Overcoming the Trade-Off between Optical Transmittance and Areal Capacitance of Transparent Supercapacitors for Practical Application

It is substantially challenging for transition metal oxide nanoparticle (NP)-based electrodes for supercapacitors to achieve high transparency and large capacity simultaneously due to the inherent trade-off between optical transmittance (T) and areal capacitance (C_A). This study demonstrates how this trade-off limitation can be overcome by replacing some electrode NPs with transparent tin oxide (SnO₂) NPs. Although SnO₂ NPs are non-capacitive, they provide effective paths for charge transport, which simultaneously increase the C_A and T_550nm of the manganese oxide (Mn₃O₄) NP electrode from 11.7 to 13.4 mF cm⁻² and 82.1% to 87.4%, respectively, when 25 wt% of Mn₃O₄ are replaced by SnO₂. The obtained C_A values at a given T are higher than those of the transparent electrodes previously reported. An energy storage window fabricated using the mixed-NP electrodes exhibits the highest energy density among transparent supercapacitors previously reported. The improved energy density enables the window to operate various electronic devices for a considerable amount of time, demonstrating its applicability in constructing a reliable and space-efficient building-integrated power supply system.     

“Salting out” in Hofmeister Effect Enhancing Mechanical and Electrochemical Performance of Amide-based Hydrogel Electrolytes for Flexible Zinc-Ion Battery

With the development of flexible and wearable electronic devices, it is a new challenge for polymer hydrogel electrolytes to combine high mechanical flexibility and electrochemical performance into one membrane. In general, the high content of water in hydrogel electrolyte membranes always leads to poor mechanical strength, and limits their applications in flexible energy storage devices. In this work, based on the “salting out” phenomenon in Hofmeister effect, a kind of gelatin-based hydrogel electrolyte membrane is fabricated with high mechanical strength and ionic conductivity by soaking pre-gelated gelatin hydrogel in 2 m ZnSO₄ aqueous. Among various gelatin-based electrolyte membranes, the gelatin-ZnSO₄ electrolyte membrane delivers the “salting out” property of Hofmeister effect, which improves both the mechanical strength and electrochemical performance of gelatin-based electrolyte membranes. The breaking strength reaches 1.5 MPa. When applied to supercapacitors and zinc-ion batteries, it can sustain over 7500 and 9300 cycles for repeated charging and discharging processes. This study provides a very simple and universal method to prepare polymer hydrogel electrolytes with high strength, toughness, and stability, and its applications in flexible energy storage devices provide a new idea for the construction of secure and stable flexible and wearable electronic devices.     

Scalable Manufacturing of Environmentally Stable All-Solid-State Plant Protein-Based Supercapacitors with Optimal Balance of Capacitive Performance and Mechanically Robust

The development of advanced biomaterial with mechanically robust and high energy density is critical for flexible electronics, such as batteries and supercapacitors. Plant proteins are ideal candidates for making flexible electronics due to their renewable and eco-friendly natures. However, due to the weak intermolecular interactions and abundant hydrophilic groups of protein chains, the mechanical properties of protein-based materials, especially in bulk materials, are largely constrained, which hinders their performance in practical applications. Here, a green and scalable method is shown for the fabrication of advanced film biomaterials with high mechanical strength (36.3 MPa), toughness (21.25 MJ m⁻³), and extraordinary fatigue-resistance (213 000 times) by incorporating tailor-made core–double-shell structured nanoparticles. Subsequently, the film biomaterials combine to construct an ordered, dense bulk material by stacking-up and hot-pressing techniques. Surprisingly, the solid-state supercapacitor based on compacted bulk material shows an ultrahigh energy density of 25.8 Wh kg⁻¹, which is much higher than those previously reported advanced materials. Notably, the bulk material also demonstrates long-term cycling stability, which can be maintained under ambient condition or immersed in H₂SO₄ electrolyte for more than 120 days. Thus, this research improves the competitiveness of protein-based materials for real-world applications such as flexible electronics and solid-state supercapacitors.     

Multicomponent Hybridization Transition Metal Oxide Electrode Enriched with Oxygen Vacancy for Ultralong-Life Supercapacitor

Transition metal oxide electrode materials for supercapacitors suffer from poor electrical conductivity and stability, which are the research focus of the energy storage field. Herein, multicomponent hybridization Ni-Cu oxide (NCO-Ar/H₂-10) electrode enriched with oxygen vacancy and high electrical conductivity including the Cu_0.2Ni_0.8O, Cu₂O and CuO is prepared by introducing Cu element into Ni metal oxide with hydrothermal, annealing, and plasma treatment. The NCO-Ar/H₂-10 electrode exhibits high specific capacity (1524 F g⁻¹ at 3 A g⁻¹), good rate performance (72%) and outstanding cyclic stability (109% after 40,000 cycles). The NCO-Ar/H₂-10//AC asymmetric supercapacitor (ASC) achieves high energy density of 48.6 Wh kg⁻¹ at 799.6 W kg⁻¹ while exhibiting good cycle life (117.5% after 10,000 cycles). The excellent electrochemical performance mainly comes from the round-trip valence change of Cu⁺/Cu²⁺ in the multicomponent hybridization enhance the surface capacitance during the redox process, and the change of electronic microstructure triggered by a large number of oxygen vacancies reduce the adsorption energy of OH⁻ ions of thin nanosheet with crack of surface edge, ensuring electron and ion-transport processes and remitting the structural collapse of material. This work provides a new strategy for improving the cycling stability of transition metal oxide electrode materials.     

Sustainable and Scalable Synthesis of 2D Ultrathin Hierarchical Porous Carbon Nanosheets for High-Performance Supercapacitor

2D carbon nanomaterials such as graphene, carbon nanosheets, and their derivatives, representing the emerging class of advanced multifunctional materials, have gained great research interest because of their extensive applications ranging from electrochemistry to catalysis. However, sustainable and scalable synthesis of 2D carbon nanosheets (CNs) with hierarchical architecture and irregular structure via a green and low-cost strategy remains a great challenge. Herein, prehydrolysis liquor (PHL), an industrial byproduct of the pulping industry, is first employed to synthesize CNs via a simple hydrothermal carbonization technique. After mild activation with NH₄Cl and FeCl₃, the as-prepared activated CNs (A-CN@NFe) display an ultrathin structure (≈3 nm) and a desirable specific surface area (1021 m² g⁻¹) with hierarchical porous structure, which enables it to be both electroactive materials and structural support materials in nanofibrillated cellulose/A-CN@NFe/polypyrrole (NCP) nanocomposite, and thus endowing nanocomposite with impressive capacitance properties of 2546.3 mF cm⁻² at 1 mA cm⁻². Furthermore, the resultant all-solid-state symmetric supercapacitor delivers a satisfactory energy storage ability of 90.1 µWh cm⁻² at 250.0 µW cm⁻². Thus, this work not only opens a new window for sustainable and scalable synthesis of CNs, but also offers a double profits strategy for energy storage and biorefinery industry.     

The Road Towards Planar Microbatteries and Micro‐Supercapacitors: From 2D to 3D Device Geometries

The rapid development and further modularization of miniaturized and self‐powered electronic systems have substantially stimulated the urgent demand for microscale electrochemical energy storage devices, e.g., microbatteries (MBs) and micro‐supercapacitors (MSCs). Recently, planar MBs and MSCs, composed of isolated thin‐film microelectrodes with extremely short ionic diffusion path and free of separator on a single substrate, have become particularly attractive because they can be directly integrated with microelectronic devices on the same side of one single substrate to act as a standalone microsized power source or complement miniaturized energy‐harvesting units. The development of and recent advances in planar MBs and MSCs from the fundamentals and design principle to the fabrication methods of 2D and 3D planar microdevices in both in‐plane and stacked geometries are highlighted. Additonally, a comprehensive analysis of the primary aspects that eventually affect the performance metrics of microscale energy storage devices, such as electrode materials, electrolyte, device architecture, and microfabrication techniques are presented. The technical challenges and prospective solutions for high‐energy‐density planar MBs and MSCs with multifunctionalities are proposed.     

Redox Poly-Counterion Doped Conducting Polymers for Pseudocapacitive Energy Storage

Conducting polymers (CPs) have been widely studied for electrochemical energy storage. However, the dopants in CPs are often electrochemically inactive, introducing “dead-weight” to the materials. Moreover, commercial-level electrode materials with high mass loadings (e.g., >10 mg cm⁻²) often encounter the problems of inferior electrical and ionic conductivity. Here, a redox-active poly-counterion doping concept is proposed to improve the electrochemical performance of CPs with ultra-high mass loadings. As a study prototype, heptamolybdate anion (Mo₇O₂₄⁶⁻) doped polypyrrole (PPy) is synthesized by electro-polymerization. A 2 mm thick PPy electrode with mass loading of ≈192 mg cm⁻² reaches a record-high areal capacitance of ≈47 F cm⁻², competitive gravimetric capacitance of 235 F g⁻¹, and volumetric capacitance of 235 F cm⁻³. With poly-counterion doping, the dopants also undergo redox reactions during charge/discharge processes, providing additional capacitance to the electrode. The interaction between polymer chains and the poly-counterions enhances the electrical conductivity of CPs. Besides, the poly-counterions with large steric hindrance could act as structural pillars and endow CPs with open structures for facile ion transport. The concept proposed in this work enriches the electrochemistry of CPs and promotes their practical applications.     

A 3D Cu-Naphthalene-Phosphonate Metal–Organic Framework with Ultra-High Electrical Conductivity

A conductive phosphonate metal–organic framework (MOF), [{Cu(H₂O)}(2,6-NDPA)_0.5] (NDPA = naphthalenediphosphonic acid), which contains a 2D inorganic building unit (IBU) comprised of a continuous edge-sharing sheet of copper phosphonate polyhedra is reported. The 2D IBUs are connected to each other via polyaromatic 2,6-NDPA's, forming a 3D pillared-layered MOF structure. This MOF, known as TUB40, has a narrow band gap of 1.42 eV, a record high average electrical conductance of 2 × 10² S m⁻¹ at room temperature based on single-crystal conductivity measurements, and an electrical conductance of 142 S m⁻¹ based on a pellet measurement. Density functional theory (DFT) calculations reveal that the conductivity is due to an excitation from the highest occupied molecular orbital on the naphthalene-building unit to the lowest unoccupied molecular orbital on the copper atoms. Temperature-dependent magnetization measurements show that the copper atoms are antiferromagnetically coupled at very low temperatures, which is also confirmed by the DFT calculations. Due to its high conductance and thermal/chemical stability, TUB40 may prove useful as an electrode material in supercapacitors.     

Integrating Flexible Ultralight 3D Ni Micromesh Current Collector with NiCo Bimetallic Hydroxide for Smart Hybrid Supercapacitors

Flexible and lightweight supercapacitors with superior mechanical flexibility and outstanding capacity are regarded as an ideal power source for wearable electronic devices. Meanwhile, incorporating additional novel characters such as transparency and electrochromism can further benefit the development of smart supercapacitors. Nevertheless, the application of the commonly used planar-structural current collectors is seriously restricted by their intrinsic properties such as poor rigidity, large thickness, and limited loading surface area. Flexible and ultralight current collectors with 3D architecture, high conductivity, and easy integration are believed to be the most appropriate alternatives to build high-performance supercapacitors. In this study, a novel and scalable manufacturing technique is developed to produce a flexible and ultralight 3D Ni micromesh (3D NM) current collector for supercapacitor. Flexible smart supercapacitor integrated by 3D NM and high active Ni–Co bimetallic hydroxide (3D NM@NiCo BH) delivers a considerable rate performance (60.6% capacity retention from 1 to 50 mA cm⁻²). Furthermore, the fabricated hybrid supercapacitor device integrated with electrochromic functionality can visually indicate the energy level by a color display. This flexible electrochromic supercapacitor based on ultralight 3D Ni micromesh provides a novel insight into multifunctional energy storage systems for smart wearable electronic devices.