Advanced 3D ordered electrodes for PEMFC applications: From structural features and fabrication methods to the controllable design of catalyst layers

The catalyst layers(CLs) electrode is the key component of the membrane electrode assembly(MEA) in proton exchange membrane fuel cells(PEMFCs). Conventional electrodes for PEMFCs are composed of carbon-supported, ionomer, and Pt nanoparticles, all immersed together and sprayed with a micron-level thickness of CLs. They have a performance trade-off where increasing the Pt loading leads to higher performance of abundant triple-phase boundary areas but increases the electrode cost. Major challenges must be overcome before realizing its wide commercialization. Literature research revealed that it is impossible to achieve performance and durability targets with only high-performance catalysts, so the controllable design of CLs architecture in MEAs for PEMFCs must now be the top priority to meet industry goals. From this perspective, a 3D ordered electrode circumvents this issue with a support-free architecture and ultrathin thickness while reducing noble metal Pt loadings. Herein, we discuss the motivation in-depth and summarize the necessary CLs structural features for designing ultralow Pt loading electrodes. Critical issues that remain in progress for 3D ordered CLs must be studied and characterized. Furthermore, approaches for 3D ordered CLs architecture electrode development, involving material design, structure optimization, preparation technology, and characterization techniques, are summarized and are expected to be next-generation CLs for PEMFCs. Finally, the review concludes with perspectives on possible research directions of CL architecture to address the significant challenges in the future.

Exceptional Performance of 3D Additive Manufactured NiFe Phosphite Oxyhydroxide Hollow Tubular Lattice Plastic Electrode for Large-Current-Density Water Oxidization

In this article,we report a 3D NiFe phosphite oxyhydroxide plastic electrode using high-resolution digital light processing(DLP)3D-printing technology via induced chemical deposition method.The as-prepared 3D plastic electrode exhibits no template requirement,freedom design,low-cost,robust,anticorrosion,lightweight,and micro-nano porous characteristics.It can be drawn to the conclusion that highly oriented open-porous 3D geometry structure will be beneficial for improving surface catalytic active area,wetting performance,and reaction–diffusion dynamics of plastic electrodes for oxygen evolution reaction(OER)catalysis process.Density functional theory(DFT)calculation interprets the origin of high activity of NiFe(PO_(3))O(OH)and demonstrates that the implantation of the–PO_(3)can effectively bind the 3d orbital of Ni in NiFe(PO_(3))O(OH),lead to the weak adsorption of intermediate,make electron more active to improve the conductivity,thereby lowing the transform free energy of*O to*OOH.The water oxidization performance of as-prepared 3D NiFe(PO_(3))O(OH)hollow tubular(HT)lattice plastic electrode has almost reached the state-of-the-art level compared with the as-reported large-current-density catalysts or 3D additive manufactured plastic/metal-based electrodes,especially for high current OER electrodes.This work breaks through the bottleneck that plagues the performance improvement of low-cost high-current electrodes.

Recent advances in 3D printed electrode materials for electrochemical energy storage devices

Electrochemical energy storage(EES)systems like batteries and supercapacitors are becoming the key power sources for attempts to change the energy dependency from inadequate fossil fuels to sustainable and renewable resources.Electrochemical energy storage devices(EESDs)operate efficiently as a result of the construction and assemblage of electrodes and electrolytes with appropriate structures and effective materials.Conventional manufacturing procedures have restrictions on regulating the morphology and architecture of the electrodes,which would influence the performance of the devices.3D printing(3DP)is an advanced manufacturing technology combining computer-aided design and has been recognised as an artistic method of fabricating different fragments of energy storage devices with its ability to precisely control the geometry,porosity,and morphology with improved specific energy and power densities.The capacity to create mathematically challenging shape or configuration designs and high-aspect-ratio 3D architectures makes 3D printing technology unique in its benefits.Nevertheless,the control settings,interactive manufacturing processes,and protracted post-treatments will affect the reproducibility of the printed components.More intelligent software,sophisticated control systems,high-grade industrial equipment,and post-treatment-free methods are necessary to develop.3D printed(3DPd)EESDs necessitate dynamic printable materials and composites that are influenced by performance criteria and fundamental electrochemistry.Herein,we review the recent advances in 3DPd electrodes for EES applications.The emphasis is on printable material synthesis,3DP techniques,and the electrochemical performance of printed electrodes.For the fabrication of electrodes,we concentrate on major 3DP technologies such as direct ink writing(DIW),inkjet printing(IJP),fused deposition modelling(FDM),and stereolithography3DP(SLA).The benefits and drawbacks of each 3DP technology are extensively discussed.We provide an outlook on the integration of synthesis of emerging nanomaterials and fabrication of complex structures from micro to macroscale to construct highly effective electrodes for the EESDs.

Electrochemical Behavior of CoSb_3-based Electrodes Using Binary PAni/PVDF Binder

The polyaniline （PAni）/polyvinylidene fluoride （PVDF） hybrid was served as a novel binder for CoSb3-based alloy electrode. The effect of PAni content on the electrochemical performances of the alloy electrode was investigated. It was found that the CoSb3 electrode using the binary PAni/PVDF binder exhibits higher reversible capacity than that using the single PVDF binder, especially in the initial cycles. As a result, the PAni/PVDF hybrid could be a promising binder for the alloy electrode.

Peptide self‐assembly as a strategy for facile immobilization of redox enzymes on carbon electrodes

Redox-enzyme‐mediated electrochemical processes such as hydrogen production,nitrogen fixation,and CO_(2) reduction are at the forefront of the green chemistry revolution.To scale up,the inefficient two‐dimensional(2D)immobilization of redox enzymes on working electrodes must be replaced by an efficient dense 3D system.Fabrication of 3D electrodes was demonstrated by embedding enzymes in polymer matrices.However,several requirements,such as simple immobilization,prolonged stability,and resistance to enzyme leakage,still need to be addressed.The study presented here aims to overcome these gaps by immobilizing enzymes in a supramolecular hydrogel formed by the self‐assembly of the peptide hydrogelator fluorenylmethyloxycarbonyldiphenylalanine.Harnessing the self‐assembly process avoids the need for tedious and potentially harmful chemistry,allowing the rapid loading of enzymes on a 3D electrode under mild conditions.Using the[FeFe]hydrogenase enzyme,high enzyme loads,prolonged resistance against electrophoresis,and highly efficient hydrogen production are demonstrated.Further,this enzyme retention is shown to arise from its interaction with the peptide nanofibrils.Finally,this method is successfully used to retain other redox enzymes,paving the way for a variety of enzyme‐mediated electrochemical applications.

Pause electrolysis for acidic CO_(2) reduction on 3-dimensional Cu

Electrochemical CO_(2) reduction reaction(CO_(2) RR)exhibits remarkable potential in producing valuable chemicals with renewable energy.Operating CO_(2) RR in acidic media is beneficial to solve the issue of low carbon utilization brought by(bi)carbonate formation at the cathode.Suppressing the competing hydrogen evolution reaction and achieving stable CO_(2) RR performance remains challenging.Herein,we constructed a 3-dimensional Cu(3D-Cu)gas diffusion electrode(GDE)to achieve efficient C_(2)H_(4) production with a partial current density(j C_(2)H_(4))of over 470 mA cm^(2) and a Faradaic efficiency(FE C_(2)H_(4)) of 40%.With pause electrolysis,the decay rate of the j C_(2)H_(4) is only half that of the traditional constant electrolysis.The GDE after constant electrolysis was found to suffer from severe salt formation,leading to the decreased activity and poor stability.

“All‐In‐One” integrated ultrathin SnS2@3D multichannel carbon matrix power high‐areal–capacity lithium battery anode

Construction of a thickness‐independent electrode with high active material mass loading is crucial for the development of high energy rechargeable lithium battery.Herein,we fabricate an all‐in‐one integrated SnS2@3D multichannel carbon matrix(SnS2@3DMCM)electrode with in‐situ growth of ultrathin SnS2 nanosheets inside the inner walls of three dimensional(3D)multichannels.The interconnected conductive carbon matrix derived from natural wood acts as an integrated porous current collector to avail the electrons transport and accommodate massive SnS2 nanosheets,while plenty of 3D aligned multichannels facilitate fast ions transport with electrode thickness‐independent even under high mass loading.As expected,the integrated SnS2@3DMCM electrode exhibits remarkable electrochemical lithium storage performance,such as exceptional high‐areal‐capacity of 6.4 mAh cm−2,high rate capability of 3 mAh cm−2 under current of 6.8 mAcm−2(10 C),and stable cycling performance of 6.8 mAcm−2 with a high mass loading of 7mg cm−2.The 3D integrated porous electrode constructing conveniently with the natural source paves new avenues towards future high‐performance lithium batteries.

Intrinsic electrochemical activity of Ni in Ni_(3)Sn_(4) anode accommodating high capacity and mechanical stability for fast-charging lithium-ion batteries

Fast interfacial kinetics derived from bicontinuous three-dimensional(3D)architecture is a strategic feature for achieving fast-charging lithium-ion batteries(LIBs).One of the main reasons is its large active surface and short diffusion path.Yet,understanding of unusual electrochemical properties still remain great challenge due to its complexity.In this study,we proposed a nickel–tin compound(Ni_(3)Sn_(4))supported by 3D Nickel scaffolds as main frame because the Ni_(3)Sn_(4) clearly offers a higher reversible capacity and stable cycling performance than bare tin(Sn).In order to verify the role of Ni,atomic-scale simulation based on density functional theory systematically addressed to the reaction mechanism and structural evolution of Ni_(3)Sn_(4) during the lithiation process.Our findings are that Ni enables Ni_(3)Sn_(4) to possess higher mechanical stability in terms of reactive flow stress,subsequently lead to improve Li storage capability.This study elucidates an understanding of the lithiation mechanism of Ni_(3)Sn_(4) and provides a new perspective for the design of high-capacity and high-power 3D anodes for fast-charging LIBs.

Porous fiber paper and 3D patterned electrodes composed high-sensitivity flexible piezoresistive sensor for physiological signal monitoring

The research on flexible pressure sensors has drawn widespread attention in recent years,especially in the fields of health care and intelligent robots.In practical applications,the sensitivity of sensors directly affects the precision and integrity of weak pressure signals.Here,a pressure sensor with high sensitivity and a wide measurement range composed of porous fiber paper and 3D patterned electrodes is proposed.Multi-walled carbon nanotubes with excellent conductivity were evenly sprayed on the fiber paper to form the natural spatial conducting networks,while the copper-deposited polydimethylsiloxane films with micropyramids array were used as electrodes and flexible substrates.Increased conducting paths between electrodes and fibers can be obtained when high-density micro-pyramids fall into the porous structures of the fiber paper under external pressure,thereby promoting the pressure sensor to show an ultra-high sensitivity of 17.65 kPa^(-1)in the pressure range of 0–2 kPa,16 times that of the device without patterned electrodes.Besides,the sensor retains a high sensitivity of 2.06 kPa^(-1)in an ultra-wide measurement range of 150 kPa.Moreover,the sensor can detect various physiological signals,including pulse and voice,while attached to the human skin.This work provides a novel strategy to significantly improve the sensitivity and measurement range of flexible pressure sensors,as well as demonstrates attractive applications in physiological signal monitoring.

Novel 3D grid porous Li_(4)Ti_(5)O_(12) thick electrodes fabricated by 3D printing for high performance lithium-ion batteries

Three-dimensional(3D)grid porous electrodes introduce vertically aligned pores as a convenient path for the transport of lithium-ions(Li-ions),thereby reducing the total transport distance of Li-ions and improving the reaction kinetics.Although there have been other studies focusing on 3D electrodes fabricated by 3D printing,there still exists a gap between electrode design and their electrochemical performance.In this study,we try to bridge this gap through a comprehensive investigation on the effects of various electrode parameters including the electrode porosity,active material particle diameter,electrode electronic conductivity,electrode thickness,line width,and pore size on the electrochemical performance.Both numerical simulations and experimental investigations are conducted to systematically examine these effects.3D grid porous Li_(4)Ti_(5)O_(12)(LTO)thick electrodes are fabricated by low temperature direct writing technology and the electrodes with the thickness of 1085μm and areal mass loading of 39.44 mg·cm^(−2) are obtained.The electrodes display impressive electrochemical performance with the areal capacity of 5.88 mAh·cm^(−2)@1.0 C,areal energy density of 28.95 J·cm^(−2)@1.0 C,and areal power density of 8.04 mW·cm^(−2)@1.0 C.This study can provide design guidelines for obtaining 3D grid porous electrodes with superior electrochemical performance.

Ferroelectric properties of Bi_4Zr_(0.5)Ti_(2.5)O_(12) thin films prepared on LaNiO_3 bottom electrode by sol-gel method

The Bi4Zr0.5Ti2.5O12 (BZT) thin films were fabricated on the LaNiO3 bottom electrode using sol-gel method. The structure and morphology of the films were character-ized using X-ray diffraction, AFM and SEM. The results show that the films have a perovskite phase and dense microstructure. The 2Pr and 2Vc of the Pt/BZT/LaNiO3 capacitor are 28.2 μC/cm2 and 14.7 V respectively at an applied voltage of 25 V. After the switching of 1×1010 cycles, the Pr value decreases to 87% of its pre-fatigue val-ues. The dielectric constant (ε) and the dissipation factor (tanδ) of the BZT thin films are about 204 and 0.029 at 1 kHz, respectively. The films show good insulating behavior according to the test of leakage current. The clockwise C-V hysteresis curve observed shows that the Pt/BZT/LaNiO3 structure has a memory effect be-cause of the BZT film’s ferroelectric polarization.

A bismuth(Ⅲ) PVC membrane ion selective electrode based on5-(3,4,5-trimethoxyphenyl)-4-amino-1,2,4-triazole-3-thiol

The construction,performance characteristics and application of a new bismuth（Ⅲ） PVC membrane electrode based on 5-（3,4,5-trimethoxyphenyl）-4-amino-1,2,4-triazole-3-thiol are reported in this paper.The designed sensor exhibited a Nernstian response for Bi^3＋ ion ranging from 5.0×10^-7 mol/L to1.0×10^-2 mol/L with a slope of 19.8 mV/decade.The operational pH range of the sensor is 3.0-6.0.The electrode shows a response time of 6 s and can be used for at least five weeks without any considerable divergence in potentials.It exhibits very good selectivity relative to a wide variety of alkali,alkaline earth,transition and heavy metal ions.The proposed electrode could be used as an indicator electrode in potentiometric titration of Bi^3＋ ions with EDTA and in the determination of Bi^3＋ content in stomach medicine.

A flexible three-dimensional electrode mesh:An enabling technology for wireless brain-computer interface prostheses

The neural interface is a key component in wireless brain–computer prostheses.In this study,we demonstrate that a unique three-dimensional(3D)microneedle electrode on a flexible mesh substrate,which can be fabricated without complicated micromachining techniques,is conformal to the tissues with minimal invasiveness.Furthermore,we demonstrate that it can be applied to different functional layers in the nervous system without length limitation.The microneedle electrode is fabricated using drawing lithography technology from biocompatible materials.In this approach,the profile of a 3D microneedle electrode array is determined by the design of a two-dimensional(2D)pattern on the mask,which can be used to access different functional layers in different locations of the brain.Due to the sufficient stiffness of the electrode and the excellent flexibility of the mesh substrate,the electrode can penetrate into the tissue with its bottom layer fully conformal to the curved brain surface.Then,the exposed contact at the end of the microneedle electrode can successfully acquire neural signals from the brain.

Copper nanowire/multi-walled carbon nanotube com- posites as all-nanowire flexible electrode for fast-charging/ discharging lithium-ion battery

A novel lightweight three-dimensional （3D） composite anode for a fast-charging] discharging Li-ion battery （LIB） was fabricated entirely using one-dimensional （1D） nanomaterials, i.e., Cu nanowires （CuNWs） and multi-walled C nanotubes （MWCNTs）. Because of the excellent electrical conductivity, high-aspect ratio structures, and large surface areas of these nanomaterials, the CuNW-MWCNT composite （CNMC） with 3D structure provides significant advantages regarding the transport pathways for both electrons and ions. As an advanced binder-free anode, a CuNW-MWCNT composite film with a controllable thickness （~ 600 prn） exhibited a considerably low sheet resistance, and internal cell resistance. Furthermore, the random CuNW network with 3D structure acting as a rigid framework not only prevented MWCNT shrinkage and expansion due to aggregation and swelling but also minimized the effect of the volume change during the charge/discharge process. Both a half cell and a full cell of LIBs with the CNMC anode exhibited high specific capacities and Coulombic efficiendes, even at a high current. More importantly, we for the first time overcame the limitation of MWCNTs as anode materials for fast-charging]discharging LIBs （both half cells and full cells） by employing CuNWs, and the resulting anode can be applied to flexible LIBs. This innovative anode structure can lead to the development of ultrafast chargeable LIBs for electric vehides.