Chengwei Wang

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.

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.

High-capacity, low-tortuosity, and channel-guided lithium metal anode

Significance Li metal is considered as the “Holy Grail” anode for Li batteries due to its highest theoretical capacity and lowest electrochemical potential. However, the infinite volume change during the Li stripping/plating process would lead to issues like solid electrolyte interphase cracks and Li dendrites. This work describes a high-capacity and low-tortuosity Li metal anode, which was prepared by infusing molten Li into carbonized wood channels. The straight channels of carbonized wood acting as an ideal host can effectively accommodate the Li volume change, which delivered a lower overpotential and better cycling performance compared with bare Li metal. This work demonstrated the importance of structure design, especially low-tortuosity Li metal structure, for enabling Li metal anode in high-energy batteries. Lithium metal anode with the highest capacity and lowest anode potential is extremely attractive to battery technologies, but infinite volume change during the Li stripping/plating process results in cracks and fractures of the solid electrolyte interphase, low Coulombic efficiency, and dendritic growth of Li. Here, we use a carbonized wood (C-wood) as a 3D, highly porous (73% porosity) conductive framework with well-aligned channels as Li host material. We discovered that molten Li metal can infuse into the straight channels of C-wood to form a Li/C-wood electrode after surface treatment. The C-wood channels function as excellent guides in which the Li stripping/plating process can take place and effectively confine the volume change that occurs. Moreover, the local current density can be minimized due to the 3D C-wood framework. Therefore, in symmetric cells, the as-prepared Li/C-wood electrode presents a lower overpotential (90 mV at 3 mA⋅cm−2), more-stable stripping/plating profiles, and better cycling performance (∼150 h at 3 mA⋅cm−2) compared with bare Li metal electrode. Our findings may open up a solution for fabricating stable Li metal anode, which further facilitates future application of high-energy-density Li metal batteries.

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.

Tree-Inspired Design for High-Efficiency Water Extraction

The solar steam process, akin to the natural water cycle, is considered to be an attractive approach to address water scarcity issues globally. However, water extraction from groundwater, for example, has not been demonstrated using these existing technologies. Additionally, there are major unaddressed challenges in extracting potable water from seawater including salt accumulation and long-term evaporation stability, which warrant further investigation. Herein, a high-performance solar steam device composed entirely of natural wood is reported. The pristine, natural wood is cut along the transverse direction and the top surface is carbonized to create a unique bilayer structure. This tree-inspired design offers distinct advantages for water extraction, including rapid water transport and evaporation in the mesoporous wood, high light absorption (≈99%) within the surface carbonized open wood channels, a low thermal conductivity to avoid thermal loss, and cost effectiveness. The device also exhibits long-term stability in seawater without salt accumulation as well as high performance for underground water extraction. The tree-inspired design offers an inexpensive and scalable solar energy harvesting and steam generation technology that can provide clean water globally, especially for rural or remote areas where water is not only scarce but also limited by water extraction materials and methods.

Rapid Thermal Annealing of Cathode-Garnet Interface toward High-Temperature Solid State Batteries

High-temperature batteries require the battery components to be thermally stable and function properly at high temperatures. Conventional batteries have high-temperature safety issues such as thermal runaway, which are mainly attributed to the properties of liquid organic electrolytes such as low boiling points and high flammability. In this work, we demonstrate a truly all-solid-state high-temperature battery using a thermally stable garnet solid-state electrolyte, a lithium metal anode, and a V2O5 cathode, which can operate well at 100 °C. To address the high interfacial resistance between the solid electrolyte and cathode, a rapid thermal annealing method was developed to melt the cathode and form a continuous contact. The resulting interfacial resistance of the solid electrolyte and V2O5 cathode was significantly decreased from 2.5 × 104 to 71 Ω·cm2 at room temperature and from 170 to 31 Ω·cm2 at 100 °C. Additionally, the diffusion resistance in the V2O5 cathode significantly decreased as well. The demonstrated high-temperature solid-state full cell has an interfacial resistance of 45 Ω·cm2 and 97% Coulombic efficiency cycling at 100 °C. This work provides a strategy to develop high-temperature all-solid-state batteries using garnet solid electrolytes and successfully addresses the high contact resistance between the V2O5 cathode and garnet solid electrolyte without compromising battery safety or performance.

In Situ Neutron Depth Profiling of Lithium Metal–Garnet Interfaces for Solid State Batteries

The garnet-based solid state electrolyte (SSE) is considered a promising candidate to realize all solid state lithium (Li) metal batteries. However, critical issues require additional investigation before practical applications become possible, among which high interfacial impedance and low interfacial stability remain the most challenging. In this work, neutron depth profiling (NDP), a nondestructive and uniquely Li-sensitive technique, has been used to reveal the interfacial behavior of garnet SSE in contact with metallic Li through in situ monitoring of Li plating-stripping processes. The NDP measurement demonstrates predictive capabilities for diagnosing short-circuits in solid state batteries. Two types of cells, symmetric Li/garnet/Li (LGL) cells and asymmetric Li/garnet/carbon-nanotubes (LGC), are fabricated to emulate the behavior of Li metal and Li-free Li metal anodes, respectively. The data imply the limitation of Li-free Li metal anode in forming reliable interfacial contacts, and strategies of excessive Li and better interfacial engineering need to be investigated.

A Solution-Processed High-Temperature, Flexible, Thin-Film Actuator.

A bilayer actuator made of carbon nanotubes (CNTs) and boron nitride (BN) is developed that can withstand high temperatures. The bilayer actuator can be powered quickly to a temperature up to 2000 K within 100 ms and can operate at frequencies from sub-Hertz to about 30 Hz due to the low heat capacity of the thin CNT layer.

Inverted battery design as ion generator for interfacing with biosystems

In a lithium-ion battery, electrons are released from the anode and go through an external electronic circuit to power devices, while ions simultaneously transfer through internal ionic media to meet with electrons at the cathode. Inspired by the fundamental electrochemistry of the lithium-ion battery, we envision a cell that can generate a current of ions instead of electrons, so that ions can be used for potential applications in biosystems. Based on this concept, we report an ‘electron battery’ configuration in which ions travel through an external circuit to interact with the intended biosystem whereas electrons are transported internally. As a proof-of-concept, we demonstrate the application of the electron battery by stimulating a monolayer of cultured cells, which fluoresces a calcium ion wave at a controlled ionic current. Electron batteries with the capability to generate a tunable ionic current could pave the way towards precise ion-system control in a broad range of biological applications.