short circuits and electrode volume variation, we demonstrate a three-dimensional (3D) bilayer garnet solid-state electrolyte framework for advanced Li metal batteries. The dense layer is reduced in thickness to a few microns and still retains good mechanical stability, thereby enabling the safe use of Li metal anodes. The thick porous layer acts as a mechanical support for the thin dense layer which serves as a host for high loading of cathode materials and provides pathways for continuous ion transport. Results show that the integrated sulfur cathode loading can reach >7 mg cm−2 while the proposed hybrid Li–S battery exhibits a high initial coulombic efficiency (>99.8%) and high average coulombic efficiency (>99%) during the subsequent cycles. This electrolyte framework represents a promising strategy to revolutionize Li-metal batteries by transitioning to all-solid-state batteries and can be extended to other cathode materials.

Self-Powered Human-Interactive Transparent Nanopaper Systems

Self-powered human-interactive but invisible electronics have many applications in anti-theft and anti-fake systems for human society. In this work, for the first time, we demonstrate a transparent paper-based, self-powered, and human-interactive flexible system. The system is based on an electrostatic induction mechanism with no extra power system appended. The self-powered, transparent paper device can be used for a transparent paper-based art anti-theft system in museums or for a smart mapping anti-fake system in precious packaging and documents, by virtue of the advantages of adding/removing freely, having no impairment on the appearance of the protected objects, and being easily mass manufactured. This initial study bridges the transparent nanopaper with a self-powered and human-interactive electronic system, paving the way for the development of smart transparent paper electronics.