Programmable DNA Interphase Layers for High-Performance Anode-Free Lithium Metal Batteries.

Anode-free lithium (Li) metal batteries are promising candidates for advanced energy storage, attributed to their appealing characteristics such as high energy density, low cost, and convenient production. However, their major challenges lie in the poor cycling and rate performance owing to the inferior reversibility and kinetics of Li plating and stripping, which significantly hinder their real-world applications. Here, it is demonstrated that deoxyribonucleic acid (DNA), the most important genetic material in nature, can serve as a highly programmable interphase layer for innovation of anode-free Li metal batteries. It is found that the abundant base pairs in DNA can contribute transient Li-N bonds that facilitate homogeneous Li+ flux, thus resulting in excellent Li plating/stripping kinetics and reversibility even at a harsh areal current of 15 mA cm-2. The anode-free LiFePO4 full batteries based on an ultrathin (0.12 µm) and ultralight (≈0.01 mg cm-2) DNA interphase layer show high CEs (≈99.1%) over 400 cycles, corresponding to an increase of ≈186% compared with bare copper (Cu) foil. These results shed light on the excellent programmability of DNA as a new family of interphase materials for anode-free batteries, and provide a new paradigm for future battery innovation toward high programmability, high sustainability, and remarkable electrochemical performance.

A dynamically stable self-healable wire based on mechanical-electrical coupling.

The rise in wearable electronics has witnessed the advancement of self-healable wires, which are capable of recovering mechanical and electrical properties upon structural damage. However, their highly fluctuating electrical resistances in the range of hundreds to thousands of ohms under dynamic conditions such as bending, pressing, stretching and tremoring may seriously degrade the precision and continuity of the resulting electronic devices, thus severely hindering their wearable applications. Here, we report a new family of self-healable wires with high strengths and stable electrical conductivities under dynamic conditions, inspired by mechanical-electrical coupling of the myelinated axon in nature. Our self-healable wire based on mechanical-electrical coupling between the structural and conductive components has significantly improved the electrical stability under dynamic scenarios, enabling precise monitoring of human health status and daily activities, even in the case of limb tremors from simulated Parkinson's disease. Our mechanical-electrical coupling strategy opens a new avenue for the development of dynamically stable electrodes and devices toward real-world wearable applications.

A rechargeable Ca/Cl2 battery.

Rechargeable calcium (Ca) metal batteries are promising candidates for sustainable energy storage due to the abundance of Ca in Earth's crust and the advantageous theoretical capacity and voltage of these batteries. However, the development of practical Ca metal batteries has been severely hampered by the current cathode chemistries, which limit the available energy and power densities, as well as their insufficient capacity retention and low-temperature capability. Here, we describe the rechargeable Ca/Cl2 battery based on a reversible cathode redox reaction between CaCl2 and Cl2, which is enabled by the use of lithium difluoro(oxalate)borate as a key electrolyte mediator to facilitate the dissociation and distribution of Cl-based species and Ca2+. Our rechargeable Ca/Cl2 battery can deliver discharge voltages of 3 V and exhibits remarkable specific capacity (1000 mAh g-1) and rate capability (500 mA g-1). In addition, the excellent capacity retention (96.5% after 30 days) and low-temperature capability (down to 0 °C) allow us to overcome the long-standing bottleneck of rechargeable Ca metal batteries.

Unlocking Reversible Silicon Redox for High-Performing Chlorine Batteries.

Chlorine (Cl)-based batteries such as Li/Cl2 batteries are recognized as promising candidates for energy storage with low cost and high performance. However, the current use of Li metal anodes in Cl-based batteries has raised serious concerns regarding safety, cost, and production complexity. More importantly, the well-documented parasitic reactions between Li metal and Cl-based electrolytes require a large excess of Li metal, which inevitably sacrifices the electrochemical performance of the full cell. Therefore, it is crucial but challenging to establish new anode chemistry, particularly with electrochemical reversibility, for Cl-based batteries. Here we show, for the first time, reversible Si redox in Cl-based batteries through efficient electrolyte dilution and anode/electrolyte interface passivation using 1,2-dichloroethane and cyclized polyacrylonitrile as key mediators. Our Si anode chemistry enables significantly increased cycling stability and shelf lives compared with conventional Li metal anodes. It also avoids the use of a large excess of anode materials, thus enabling the first rechargeable Cl2 full battery with remarkable energy and power densities of 809 Wh kg-1 and 4,277 W kg-1 , respectively. The Si anode chemistry affords fast kinetics with remarkable rate capability and low-temperature electrochemical performance, indicating its great potential in practical applications.

Unlocking Deep and Fast Potassium-Ion Storage through Phosphorus Heterostructure.

Potassium-ion battery represents a promising alternative of conventional lithium-ion batteries in sustainable and grid-scale energy storage. Among various anode materials, elemental phosphorus (P) has been actively pursued owing to the ideal natural abundance, theoretical capacity, and electrode potential. However, the sluggish redox kinetics of elemental P has hindered fast and deep potassiation process toward the formation of final potassiation product (K3 P), which leads to inferior reversible capacity and rate performance. Here, it is shown that rational design on black/red P heterostructure can significantly improve K-ion adsorption, injection and immigration, thus for the first time unlocking K3 P as the reversible potassiation product for elemental P anodes. Density functional theory calculations reveal the fast adsorption and diffusion kinetics of K-ion at the heterostructure interface, which delivers a highly reversible specific capacity of 923 mAh g-1 at 0.05 A g-1 , excellent rate capability (335 mAh g-1 at 1 A g-1 ), and cycling performance (83.3% capacity retention at 0.8 A g-1 after 300 cycles). These results can unlock other sluggish and irreversible battery chemistries toward sustainable and high-performing energy storage.

Chain-ring covalently interconnected cellulose nanofiber/MWCNT aerogel for supercapacitors and sensors.

Bending multi-walled carbon nanotubes (MWCNTs) into rings and structuring them into aerogels is difficult. In this study, cellulose nanofiber (CNF)-MWCNT composite fibers with chain-ring structures were prepared by covalently interconnecting carboxylated CNF and aminated MWCNT by dehydration condensation, solving the problems of the formation of MWCNT aerogels and their phase separation during the compounding process and providing CNF-based aerogels with electrical conductivity. The covalently interconnected aerogels (CAs) had hierarchical porous structures with mechanical resilience and chain-ring fibers, which drove the CNF and MWCNT to form a continuous homogeneous network resulting in a high compression resistance of 269.02 kPa. The CA-based flexible all-solid-state supercapacitor had a quality specific capacitance of 114.8 F g-1, a capacitance retention rate of 94.78% and a Coulomb efficiency of 100%. The CA-based flexible sensor can sense different pressures with a stable response for 1000 cycles. This first study of pulling and bending MWCNT through CNF is expected to inspire more applications of MWCNTs in the fields of flexible supercapacitors and sensors.

Multifunctional Biosensors Made with Self-Healable Silk Fibroin Imitating Skin.

We report on robust silk fibroin (SF) gels fabricated by incorporating cellulose nanocrystals (SF/CNC) as a "tough" unit and photopolymerization of acrylamide as an "elastic" segment. The addition of CNC affects the refolding process of SF molecules controlled by nucleation via templating, resulting in a stable mesoscopic structure. The gel shows robust mechanical stability (88.8% of initial stress after 1000 compression cycles) and excellent adhesion to various materials. The connected gel can recover its ionic conductivity within 20 s and be stretched to a maximum strain of 498% after healing for 10 h with an efficiency of 95.2%. This multifunctional gel sensor can sensitively detect different toxic gases and small-scale and large-scale human motions in real-time. Its sensitivity is calculated as GF = 3.84 at 0-200% strain. Especially, the gel with 5 wt % thermochromic pigments as a visual temperature indicator can quickly reflect abnormal human body temperature according to the color change. Therefore, the strategy shows potential applications in flexible electrodes, biomimetic sensors, and visual biosensors.

Highly sensitive self-healable strain biosensors based on robust transparent conductive nanocellulose nanocomposites: Relationship between percolated network and sensing mechanism.

The conventional skin sensor detection of human physiological signals can be an effective method for disease diagnosis and health monitoring, but the poor biocompatibility, low sensitivity and complex design largely limit their applications. Developing natural nanofiller-reinforced composites as strain biosensors is an appealing solution to reduce environmental impacts and overcome technical bottleneck. Herein, a versatile nature skin-inspired composite film as flexible strain biosensor was developed based on cellulose nanocrystals-polyaniline (CNC-PANI) composites by utilizing their percolated conductive network in polyvinyl alcohol (PVA) matrix. The composite electronic skin showed robust mechanical strength (50.62 MPa) and high sensitivity (Gauge Factor = 11.467) with easy water-induced self-healing abilities. Moreover, we investigated the functioning mechanism of percolated network and the sensory behavior determined by CNC nanocomposite alignment. The percolation threshold of CNC-polyaniline (PANI) was determined at 4.278% and 5% CNC-PANI composite film shows the best overall sensing property. It was also discovered that the sensitivity of this type of conductive-filler electronic skin can be divided into two separate regions at different strain range due to its percolated network. With films prepared by dry casting and dip coating, the alignment of CNC-PANI also contributes to this unique change in electrical property. Generally, our results demonstrated the mechanism and tunability of conductive nanofiller-based composite strain biosensors as a potential alternative to commercial synthetic sensors.

Magnetic cellulose nanocrystals hybrids reinforced phase change fiber composites with highly thermal energy storage efficiencies.

The intrinsic intermittence of solar energy raises the necessity for thermal energy storage (TES) systems to balance the contradiction between energy supply and demand energy. This work experimentally provides solid-liquid phase change materials (PCMs) with sufficient storage capacity and discharging rate to offer heating for agriculture products by enhancing heat transfer in phase change fiber composites (PCF). To achieve this, we prepared dipole responsive magnetic/solar-driven PCF composites reinforced with magnetic cellulose nanocrystals hybrids (MCNC). The obtained PCF/MCNC-5% showed excellent magnetic property with a saturation magnetization (MS) value of 1.3 emu/g and effective latent heat phase change enthalpies of 69.2 ± 3.5 J/g - 83.1 ± 4.2 J/g. More importantly, PCF/MCNC-5% showed robust high magnetic to thermal energy storage efficiency of 32.5 % and solar light accelerated energy storage efficiency of 58.5 %. These advantages make the PCF composites promising and more desirable for drying and preservation of the fruits and other agriculture products.