High Conductivity Research Articles

Highly stretchable dynamic hydrogels for soft multilayer electronics.

Recent progress in the development of synthetic polymer networks has enabled the next generation of hydrogel-based machines and devices. The ability to mimic the mechanical and electrical properties of human tissue gives great potential toward the fields of bioelectronics and soft robotics. However, fabricating hydrogel devices that display high ionic conductivity while maintaining high stretchability and softness remains unmet. Here, we synthesize supramolecular poly(ionic) networks, which display high stretchability (>1500%), compressibility (>90%), and rapid self-recovery (<30 s), while achieving ionic conductivities of up to 0.1 S cm -1. Dynamic cross-links give rise to inter-layer adhesion and a stable interface is formed on account of ultrahigh binding affinities (>1013 M-2). Superior adherence between layers enabled the fabrication of an intrinsically stretchable hydrogel power source, paving the way for the next generation of multi-layer tissue mimetic devices.

Water-in-Salt Gel Biopolymer Electrolytes for Flexible and Wearable Zn/Alkali Metal Dual-Ion Batteries.

Zn/alkali metal dual-ion batteries (ZM DIBs) with highly concentrated water-in-salt (WiS) electrolytes are promising next-generation energy storage systems. This enhanced design of Zn-ion rechargeable batteries offers intrinsic safety, high operating voltage, satisfactory capacity, and outstanding cyclic stability. Herein, taking the concept of highly concentrated electrolytes one step further, we introduce water-in-salt gel biopolymer electrolytes (WiS-GBEs) by encapsulating Zn/Li or Zn/Na bisalt compositions in a cellulose membrane. WiS-GBEs inherit the electrochemical merits of highly concentrated electrolytes (i.e., wide voltage window, high ionic conductivity, etc.) and excellent durability of gel biopolymer structures. Both types of WiS-GBEs apply to coin- and pouch-cell compartments of ZM DIBs, offering a high plateau voltage (>1.8 V vs. Zn2+/Zn), good and reversible capacity (118 and 57 mAh g-1 for Zn/Li and Zn/Na cells, respectively), and outstanding cycling stability (more than 90% after 1,000 cycles). Essentially, the pouch cells with WiS-GBEs present superior durability, flexibility, and capacity endurance under various bending stress conditions (90% capacity retention under 0-180° bending modes), indicating their potential capability to power wearable electronics. The practical powering ability of Li- and Na-based pouch systems is demonstrated by the example of a wearable digital timer.

Semiconductor Heterostructure (SrFe0.3TiO3-ZnO) Electrolyte with High Proton Conductivity for Low-Temperature Ceramic Electrochemical Cells.

In recent years, ceramic cells based on high proton conductivity have attracted much attention and can be employed for hydrogen production and electricity generation, especially at low temperatures. Nevertheless, attaining a high power output and durability is challenging, especially at low operational temperatures. In this regard, we design semiconductor heterostructure SFT-ZnO (SrFe0.3TiO3-ZnO) materials to function as an electrolyte for fuel cell and electrolysis applications. Using this approach, the functional semiconductor heterostructure can deliver a better power output and high ionic and proton conductivity at low operational temperatures. The prepared cell in fuel cell mode has demonstrated excellent performance of 700 mW cm-2 and proton performance of 540 mW cm-2 at the low temperature of 520 °C, suggesting dominant proton conduction. Further, the prepared cell delivers exceptional current densities of 1.18 and 0.38 A cm-2 (at 1.6 and 1.3 V, respectively) at 520 °C in the electrolysis mode. Our electrochemical cell is stable in fuel and electrolysis mode at a low temperature of 500 °C.

Compensation of capacitive currents in high-throughput dielectrophoretic separators

Separation and classification are important operations in particle technology, but they are still limited in terms of suspended particles in the micrometer and nanometer size-range. Electrical fields can be beneficial for sorting such particles according to material properties. A mechanism based on strong and inhomogeneous fields is dielectrophoresis (DEP). It can be used to separate microparticles according to their material properties, such as conductivity and permittivity, by selectively trapping one particle type while the other can pass the separator. Conventional DEP-separators show either a limitation in throughput or frequency bandwidth. A low throughput limits the economical feasibility in many cases. A lower frequency bandwidth limits the variety of materials that can be sorted by DEP. To separate semiconducting particles from a mixture containing particles with higher conductivity according to their material, high frequencies are required. Possible applications are the separation of semiconducting and metallic carbon nanotubes or the separation of carbon-coated lithium iron phosphate particles from graphite in the recycling process of spent lithium-ion batteries. In this publication, we aim to display how to tune the electrical impedance of a high-throughput DEP separator based on custom-designed printed circuit boards to increase its frequency bandwidth. By adding inductors to the electrical circuit, we were able to increase the frequency bandwidth from 500 kHz to over 11 MHz. The experiments in this study act as proof-of-principle. Furthermore, a non-deterministic way to increase the impedance of the setup is shown, yielding a maximum frequency of 39.16 MHz.

Highly tough slide-crosslinked gel polymer electrolyte for stable lithium metal batteries.

Gel polymer electrolytes (GPEs) hold great promise for the practical application of lithium metal batteries. However, conventional GPEs hardly resists lithium dendrites growth and maintains long-term cycling stability of the battery due to its poor mechanical performance. Inspired by the slide-ring structure of polyrotaxanes (PRs), herein we developed a dynamic slide-crosslinked gel polymer electrolyte (SCGPE) with extraordinary stretchability of 970.93% and mechanical strength of 1.15 MPa, which is helpful to buffer the volume change of electrodes and maintain mechanical integrity of the battery structure during cycling. Notably, the PRs structures can provide fast ion transport channels to obtain high ionic conductivity of 1.73×10-3 S cm-1 at 30°C. Additionally, the strong polar groups in SCGPE restrict the free movement of anions to achieve high lithium-ion transference number of 0.71, which is favorable to enhance Li+ transport dynamics and induce uniform Li+ deposition. Benefiting from these features, the constructed Li|SCGPE-3|LFP cells exhibit ultra-long and stable cycle life over 1000 cycles and high-capacity retention (89.6% after 1000 cycles). Even at a high rate of 16C, the cells deliver a high capacity of 79.2 mAh g-1. The slide-crosslinking strategy in this work provides a new perspective on the design of advanced GPEs for LMBs.

A Universal Biocompatible and Multifunctional Solid Electrolyte in p-Type and n-Type Organic Electrochemical Transistors for Complementary Circuits and Bioelectronic Interfaces.

The development of soft and flexible devices for collection of bioelectrical signals is gaining momentum for wearable and implantable applications. Among these devices, organic electrochemical transistors (OECTs) stand out due to their low operating voltage and large signal amplification capable of transducing weak biological signals. While liquid electrolytes have demonstrated efficacy in OECTs, they limit its operating temperature and pose challenges for electronic packaging due to potential leakage. Conversely, solid electrolytes offer advantages such as mechanical flexibility, robustness against environmental factors, and ability to bridge the interface between rigid dry electronics systems and soft wet biological tissues. However, few systems have demonstrated generality and compatibility with a wide range of state-of-the-art organic mixed ionic-electronic conductors (OMIECs). This paper introduces a highly stretchable, flexible, biocompatible, self-healable gelatin-based solid-state electrolyte, compatible with both p- and n-type OMIEC channels while maintaining high performance and excellent stability. Furthermore, this nonvolatile electrolyte is stable up to 120°C and exhibits high ionic conductivity even in dry environment. Additionally, an OECT-based complementary inverter with a record-high normalized-gain of 228 V-1 and a corresponding ultralow static power consumption of 1 nW is demonstrated. These advancements pave the way for versatile applications ranging from bioelectronics to power-efficient implants.

Interfacial Stereoelectronic Effect Induced by Anchoring Orientation.

Heterogeneous interfaces in most devices play a key role in the material performance. Exploring the atomic structure and electronic properties of metal-molecule interfaces is critical for various potential applications, such as surface sensing, molecular recognition, and molecular electronic devices. This study unveils a ubiquitous interfacial stereoelectronic effect in conjugated molecular junctions by combining first-principles simulation and scanning tunneling microscopy break junction technology. Single-molecule junctions with same-side interfacial anchoring (cis configuration) exhibit higher conductance than those with opposite-side interfacial anchoring (trans configuration). The cis and trans configurations can undergo reversible conversions, resulting in a conductance switching. The stability of these configurations can be adjusted by an electric field, achieving precise regulation of conductance states. Our findings provide important insights for designing high-quality materials and enhancing the device performance.

Scalable Compliant Graphene Fiber-Based Thermal Interface Material with Metal-Level Thermal Conductivity via Dual-Field Synergistic Alignment Engineering.

High-performance thermal interface materials (TIMs) are highly desired for high-power electronic devices to accelerate heat dissipation. However, the inherent trade-off conflict between achieving high thermal conductivity and excellent compliance of filler-enhanced TIMs results in the unsatisfactory interfacial heat transfer efficiency of existing TIM solutions. Here, we report the graphene fiber (GF)-based elastic TIM with metal-level thermal conductivity via mechanical-electric dual-field synergistic alignment engineering. Compared with state-of-the-art carbon fiber (CF), GF features both superb high thermal conductivity of ∼1200 W m-1 K-1 and outstanding flexibility. Under dual-field synergistic alignment regulation, GFs are vertically aligned with excellent orientation (0.88) and high array density (33.5 mg cm-2), forming continuous thermally conductive pathways. Even at a low filler content of ∼17 wt %, GF-based TIM demonstrates extraordinarily high through-plane thermal conductivity of up to 82.4 W m-1 K-1, exceeding most CF-based TIMs and even comparable to commonly used soft indium foil. Benefiting from the low stiffness of GF, GF-based TIM shows a lower compressive modulus down to 0.57 MPa, an excellent resilience rate of 95% after compressive cycles, and diminished contact thermal resistance as low as 7.4 K mm2 W-1. Our results provide a superb paradigm for the directed assembly of thermally conductive and flexible GFs to achieve scalable and high-performance TIMs, overcoming the long-standing bottleneck of mechanical-thermal mismatch in TIM design.

Amorphous Boron Nitride Nanosheet‐Based Solid State Electrolytes with High Ionic Conductivity

AbstractAmorphous boron nitride nanosheets, with natural electrical insulation, outstanding chemical stability and mechanical properties, are introduced as a matrix to be incorporated with lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) and polymer polyvinylidene fluoride‐hexafluoropropylene copolymer (PVDF‐HFP), for constructing a novel composite solid‐state electrolyte by a simple solution‐casting method. Amorphous boron nitride nanosheets are produced via a combination method of ball milling and pure water exfoliation. The obtained composite solid‐state electrolyte containing 40 % (mass fraction) PVDF‐HFP shows a high lithium ion conductivity (1.936×10−3 S cm−1) and lithium ion transference number (0.47), and a wide electrochemical stability window (5 V) at room temperature. The LiFePO4/Li based all solid‐state battery, consisting of the composite solid electrolyte (40 % PVDF‐HFP), delivers a capacity of 128.1 mAh g−1, a Coulombic efficiency of 99.79 % after 500 cycles and a capacity retention rate of 94.5 % at 1.0 C and 25 °C. The composite solid electrolyte (40 % PVDF‐HFP) can maintain flat and stable stripping/plating plateaus for over 800 hours in symmetrical cells. The amorphous boron nitride nanosheets with high lithium ion conductivity are employed to construct solid‐state electrolytes, which is important significant for the development of high energy density, high safety, and long cycle life all‐solid‐state lithium‐ion batteries.

Harnessing Cold Sintering to Fabricate Composite Polymer Electrolytes - A Paradigm Shift in Organic-Inorganic Material Assembly

Abstract The development of composite electrolytes for all-solid-state batteries is an emerging field, but the creation of predominantly inorganic electrolytes remains challenging. In this study, Li6.25Al0.25La3Zr2O12 (Al-LLZO), a ceramic material selected for its high ionic conductivity (1x104 S.cm-1 at ambient temperature) was shaped by the cold-sintering process (CSP). The organic phase was synthesized by free-radical polymerization of two poly(ethylene oxide) methacrylate derivatives in the presence of lithium bis(trifluoromethanesulfonyl)imide salts (LiTFSI). The polymethacrylate network with dangling poly(ethylene oxide) (PEO) chains was thus obtained. This in-situ polymerization allows the one-pot synthesis of the composite electrolyte during CSP. Remarkably, the ionic conductivity of the CSP pellet varied with the nature of the organic phase, ranging from 1x10−4 to 1x10−5 S.cm-1 for non-grafted and grafted TFSI anion on the PEO-based network, respectively. Additionally, the transport of Li+ remained unaffected by the inorganic material's nature as long as it contained Li species. Furthermore, a significant enhancement of the ionic conductivity was observed in the composite pellet compared to the TFSI grafted network (10−5 to 10−7 S.cm-1, respectively). Electrochemical impedance spectroscopy measurements revealed changes in the Al-LLZOPEO-based polymer interface during CSP with the formation of an interphase, confirmed by a low activation energy value (0.1 eV).

Ordering Sulfonic Groups Facilitate a Li3N‐Enriched Interphase via Directing the Decomposition of LiNO3

AbstractThe practical application of high‐energy lithium (Li) metal anodes is plagued by the severe issues of interfacial instability. The Li3N originated from the decomposition of LiNO3 is believed to endow the solid electrolyte interphase (SEI) with high stability and ionic conductivity. However, the precise control on the decomposition of LiNO3 is still challenging due to the sophisticated reaction pathways and high energy barriers. In this study, a self‐assembled monolayers (SAMs) with densely packed and long‐range ordered sulfonic acid groups on an alumina‐coated separator are designed. By providing a strong dipole moment, this SAMs efficiently facilitate the rapid and deep decomposition of LiNO3, leading to the formation of an SEI rich in Li3N nanocrystals. Notably, under the stringent conditions of 5 mA cm−2 and 5 mAh cm−2, the Li/Li symmetric cell is still able to cycle stably for 1000 h under the stable nitrided interface induced by the SAMs. Consequently, the application scenarios of SAMs technology in precisely controlling electrolyte decomposition processes are successfully expanded to stabilize the interphase of metallic Li anode with high energy‐density.

Binderless Electrodeposited NiCo2S4-MWCNT as a Potential Anode Material for Sodium-Ion Batteries

Abstract Conversion type ternary NiCo2S4, exhibiting high electrical conductivity (~1.25 × 106 S m-1) and high theoretical capacity (703 mAh g-1), has gained interest as an anode material for sodium-ion batteries (SIBs). Despite its potential, NiCo2S4 (NCS) has extensive volume expansion during cycling. This study introduces the NCS-multi-walled carbon nanotube (MWCNT) onto a carbon fiber (CF) electrode (NCS and NCS-MWCNT@CF), developed through electrodeposition, which addresses these limitations. The unique sheet-like morphology of NCS, featuring abundant pores, ensures good access to the electrolyte. Incorporating a three-dimensional conductive CF framework that acts as a free-standing current collector helps prevent the agglomeration of NCS particles and mitigates volume expansion by providing enough buffer space in the layers of the CF matrix. Our findings reveal that NCS on CF electrodes deliver a second cycle capacity of 620 mA g-1 at 30 mA g-1 and retain 72 % capacity after 200 cycles. At 200 mA g-1, the NCS@CF electrodes deliver 378 mAh g-1 in the second cycle with 68% capacity retention in the 200th cycle, whereas NCS-MWCNT@CF delivers 538 mAh g-1 at 200 mA g-1, maintaining 86 % capacity after 100 cycles, making it a potential anode for SIBs.

Energy Filtering in Doping Modulated Nanoengineered Thermoelectric Materials: A Monte Carlo Simulation Approach

Using Monte Carlo electronic transport simulations, coupled self-consistently with the Poisson equation for electrostatics, we explore the thermoelectric power factor of nanoengineered materials. These materials consist of alternating highly doped and intrinsic regions on the scale of several nanometers. This structure enables the creation of potential wells and barriers, implementing a mechanism for filtering carrier energy. Our study demonstrates that by carefully designing the nanostructure, we can significantly enhance its thermoelectric power factor compared to the original pristine material. Importantly, these enhancements stem not only from the energy filtering effect that boosts the Seebeck coefficient but also from the utilization of high-energy carriers within the wells and intrinsic barrier regions to maintain relatively high electronic conductivity. These findings can offer guidance for the design and optimization of new-generation thermoelectric materials through improvements in the power factor.

Unusual negative thermal expansion of inter-cluster –C–BC–C– bond in carbon rich boron carbide observed using in situ x-ray diffraction technique

Temperature dependent bonding behavior plays a significant role in deciding properties of high temperature ceramics like boron carbide. However, few studies to date have addressed the physical properties of this class of materials with respect to their temperature dependent bonding nature. In addition, materials with the flexibility to accommodate variations in interatomic bonding and lattice vibrations over a wide range of temperatures are less known. In this work, temperature dependent structural analyses of carbon-rich boron carbide microflakes using in situ powder x-ray diffraction techniques (up to 1000 °C) supported by transmission electron microscopy measurements reveal that while most bonds in the rhombohedral structure increase in length with temperature; there is no change in certain bond lengths. However, there is an unusual decrease in length (∼1.03%) of the inter-cluster –C–(central boron)BC–C– without any polyhedral redistribution. This is accompanied by an increase in lattice vibrations without significant alteration to the crystal structure over the wide temperature range studied. Temperature dependent micro-Raman experiments further confirmed the above observations. The above bonding behavior could be directly correlated to the trends in reported results of high temperature conductivity via the model of hole hopping through specific atomic positions of the rhombohedral framework, thus opening the scope to investigate structure–property relationships in high temperature functional materials.

Dimensionality Control of Li Transport by MOFs Based Quasi‐Solid to Solid Electrolyte (Q‐SSEs) for Li−Metal Batteries

AbstractNowadays, lithium‐ion batteries (LIBs) are widely used in all walks of life and play a very important role. As complex systems composed of multiple materials with diverse chemical compositions, where different electrochemical reactions take place, battery interfaces are essential for determining the operation, performance, durability and safety of the battery. This work, set out to study the incorporation of lithium bis(fluorosulfonyl)amide (LiFSI) doped 1‐ethyl‐3‐methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIm][TFSI]) ionic liquid into an archetype Ti‐based Metal Organic Framework (MOF) ((Ti) MIL125−NH2) to create a solid to quasi‐solid (depending on the amount of IL in the system), and how it affects not only ionic transport but also the structural properties of the IL/MOF electrolyte. Remarkably high ionic conductivity values (2.13×10−3 S ⋅ cm−1 at room temperature) as well as a lithium transference number (tLi=0.58) were achieved, supported by pulsed field gradient (PFG) NMR experiments. Electrochemical characterization revealed reversible plating‐stripping of lithium and lower overpotential after 750 h at 50 °C. Additionally, a proof‐of‐concept solid state battery was fabricated resulting in a discharge capacity of 160 mAh ⋅ g−1 at 50 °C and 0.1 C rate after 50 cycles. This work presents a suitable strategy to dendrite suppression capability, allowing its implementation as interface modifiers in next‐generation solid‐state batteries.

Scalable CIGS Solar Cells Employing a New Device Design of Nontoxic Buffer Layer and Microgrid Electrode.

The efficiency of copper indium gallium selenide (CIGS) solar cells that use transparent conductive oxide (TCO) as the top electrode decreases significantly as the device area increases owing to the poor electrical properties of TCO. Therefore, high-efficiency, large-area CIGS solar cells require the development of a novel top electrode with high transmittance and conductivity. In this study, a microgrid/TCO hybrid electrode is designed to minimize the optical and resistive losses that may occur in the top electrode of a CIGS solar cell. In addition, the buffer layer of the CIGS solar cells is changed from the conventional CdS buffer to a dry-processed wide-band gap ZnMgO (ZMO) buffer, resulting in increased device efficiency by minimizing parasitic absorption in the short-wavelength region. By optimizing the combination of ZMO buffer and the microgrid/TCO hybrid electrode, a device efficiency of up to 20.5% (with antireflection layers) is achieved over a small device area of 5 mm × 5 mm (total area). Moreover, CIGS solar cells with an increased device area of up to 20 mm × 70 mm (total area) exhibit an efficiency of up to 19.7% (with antireflection layers) when a microgrid/TCO hybrid electrode is applied. Thus, this study demonstrates the potential for high-efficiency, large-area CIGS solar cells with novel microgrid electrodes.

Giant thermal conductivity and strain thermal response of nitrogen substituted diamane: a machine-learning-based prediction.

With the ongoing trend of seeking miniaturization and enhanced performance for electronic devices, effective thermal management has emerged as a critical concern. The discovery and investigation of high thermal conductivity (κ) materials have proved to be pivotal in addressing this challenge. This study aims to explore the distinctive properties and potential applications of nitrogen substituted diamane (NCCN), a two-dimensional material with a diamond-like structure composed of carbon and nitrogen atoms. This work systematically delves into NCCN's thermal, mechanical, and electrical properties. It is predicted that NCCN exhibits an exceptional κ, ∼2288 W m-1 K-1, at room temperature (300 K) by combining the machine-learning interatomic potential method and the phonon Boltzmann transport equation, surpassing that of H-diamane and rivaling that of diamond, and an impressive electronic band gap of ∼4.47 eV (PBE). For mechanical properties, the stress-strain relationship reveals that NCCN exhibits isotropic elastic properties and anisotropic tensile strengths. Additionally, the variations in NCCN's κ and electronic energy band structure under different strains underscore its substantial potential in the field of thermoelectric applications.

Entropy-Assisted Anion-Reinforced Solvation Structure for Fast-Charging Sodium-Ion Full Batteries.

Anion-reinforced solvation structure favors the formation of inorganic-rich robust electrode-electrolyte interface, which endows fast ion transport and high strength modulus to enable improved electrochemical performance. However, such a unique solvation structure inevitably injures the ionic conductivity of electrolytes and limits the fast-charging performance. Herein, a trade-off in tuning anion-reinforced solvation structure and high ionic conductivity is realized by the entropy-assisted hybrid ester-ether electrolyte. Anion-reinforced solvation sheath with more anions occupying the inner Na+ shell is constructed by introducing the weakly coordinated ether tetrahydrofuran into the commonly used ester-based electrolyte, which merits the accelerated desolvation energy and gradient inorganic-rich electrode-electrolyte interface. The improved ionic conductivity is attributed to the weakly diverse solvation structures induced by entropy effect. These enable the enhanced rate performance and cycling stability of Prussian blue||hard carbon full cells with high electrode mass loading. More importantly, the practical application of the designed electrolyte was further demonstrated by industry-level 18650 cylindrical cells.

Entropy‐Assisted Anion‐Reinforced Solvation Structure for Fast‐Charging Sodium‐Ion Full Batteries

Anion‐reinforced solvation structure favors the formation of inorganic‐rich robust electrode‐electrolyte interface, which endows fast ion transport and high strength modulus to enable improved electrochemical performance. However, such a unique solvation structure inevitably injures the ionic conductivity of electrolytes and limits the fast‐charging performance. Herein, a trade‐off in tuning anion‐reinforced solvation structure and high ionic conductivity is realized by the entropy‐assisted hybrid ester‐ether electrolyte. Anion‐reinforced solvation sheath with more anions occupying the inner Na+ shell is constructed by introducing the weakly coordinated ether tetrahydrofuran into the commonly used ester‐based electrolyte, which merits the accelerated desolvation energy and gradient inorganic‐rich electrode‐electrolyte interface. The improved ionic conductivity is attributed to the weakly diverse solvation structures induced by entropy effect. These enable the enhanced rate performance and cycling stability of Prussian blue||hard carbon full cells with high electrode mass loading. More importantly, the practical application of the designed electrolyte was further demonstrated by industry‐level 18650 cylindrical cells.

High ionic conduction in a robust anionic metal-organic framework containing Mg2+ under guest vapors.

We report on the synthesis and high ionic conductivity of a highly crystalline Mg2+-containing metal-organic framework (MOF) with Type A feature (i.e., anionic framework having Mg2+ as a counter cation). We synthesized Mg[Zr(C14H3O8)2] (SU-102-Mg) through ion exchange reaction. SU-102-Mg showed a high ionic conductivity of 3.6 × 10-5 S cm-1 (25 °C, under MeCN vapor).