Enabling Deformable and Stretchable Batteries

Deformable energy storage devices are needed to power next‐generation wearable electronics that interface intimately with human skin. Currently, deformable energy storage devices demonstrate poor performance compared to their rigid lithium‐ion counterparts, forcing wearable manufacturers to design their devices around bulky battery compartments. However, technological advances to create deformable batteries at the component and device level have yielded continuous improvement in stretchable batteries over the last five years. In this Essay, the major strategies at the component and device level that have been successfully employed to create stretchable batteries are reviewed. The outstanding challenges facing deformable energy storage are also discussed, namely, energy density, packaging, delamination, device integration, and manufacturing. This Essay will give researchers who are interested in contributing to the development of deformable batteries a cursory understanding of the most successful strategies to date, and provide insights into the most important directions to pursue in the future.     

Stretchable Polymerized High Internal Phase Emulsion Separators for High Performance Soft Batteries

Powering soft embodiments of robots, machines and electronics is a key issue that impacts emerging human friendly forms of technologies. Batteries as energy source enable their untethered operation at high power density but must be rendered elastic to fully comply with (soft) robots and human beings. Current intrinsically stretchable batteries typically show decreased performance when deformed due to design limitations, mainly imposed by the separator material. High quality stretchable separators such as gel electrolytes represent a key component of soft batteries that affects power, internal resistance, and capacity independently of battery chemistry. Here, polymerized high internal phase emulsions (polyHIPEs) are introduced as highly ionically conductive separators in stretchable (rechargeable) batteries. Highly porous (>80%) separators result in electrolyte to polyHIPE conductivity ratios of below 2, while maintaining stretchability of ≈50% strain. The high stretchability, tunable porosity, and fast ion transport enable stretchable batteries with internal resistance below 3 Ω and 16.8 mAh cm^?2 capacity that power on‐skin processing and communication electronics. The battery/separator architecture is universally applicable to boost battery performance and represents a step towards autonomous operation of conformable electronic skins for healthcare, robotics, and consumers.     

Highly Stretchable,Sparse, Metallized Nanofiber Webs as Thin,Transferrable Transparent Conductors

The need for transparent conductors (TCs) that are capable of withstanding high mechanical deformation in comparison to the brittle indium tin oxide (ITO) films is paramount for roll‐to‐roll production of flexible and stretchable displays, signage systems, lighting devices and solar panels with stringent weatherability requirements. This paper reports a highly stretchable TC comprising of a web of core‐shell nanofibers, which mimics the fibrous structure of natural systems such as veins of a leaf or nerve systems. The TC web demonstrates high transparency, low sheet resistance, and unprecedented stretchability and stability over repeated stretching. The nanofiber TC web can be transferred to different substrates, which is manifested by the transfer onto an organic solar cell, demonstrating a photovoltaic performance comparable to that of a device with an ITO electrode. This work presents a technological platform, scalable for the manufacturing of large area transparent conductors for flexible and stretchable displays, electronics and solar cells on unconventional substrates such as rubber, fabric and paper.     

Textile‐Based Electrochemical Energy Storage Devices

In the past few years, insensitive attentions have been drawn to wearable and flexible energy storage devices/systems along with the emergence of wearable electronics. Much progress has been achieved in developing flexible electrochemical energy storage devices with high end‐use performance. However, challenges still remain in well balancing the electrochemical properties, mechanical properties, and the processing technologies. In this review, a specific perspective on the development of textile‐based electrochemical energy storage devices (TEESDs), in which textile components and technologies are utilized to enhance the energy storage ability and mechanical properties of wearable electronic devices, is provided. The discussion focuses on the material preparation and characteristics, electrode and device fabrication strategies, electrochemical performance and metrics, wearable compatibility, and fabrication scalability of TEESDs including textile‐based supercapacitors and lithium‐ion batteries.     

3D‐Printed Stretchable Micro‐Supercapacitor with Remarkable Areal Performance

While stretchable micro‐supercapacitors (MSCs) have been realized, they have suffered from limited areal electrochemical performance, thus greatly restricting their practical electronic application. Herein, a facile strategy of 3D printing and unidirectional freezing of a pseudoplastic nanocomposite gel composed of Ti₃C₂T_x MXene nanosheets, manganese dioxide nanowire, silver nanowires, and fullerene to construct intrinsically stretchable MSCs with thick and honeycomb‐like porous interdigitated electrodes is introduced. The unique architecture utilizes thick electrodes and a 3D porous conductive scaffold in conjunction with interacting material properties to achieve higher loading of active materials, larger interfacial area, and faster ion transport for significantly improved areal energy and power density. Moreover, the oriented cellular scaffold with fullerene‐induced slippage cell wall structure prompts the printed electrode to withstand large deformations without breaking or exhibiting obvious performance degradation. When imbued with a polymer gel electrolyte, the 3D‐printed MSC achieves an unprecedented areal capacitance of 216.2 mF cm^?2 at a scan rate of 10 mV s^?1, and remains stable when stretched up to 50% and after 1000 stretch/release cycles. This intrinsically stretchable MSC also exhibits high rate capability and outstanding areal energy density of 19.2 µWh cm^?2 and power density of 58.3 mW cm^?2, outperforming all reported stretchable MSCs.     

A Stretchable Nanogenerator with Electric/Light Dual‐Mode Energy Conversion

As an alternative technology, stretchable electronics attract long‐lasting attention. A newly‐designed stretchable nanogenerator with unique dual‐mode energy conversion is reported. The ability of converting the input mechanical stimuli to either electric or light output is achieved by monolithically integrating a transparent single‐electrode triboelectric nanogenerator (S‐TENG) with a ZnS based mechanoluminescence (ML) composite. This stretchable device with versatile functions promotes the development of the smart systems to efficiently and diversely utilize ubiquitous mechanical energy and demonstrates great potential for artificial e‐skins.     

Jabuticaba‐Inspired Hybrid Carbon Filler/Polymer Electrode for Use in Highly Stretchable Aqueous Li‐Ion Batteries

Stretchable electronics are considered as next‐generation devices; however, to realize stretchable electronics, it is first necessary to develop a deformable energy device. Of the various components in energy devices, the fabrication of stretchable current collectors is crucial because they must be mechanically robust and have high electrical conductivity under deformation. In this study, the authors present a conductive polymer composite composed of Jabuticaba‐like hybrid carbon fillers containing carbon nanotubes and carbon black in a simple solution process. The hybrid carbon/polymer (HCP) composite is found to effectively retain its electrical conductivity, even when under high strain of ≈200%. To understand the behavior of conductive fillers in the polymer matrix when under mechanical strain, the authors investigate the microstructure of the composite using an in situ small‐angle X‐ray scattering analysis. The authors observe that the HCP produces efficient electrical pathways for filler interconnections upon stretching. The authors develop a stretchable aqueous rechargeable lithium‐ion battery (ARLB) that utilizes this HCP composite as a stretchable current collector. The ARLB exhibits excellent rate capability (≈90 mA h g^?1 at a rate of 20 C) and outstanding capacity retention of 93% after 500 cycles. Moreover, the stretchable ARLB is able to efficiently deliver power even when under 100% strain.     

Super‐Stretchable Zinc–Air Batteries Based on an Alkaline‐Tolerant Dual‐Network Hydrogel Electrolyte

Stretchable devices need elastic hydrogel electrolyte as an essential component, while most hydrogels will lose their stretchability after being incorporated with strong alkaline solution. This is why highly stretchable zinc–air batteries have never been reported so far. Herein, super‐stretchable, flat‐ (800% stretchable) and fiber‐shaped (500% stretchable) zinc–air batteries are first developed by designing an alkaline‐tolerant dual‐network hydrogel electrolyte. In the dual‐network hydrogel electrolyte, sodium polyacrylate (PANa) chains contribute to the formation of soft domains and the carboxyl groups neutralized by hydroxyls as well as cellulose as potassium hydroxide stabilizer are responsible for vastly enhanced alkaline tolerance. The obtained super‐stretchable, flat zinc–air battery exhibits a high power density of 108.6 mW?cm^?2, increasing to 210.5 mW?cm^?2 upon being 800% stretched. Similar phenomena are observed for the 500% stretchable fiber‐shaped batteries. The devices can maintain stable power output even after being heavily deformed benefiting from the highly soft, alkaline‐tolerant hydrogel electrolyte developed. A bendable battery‐display system and water proof weavable fiber zinc–air battery are also demonstrated. This work will facilitate the progress of using zinc–air battery powering flexible electronics and smart clothes. Moreover, the developed alkaline‐tolerant super‐stretchable electrolyte can also be applied for many other alkaline electrolyte‐based energy storage/conversion devices.     

Stretchable Lithium‐Ion Batteries Enabled by Device‐Scaled Wavy Structure and Elastic‐Sticky Separator

Fast developments and substantial achievements have been shaping the field of wearable electronic devices, resulting in the persistent requirement for stretchable lithium‐ion batteries (LIBs). Despite recent progress in stretchable electrodes, stretching full batteries, including electrodes, separator, and sealing material, remains a great challenge. Here, a simple design concept for stretchable LIBs via a wavy structure at the full battery device scale is reported. All components including the package are capable of being reversibly stretched by folding the entire pouch cell into a wavy shape with polydimethylsiloxane filled in each valley region. In addition, the stretchable, sticky, and porous polyurethane/poly(vinylidene fluoride) membrane is adopted as a separator for the first time, which can maintain intimate contact between electrodes and separator to continuously secure ion pathway under dynamic state. Commercial cathode, anode, and package can be utilized in this rationally designed wavy battery to enable stretchability. The results indicate good electrochemical performances and long‐term stability at repeatable release–stretch cycles. A high areal capacity of 3.6 mA h cm^?2 and energy density of up to 172 W h L^?1 can be achieved for the wavy battery. The promising results of the cost‐effective wavy battery with high stretchability shed light on the development of stretchable energy storages.     

Intrinsically Stretchable Fuel Cell Based on Enokitake‐Like Standing Gold Nanowires

Conventional fuel cells are based on rigid electrodes, limiting their applications in wearable and implantable electronics. Here, it is demonstrated that enokitake‐like vertically‐aligned standing gold nanowires (v‐AuNWs) can also serve as powerful platform for stretchable fuel cells by using ethanol as model system. Unlike traditional fuel cell electrodes, the v‐AuNWs have “Janus Morphology” on both sides of the film and also are highly stretchable. The comparative studies demonstrate that tail side exposed v‐AuNWs based stretchable electrodes outperform the head‐side exposed v‐AuNWs toward the electro‐oxidation of ethanol due to the direct exposure of high‐surface‐area nanowires to the fuels. Therefore, a stretchable fuel cell is fabricated utilizing tail side based interdigitated electrodes, where v‐AuNWs and Pt black modified v‐AuNWs serve as the anode and cathode, respectively. The as‐prepared stretchable fuel cell exhibits good overall performance, including high power density, current density, open‐circuit voltage, stretchability, and durability. Most importantly, a wearable fuel cell is also achieved by integrating tattoo‐like interdigitated electrodes with a thin layer of sponge as a fuel container, exhibiting good performance under various deformations (compression, stretching, and twisting). Such attractive performance in conjunction with skin‐like in‐plane design indicates its great potential to power the next‐generation of wearable and implantable devices.     

Rechargeable Soft‐Matter EGaIn‐MnO2 Battery for Stretchable Electronics

A rechargeable, stretchable battery composed of a liquid metal alloy (eutectic gallium‐indium; EGaIn) anode, a carbon paste, and MnO₂ slurry cathode, an alkaline electrolytic hydrogel, and a soft elastomeric package is presented. The battery can stably cycle within a voltage range of 1.40–1.86 V at 1 mA cm^?2 while being subject to 100% tensile strain. This is accomplished through a mechanism that involves reversible stripping and plating of gallium along with MnO₂ chemical conversion. Moreover, a technique to increase the contact area between the EGaIn anode and hydrogel interface using CaCl₂ additives, which reduces polarization and therefore reduces the effective current density, leading to higher discharge plateaus and lower charge plateaus. Relative to previous attempts at energy storage with liquid metal, the EGaIn‐MnO₂ battery presented here shows an exceptional areal specific capacity (≈3.8 mAh cm^?2) and robust, stable rechargeability over >100 charging cycles. The battery is also stable under bending, with negligible change in electrochemical properties when bent to a 2 mm radius of curvature. Batteries embedded within a wearable elastomeric sleeve can power a blue light‐emitting diode and strain‐sensing circuit. These demonstrations suggest that stretchable EGaIn‐MnO₂ batteries are feasible for applications in wearable energy‐storage electronics.     

Trends in Aluminium‐Based Intercalation Batteries

Over the last decade, optimizing energy storage has become significantly important in the field of energy conversion and sustainability. As a result of immense progress in the field, cost‐effective and high performance batteries are imperative to meeting the future demand of sustainability. Currently, the best performing batteries are lithium‐ion based, but limited lithium (Li) resources make research into alternatives essential. In recent years, the performance of aluminium‐ion batteries has improved remarkably in all battery‐relevant metrics, which renders them a promising alternative. Compared with monovalent Li‐ion batteries, aluminium (Al) cations can carry three positive charges, which could result in higher energy densities. This review describes recent developments in Al‐based cathode materials. The major goal of this review is to highlight strengths and weaknesses of various different approaches and provide guidelines for future research.