Single‐Step Spray Printing of Symmetric All‐Organic Solid‐State Batteries Based on Porous Textile Dye Electrodes

A symmetric solid‐state battery based on organic porous electrodes is fabricated using scalable spray‐printing. The active electrode material is based on a textile dye (disperse blue 134 anthraquinone) and is capable of forming divalent cations and anions in oxidation and reduction processes. The resulting molecule can be used in both negative and positive electrode reactions. After spray printing an inter‐connected pore honeycomb electrode, a solid‐state electrolyte (σ_Li: × 10^?4 S cm^?1) based on a polymeric ionic liquid is spray‐printed as a second layer and infiltrated through the porous electrodes. A symmetric all‐organic battery is then formed with the addition of another identical set of electrode and electrolyte layers. Both density functional theory calculations and charge‐discharge profiles show that the potentials for the negative and positive electrode reactions are amongst the lowest (≈2.0 V vs Li) and the highest (≈3.5 V vs Li), respectively, for quinone‐type molecules. Over the C‐rate range 0.2 to 5 C, the battery has a discharge cell voltage of more than 1 V even up to 250 charge‐discharge cycles and capacities are in the range 50–80 mA h g^?1 at 0.5 C.     

Inkjet Printing of Back Electrodes for Inverted Polymer Solar Cells

Evaporation is the most commonly used deposition method in the processing of back electrodes in polymer solar cells used in scientific studies. However, vacuum‐based methods such as evaporation are uneconomical in the upscaling of polymer solar cells as they are throughput limiting steps in an otherwise fast roll‐to‐roll production line. In this paper, the applicability of inkjet printing in the ambient processing of back electrodes in inverted polymer solar cells with the structure ITO/ZnO/P3HT:PCBM/PEDOT:PSS/Ag is investigated. Furthermore, the limitation of screen printing, the commonly employed method in the ambient processing of back electrode, is demonstrated and discussed. Both inkjet printing and screen printing of back electrodes are studied for their impact on the photovoltaic properties of the polymer solar cells measured under 1000 Wm^?2 AM1.5. Each ambient processing technique is compared with evaporation in the processing of back electrode. Laser beam induced current (LBIC) imaging is used to investigate the impact of the processing techniques on the current collection in the devices. We report that inkjet printing of back electrode delivers devices having photovoltaic performance comparable to devices with evaporated back electrodes. We further confirm that inkjet printing represent an efficient alternative to screen printing.     

Combinatorial Screening of Polymer:Fullerene Blends for Organic Solar Cells by Inkjet Printing

Polymer:fullerene blends were screened in a combinatorial approach using inkjet printing thin film libraries for photovoltaic devices. The application of inkjet printing enabled a fast and simple experimental workflow from film preparation to the study of structure‐property‐relationships with a very high material efficiency. Inkjet printing requires less material for the preparation of thin film libraries in comparison to other dispensing techniques, like spin‐coating. Two polymers (PCPDTBT, PSBTBT) and two fullerene derivatives (mono‐PCBM, bis‐PCBM) were investigated in various blend ratios, concentrations, solvent ratios, and film thicknesses. Morphological and optical properties of the inkjet printed films were investigated and compared with spin‐coated films. This study shows the principle of an experimental setup from solution preparation to film characterization for the combinatorial investigation of large polymer:fullerene libraries.     

Carbonyls: Powerful Organic Materials for Secondary Batteries

The application of organic carbonyl compounds as high performance electrode materials in secondary batteries enables access to metal‐free, low‐cost, environmental friendly, flexible, and functional rechargeable energy storage systems. Organic compounds have so far not received much attention as potential active materials in batteries, mainly because of the success of inorganic materials in both research and commercial applications. However, new requirements in secondary batteries such as flexibility accompanied with low production costs and environmental friendliness, in particular for portable devices, reach the limit of inorganic electrode materials. Organic carbonyl compounds represent the most promising materials to satisfy these needs. Here, recent efforts of the research in the field of organic carbonyl materials for secondary batteries are summarized, and the working principle and the structural design of different groups of carbonyl material is presented. Finally, the influence of conductive additives and binders on the cell performance is closely evaluated for each class of materials.     

Human Cartilage Tissue Fabrication Using Three-dimensional Inkjet Printing Technology

Bioprinting, which is based on thermal inkjet printing, is one of the most attractive enabling technologies in the field of tissue engineering and regenerative medicine. With digital control cells, scaffolds, and growth factors can be precisely deposited to the desired two-dimensional (2D) and three-dimensional (3D) locations rapidly. Therefore, this technology is an ideal approach to fabricate tissues mimicking their native anatomic structures. In order to engineer cartilage with native zonal organization, extracellular matrix composition (ECM), and mechanical properties, we developed a bioprinting platform using a commercial inkjet printer with simultaneous photopolymerization capable for 3D cartilage tissue engineering. Human chondrocytes suspended in poly(ethylene glycol) diacrylate (PEGDA) were printed for 3D neocartilage construction via layer-by-layer assembly. The printed cells were fixed at their original deposited positions, supported by the surrounding scaffold in simultaneous photopolymerization. The mechanical properties of the printed tissue were similar to the native cartilage. Compared to conventional tissue fabrication, which requires longer UV exposure, the viability of the printed cells with simultaneous photopolymerization was significantly higher. Printed neocartilage demonstrated excellent glycosaminoglycan (GAG) and collagen type II production, which was consistent with gene expression. Therefore, this platform is ideal for accurate cell distribution and arrangement for anatomic tissue engineering.     

Covalent–Organic Frameworks: Advanced Organic Electrode Materials for Rechargeable Batteries

Covalent–organic frameworks (COFs), featuring structural diversity, framework tunability and functional versatility, have emerged as promising organic electrode materials for rechargeable batteries and garnered tremendous attention in recent years. The adjustable pore configuration, coupled with the functionalization of frameworks through pre‐ and post‐synthesis strategies, enables a precise customization of COFs, which provides a novel perspective to deepen the understanding of the fundamental problems of organic electrode materials. In this review, a summary of the recent research into COFs electrode materials for rechargeable batteries including lithium‐ion batteries, sodium‐ion batteries, potassium‐ion batteries, and aqueous zinc batteries is provided. In addition, this review will also cover the working principles, advantages and challenges, strategies to improve electrochemical performance, and applications of COFs in rechargeable batteries.     

Metal‐Organic Framework Cathodes Based on a Vanadium Hexacyanoferrate Prussian Blue Analogue for High‐Performance Aqueous Rechargeable Batteries

Despite the unique advantages of the metal‐organic framework of Prussian blue analogues (PBAs), including a favorable crystallographic structure and facile diffusion kinetics, the capacity of PBAs delivered in aqueous systems has been limited to ≈60 mA h g^?1 because only single species of transition metal ions incorporated into the PBAs are electrochemically activated. Herein, vanadium hexacyanoferrate (V/Fe PBA) is proposed as a breakthrough to this limitation, and its electrochemical performance as a cathode for aqueous rechargeable batteries (ARBs) is investigated for the first time. V/Fe PBAs are synthesized by a simple co‐precipitation method with optimization of the acidity and molar ratios of precursor solutions. The V/Fe PBAs provide an improved capacity of 91 mA h^?1 under a current density of 110 mA g^?1 (C‐rate of ≈1.2 C), taking advantage of the multiple‐electron redox reactions of V and Fe ions. Under an extremely fast charge/discharge rate of 3520 mA g^?1, the V/Fe PBA exhibits a sufficiently high discharge capacity of 54 mA h g^?1 due to its opened structure and 3D hydrogen bonding networks. V/Fe PBA‐based ARBs are the most promising candidates for large‐scale stationary energy storage systems due to their high electrochemical performance, reasonable cost, and high efficiency.     

Additional Sodium Insertion into Polyanionic Cathodes for Higher‐Energy Na‐Ion Batteries

Na‐ion technology is increasingly studied as a low‐cost solution for grid storage applications. Many positive electrode materials have been reported, mainly among layered oxides and polyanionic compounds. The vanadium oxy/flurophosphate solid solution Na₃V₂(PO₄)₂F_3‐y O_2y (0 ≤ y ≤ 1), in particular, has proven the ability to deliver ≈500 Wh kg^‐1, operating on the V³⁺/V⁴⁺ (y = 0) or V⁴⁺/V⁵⁺ redox couples (y = 1). This paper reports here on a significant increase in specific energy by enabling sodium insertion into Na₃V₂(PO₄)₂FO₂ to reach Na₄V₂(PO₄)₂FO₂ upon discharge. This occurs at ≈1.6 V and increases the theoretical specific energy to 600 Wh kg^?1, rivaling that of several Li‐ion battery cathodes. This improvement is achieved by the judicious modification of the composition either as O for F substitution, or Al for V substitution, both of which disrupt Na‐ion ordering and thereby enable insertion of the 4th Na. This paper furthermore shows from operando X‐Ray Diffraction (XRD) that this energy is obtained in the cycling range Na₄V₂(PO₄)₂FO₂–NaV₂(PO₄)₂FO₂ with a very small overall volume change of 1.7%, which is one of the smallest volume changes for Na‐ion cathodes and which is a crucial requisite for stable long‐term cycling.     

Flexible Pseudocapacitive Electrochromics via Inkjet Printing of Additive‐Free Tungsten Oxide Nanocrystal Ink

Direct inkjet printing of functional inks is an emerging and promising technique for the fabrication of electrochemical energy storage devices. Electrochromic energy devices combine electrochromic and energy storage functions, providing a rising and burgeoning technology for next‐generation intelligent power sources. However, printing such devices has, in the past, required additives or other second phase materials in order to create inks with suitable rheological properties, which can lower printed device performance. Here, tungsten oxide nanocrystal inks are formulated without any additives for the printing of high‐quality tungsten oxide thin films. This allows the assembly of novel electrochromic pseudocapacitive zinc‐ion devices, which exhibit a relatively high capacity (≈260 C g^?1 at 1 A g^?1) with good cycling stability, a high coloration efficiency, and fast switching response. These results validate the promising features of inkjet‐printed electrochromic zinc‐ion energy storage devices in a wide range of applications in flexible electronic devices, energy‐saving buildings, and intelligent systems.     

Exfoliated Triazine‐Based Covalent Organic Nanosheets with Multielectron Redox for High‐Performance Lithium Organic Batteries

The development of the next‐generation lithium ion battery requires environmental‐friendly electrode materials with long cycle life and high energy density. Organic compounds are a promising potential source of electrode materials for lithium ion batteries due to their advantages of chemical richness at the molecular level, cost benefit, and environmental friendliness, but they suffer from low capacity and dissatisfactory cycle life mainly due to hydrophobic dissolution in organic electrolytes and poor electronic conductivity. In this work, two types of triazine‐based covalent organic nanosheets (CONs) are exfoliated and composited with carbon nanotubes. The thin‐layered 2D structure for the exfoliated CONs can activate more functional groups for lithium storage and boost the utilization efficiency of redox sites compared to its bulk counterpart. Large reversible capacities of above 1000 mAh g^?1 can be achieved after 250 cycles, which is comparable to high‐capacity inorganic electrodes. Moreover, the lithium‐storage mechanism is determined to be an intriguing 11 and 16 electron redox reaction, associated with the organic groups (unusual triazine ring, piperazine ring, and benzene ring, and common C?N, ? NH? groups).     

3D Printing Sulfur Copolymer‐Graphene Architectures for Li‐S Batteries

3D printing is becoming an efficient approach to facilely and accurately fabricate diverse complex architectures with broad applications. However, suitable inks and 3D print favorable architectures with high electrochemical performances for energy storage are still being explored. Here, sulfur copolymer‐graphene architectures with well‐designed periodic microlattices are 3D printed as a cathode for Li‐S batteries using a suitable ink composed of sulfur particles, 1,3‐diisopropenylbenzene (DIB), and condensed graphene oxide dispersion. Using thermal treatment, elemental sulfur can be reacted with DIB to produce sulfur copolymer, which can partially suppress the dissolution of polysulfides. Moreover, graphene in the architecture can provide high electrical conductivity for whole electrode. Hence, 3D printed sulfur copolymer‐graphene architecture exhibits a high reversible capacity of 812.8 mA h g^?1 and good cycle performance. Such a simple 3D printing approach can be further extended to construct many complex architectures for various energy storage devices.     

Extremely Flexible Transparent Conducting Electrodes for Organic Devices

Extremely flexible transparent conducting electrodes are developed using a combination of metal‐embedding architecture into plastic substrate and ultrathin transparent electrodes, which leads to highly transparent (optical transmittance ≈93% at a wavelength of 550 nm), highly conducting (sheet resistance ≈13 Ω □^?1), and extremely flexible (bending radius ≈ 200 μm) electrodes. The electrodes are used to fabricate flexible organic solar cells and organic light‐emitting diodes that exhibit performance similar or superior to that of devices fabricated on glass substrates. Moreover, the flexible devices do not show degradation in their performance even after being folded with a radius of ≈200 μm.     

Diluents Effect on Inhibiting Dissolution of Organic Electrode for Highly Reversible Li-Ion Batteries

The potential of organic electrodes in lithium-ion batteries (LIBs) is highlighted by their cost-effectiveness and natural abundance. However, the dissolution of the active material in the electrolyte is a major obstacle to their use in LIBs. Although high-concentration electrolytes (HCEs) have been proposed to address this issue, they face challenges such as high viscosity, poor wettability, and suboptimal ion conductivity. Hence, this study introduces diluted electrolytes as non-solvating electrolytes to offset the physical limitations of HCEs and suppress the dissolution of organic electrodes. When a diluted electrolyte is used, perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA)—a notable organic electrode material—demonstrates superior capacity retention and rate performance, achieving 91% of capacity retained at 1000 mA g⁻¹ over 1000 cycles. Through electrochemical and spectroscopic measurements and molecular dynamics simulations, the diluted electrolyte successfully inhibits and demonstrates the dissolution of the active material, preventing capacity loss and the detrimental shuttle effect. This study presents a promising strategy for achieving highly reversible organic electrode-based LIBs through the development of nonsolvating electrolytes.     

Planar and Three-Dimensional Printing of Conductive Inks

Printed electronics rely on low-cost, large-area fabrication routes to create flexible or multidimensional electronic, optoelectronic, and biomedical devices^1-3. In this paper, we focus on one- (1D), two- (2D), and three-dimensional (3D) printing of conductive metallic inks in the form of flexible, stretchable, and spanning microelectrodes.Direct-write assembly^4,5 is a 1-to-3D printing technique that enables the fabrication of features ranging from simple lines to complex structures by the deposition of concentrated inks through fine nozzles (~0.1 - 250 μm). This printing method consists of a computer-controlled 3-axis translation stage, an ink reservoir and nozzle, and 10x telescopic lens for visualization. Unlike inkjet printing, a droplet-based process, direct-write assembly involves the extrusion of ink filaments either in- or out-of-plane. The printed filaments typically conform to the nozzle size. Hence, microscale features (< 1 μm) can be patterned and assembled into larger arrays and multidimensional architectures.In this paper, we first synthesize a highly concentrated silver nanoparticle ink for planar and 3D printing via direct-write assembly. Next, a standard protocol for printing microelectrodes in multidimensional motifs is demonstrated. Finally, applications of printed microelectrodes for electrically small antennas, solar cells, and light-emitting diodes are highlighted.     

In Situ Formation of Protective Coatings on Sulfur Cathodes in Lithium Batteries with LiFSI‐Based Organic Electrolytes

Development of sulfur cathodes with 100% coulombic efficiency (CE) and good cycle stability remains challenging due to the polysulfide dissolution in electrolytes. Here, it is demonstrated that electrochemical reduction of lithium bis(fluorosulfonyl)imide (LiFSI) based electrolytes at a potential close to the sulfur cathode operation forms in situ protective coating on both cathode and anode surfaces. Quantum chemistry studies suggest the coating formation is initiated by the FSI(‐F) anion radicals generated during electrolyte reduction. Such a reduction additionally results in the formation of LiF. Accelerated cycle stability tests at 60 °C in a very simple electrolyte (LiFSI in dimethoxyethane with no additives) show an average CE approaching 100.0% over 1000 cycles with a capacity decay less than 0.013% per cycle after stabilization. Such a remarkable performance suggests a great promise of both an in situ formation of protective solid electrolyte coatings to avoid unwanted side reactions and the use of a LiFSI salt for this purpose.     

Liquid Metal Electrodes for Energy Storage Batteries

The increasing demands for integration of renewable energy into the grid and urgently needed devices for peak shaving and power rating of the grid both call for low‐cost and large‐scale energy storage technologies. The use of secondary batteries is considered one of the most effective approaches to solving the intermittency of renewables and smoothing the power fluctuations of the grid. In these batteries, the states of the electrode highly affect the performance and manufacturing process of the battery, and therefore leverage the price of the battery. A battery with liquid metal electrodes is easy to scale up and has a low cost and long cycle life. In this progress report, the state‐of‐the‐art overview of liquid metal electrodes (LMEs) in batteries is reviewed, including the LMEs in liquid metal batteries (LMBs) and the liquid sodium electrode in sodium‐sulfur (Na–S) and ZEBRA (Na–NiCl₂) batteries. Besides the LMEs, the development of electrolytes for LMEs and the challenge of using LMEs in the batteries, and the future prospects of using LMEs are also discussed.     

Contact‐Induced Mechanisms in Organic Photovoltaics: A Steady‐State and Transient Study

The role of the contacts in thin‐film, blended heterojunctions (<100 nm thick) organic photovoltaics is explored, specifically considering concepts of carrier selectivity, injection, and extraction efficiency, relative to recombination. Contact effects are investigated by comparing two hole‐collecting interlayers: a phosphonic acid monolayer on indium tin oxide (ITO) and a nickel oxide thin film. The interlayers have equivalent work functions (≈5.4 eV) but widely variant energy band offsets relative to the lowest unoccupied molecular orbital of the acceptor (electron blocking versus not), which are coupled to large differences in carrier density. Trends in open‐circuit voltages (V_OC) as a function of light intensity and temperature are compared and it is concluded that the dominant mechanism limiting V_OC for high density of states contacts is free carrier injection, not surface recombination or extraction barriers. Transient photocurrent decay measurements confirm excess reinjected carriers decrease the extraction efficiency via increased recombination and decrease free carrier lifetime, even at high internal electric fields, due to space charge accumulation. These results demonstrate that the energetics and injection dynamics of the interface between interlayers and high carrier density electrodes (typically ITO and metals) must be considered with fabrication and processing of interlayers, in addition to possible carrier selectivity and the interface with the active layer.