Correlation between hydration properties and electrochemical performances on Ln cation size effect in layered perovskite for protonic ceramic fuel cells

PrBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(PrBSCF) has attracted much research interest as a potential triple ionic and electronic conductor(TIEC) electrode for protonic ceramic fuel cells(PCFCs). The chemical formula for Pr BSCF is AA'B_(2)O_(5+δ), with Pr(A-site) and Ba/Sr(A'-site) alternately stacked along the c-axis. Due to these structural features, the bulk oxygen ion diffusivity is significantly enhanced through the disorder-free channels in the PrO layer;thus, the A site cations(lanthanide ions) play a pivotal role in determining the overall electrochemical properties of layered perovskites. Consequently, previous research has predominantly focused on the electrical properties and oxygen bulk/surface kinetics of Ln cation effects,whereas the hydration properties for PCFC systems remain unidentified. Here, we thoroughly examined the proton uptake behavior and thermodynamic parameters for the hydration reaction to conclusively determine the changes in the electrochemical performances depending on LnBa_(0.5)Sr_(0.5)Co_(1.5)Fe_(0.5)O_(5+δ)(LnBSCF,Ln=Pr, Nd, and Gd) cathodes. At 500 ℃, the quantitative proton concentration of PrBSCF was 2.04 mol% and progressively decreased as the Ln cation size decreased. Similarly, the Gibbs free energy indicated that less energy was required for the formation of protonic defects in the order of Pr BSCF < Nd BSCF < Gd BSCF. To elucidate the close relationship between hydration properties and electrochemical performances in LnBSCF cathodes, PCFC single cell measurements and analysis of the distribution of relaxation time were further investigated.

Conceptual design of a 714-MHz RFQ for compact proton injectors and development of a new tuning algorithm on its aluminium prototype

Radio frequency quadrupoles(RFQs),which are crucial components of proton injectors,significantly affect the performance of proton accelerator facilities.An RFQ with a high frequency of 714 MHz dedicated to compact proton injectors for medi-cal applications is designed in this study.The RFQ is designed to accelerate proton beams from 50 keV to 4 MeV within a short length of 2 m and can be matched closely with the downstream drift tube linac to capture more particles through a preliminary optimization.To develop an advanced RFQ,challenging techniques,including fabrication and tuning method,must be evaluated and verified using a prototype.An aluminium prototype is derived from the conceptual design of the RFQ and then redesigned to confirm the radio frequency performance,fabrication procedure,and feasibility of the tuning algorithm.Eventually,a new tuning algorithm based on the response matrix and least-squares method is developed,which yields favorable results based on the prototype,i.e.,the errors of the dipole and quadrupole components reduced to a low level after several tuning iterations.Benefiting from the conceptual design and techniques obtained from the prototype,the formal mechanical design of the 2-m RFQ is ready for the next manufacturing step.

Molecular-level proton acceptor boosts oxygen evolution catalysis to enable efficient industrial-scale water splitting

Industrial water splitting has long been suppressed by the sluggish kinetics of the oxygen evolution reaction(OER),which requires a catalyst to be efficient.Herein,we propose a molecular-level proton acceptor strategy to produce an efficient OER catalyst that can boost industrial-scale water splitting.Molecular-level phosphate(-PO_(4))group is introduced to modify the surface of PrBa_(0.5)Ca_(0.5)Co_(2)O_(5)+δ(PBCC).The achieved catalyst(PO_(4)-PBCC)exhibits significantly enhanced catalytic performance in alkaline media.Based on the X-ray absorption spectroscopy results and density functional theory(DFT)calculations,the PO_(4)on the surface,which is regarded as the Lewis base,is the key factor to overcome the kinetic limitation of the proton transfer process during the OER.The use of the catalyst in a membrane electrode assembly(MEA)is further evaluated for industrial-scale water splitting,and it only needs a low voltage of 1.66 V to achieve a large current density of 1 A cm^(-2).This work provides a new molecular-level strategy to develop highly efficient OER electrocatalysts for industrial applications.

Moisture‑Electric–Moisture‑Sensitive Heterostructure Triggered Proton Hopping for Quality‑Enhancing Moist‑Electric Generator

Moisture-enabled electricity(ME)is a method of converting the potential energy of water in the external environment into electrical energy through the interaction of functional materials with water molecules and can be directly applied to energy harvesting and signal expression.However,ME can be unreliable in numerous applications due to its sluggish response to moisture,thus sacrificing the value of fast energy harvesting and highly accurate information representation.Here,by constructing a moisture-electric-moisture-sensitive(ME-MS)heterostructure,we develop an efficient ME generator with ultra-fast electric response to moisture achieved by triggering Grotthuss protons hopping in the sensitized ZnO,which modulates the heterostructure built-in interfacial potential,enables quick response(0.435 s),an unprecedented ultra-fast response rate of 972.4 mV s^(−1),and a durable electrical signal output for 8 h without any attenuation.Our research provides an efficient way to generate electricity and important insight for a deeper understanding of the mechanisms of moisture-generated carrier migration in ME generator,which has a more comprehensive working scene and can serve as a typical model for human health monitoring and smart medical electronics design.

In-situ coating and surface partial protonation co-promoting performance of single-crystal nickel-rich cathode in all-solid-state batteries

The poor electrochemical performance of all-solid-state batteries(ASSBs),which is assemblied by Ni-rich cathode and poly(ethylene oxide)(PEO)-based electrolytes,can be attributed to unstable cathodic interface and poor crystal structure stability of Ni-rich cathode.Several coating strategies are previously employed to enhance the stability of the cathodic interface and crystal structure for Ni-rich cathode.However,these methods can hardly achieve simplicity and high efficiency simultaneously.In this work,polyacrylic acid(PAA)replaced traditional PVDF as a binder for cathode,which can achieve a uniform PAA-Li(LixPAA(0<x≤1))coating layer on the surface of single-crystal LiNi_(0.83)Co_(0.12)Mn_(0.05)O_(2)(SC-NCM83)due to H^(+)/Li^(+)exchange reaction during the initial charging-discharging process.The formation of PAA-Li coating layer on cathode can promote interfacial Li^(+)transport and enhance the stability of the cathodic interface.Furthermore,the partially-protonated surface of SC-NCM83 casued by H^(+)/Li^(+)exchange reaction can restrict Ni ions transport to enhance the crystal structure stability.The proposed SC-NCM83-PAA exhibits superior cycling performance with a retention of 92%compared with that(57.3%)of SC-NCM83-polyvinylidene difluoride(PVDF)after 200 cycles.This work provides a practical strategy to construct high-performance cathodes for ASSBs.

Sensitivity investigation of 100-MeV proton irradiation to SiGe HBT single event effect

The single event effect(SEE) sensitivity of silicon–germanium heterojunction bipolar transistor(Si Ge HBT) irradiated by 100-Me V proton is investigated. The simulation results indicate that the most sensitive position of the Si Ge HBT device is the emitter center, where the protons pass through the larger collector-substrate(CS) junction. Furthermore, in this work the experimental studies are also carried out by using 100-Me V proton. In order to consider the influence of temperature on SEE, both simulation and experiment are conducted at a temperature of 93 K. At a cryogenic temperature, the carrier mobility increases, which leads to higher transient current peaks, but the duration of the current decreases significantly.Notably, at the same proton flux, there is only one single event transient(SET) that occurs at 93 K. Thus, the radiation hard ability of the device increases at cryogenic temperatures. The simulation results are found to be qualitatively consistent with the experimental results of 100-Me V protons. To further evaluate the tolerance of the device, the influence of proton on Si Ge HBT after gamma-ray(^(60)Coγ) irradiation is investigated. As a result, as the cumulative dose increases, the introduction of traps results in a significant reduction in both the peak value and duration of the transient currents.

Static superconducting gantry‑based proton CT combined with X‑ray CT as prior image for FLASH proton therapy

Proton FLASH therapy with an ultra-high dose rate is in urgent need of more accurate treatment plan system(TPS)to promote the development of proton computed tomography(CT)without intrinsic error compared with the transformation from X-ray CT.This paper presents an imaging mode of proton CT based on static superconducting gantry different from the conventional rotational gantry.The beam energy for proton CT is fixed at 350 MeV,which is boosted by a compact proton linac from 230 MeV,and then delivered by the gantry to scan the patient’s body for proton imaging.This study demonstrates that the static superconducting gantry-based proton CT is effective in clinical applications.In particular,the imaging mode,which combines the relative stopping power(RSP)map from X-ray CT as prior knowledge,can produce much a higher accuracy RSP map for TPSs and positioning and achieve ultra-fast image for real-time image-guided radiotherapy.This paper presents the conceptual design of a boosting linac,static superconducting gantry and proton CT imaging equipment.The feasibility of energy enhancement is verified by simulation,and results from Geant4 simulations and reconstruction algorithms are presented,including the simulation verification of the advantage of the imaging mode.

A new imaging mode based on X-ray CT as prior image and sparsely sampled projections for rapid clinical proton CT

Proton computed tomography(CT)has a distinct practical significance in clinical applications.It eliminates 3–5%errors caused by the transformation of Hounsfield unit(HU)to relative stopping power(RSP)values when using X-ray CT for positioning and treatment planning systems(TPSs).Following the development of FLASH proton therapy,there are increased requirements for accurate and rapid positioning in TPSs.Thus,a new rapid proton CT imaging mode is proposed based on sparsely sampled projections.The proton beam was boosted to 350 MeV by a compact proton linear accelerator(LINAC).In this study,the comparisons of the proton scattering with the energy of 350 MeV and 230 MeV are conducted based on GEANT4 simulations.As the sparsely sampled information associated with beam acquisitions at 12 angles is not enough for reconstruction,X-ray CT is used as a prior image.The RSP map generated by converting the X-ray CT was constructed based on Monte Carlo simulations.Considering the estimation of the most likely path(MLP),the prior image-constrained compressed sensing(PICCS)algorithm is used to reconstruct images from two different phantoms using sparse proton projections of 350 MeV parallel proton beam.The results show that it is feasible to realize the proton image reconstruction with the rapid proton CT imaging proposed in this paper.It can produce RSP maps with much higher accuracy for TPSs and fast positioning to achieve ultra-fast imaging for real-time image-guided radiotherapy(IGRT)in clinical proton therapy applications.

Efficient proton conduction in porous and crystalline covalent-organic frameworks(COFs)

To attain the objectives of carbon peaking and carbon neutrality,the development of stable and highperformance ion-conducting materials holds enormous relevance in various energy storage and conversion devices.Particularly,crystalline porous materials possessing built-in ordered nanochannels exhibit remarkable superiority in comprehending the ion transfer mechanisms with precision.In this regard,covalent organic frameworks(COFs)are highly regarded as a promising alternative due to their preeminent structural tunability,accessible well-defined pores,and excellent thermal/chemical stability under hydrous/anhydrous conditions.By the availability of organic units and the diversity of topologies and connections,advances in COFs have been increasing rapidly over the last decade and they have emerged as a new field of proton-conducting materials.Therefore,a comprehensive summary and discussion are urgently needed to provide an"at a glance"understanding of the prospects and challenges in the development of proton-conducting COFs.In this review,we target a comprehensive review of COFs in the field of proton conductivity from the aspects of design strategies,the proton conducting mechanism/features,the relationships of structure-function,and the application of research.The relevant content of theoretical simulation,advanced structural characterizations,prospects,and challenges are also presented elaborately and critically.More importantly,we sincerely hope that this progress report will form a consistent view of this field and provide inspiration for future research.

Spatial and spectral measurement of laser-driven protons through radioactivation

The simultaneous measurement of the spatial profile and spectrum of laser-accelerated protons is important for further optimization of the beam qualities and applications.We report a detailed study regarding the underlying physics and regular procedure of such a measurement through the radioactivation of a stack composed of aluminum,copper,and CR-39 plates as well as radiochromic films(RCFs).After being radioactivated,the copper plates are placed on imaging plates(IPs)to detect the positrons emitted by the reaction products through contact imaging.The spectrum and energy-dependent spatial profile of the protons are then obtained from the IPs and confirmed by the measured ones from the RCFs and CR-39 plates.We also discuss the detection range,influence of electrons,radiation safety,and spatial resolution of this measurement.Finally,insights regarding the extension of the current method to online measurements and dynamic proton imaging are also provided.

Development and Challenges of Electrode Ionomers Used in the Catalyst Layer of Proton-Exchange Membrane Fuel Cells:A Review

The electrode ionomer plays a crucial role in the catalyst layer(CL) of a proton-exchange membrane fuel cell(PEMFC) and is closely associated with the proton conduction and gas transport properties,structural stability,and water management capability.In this review,we discuss the CL structural characteristics and highlight the latest advancements in ionomer material research.Additionally,we comprehensively introduce the design concepts and exceptional performances of porous electrode ionomers,elaborate on their structural properties and functions within the fuel cell CL,and investigate their effect on the CL microstructure and performance.Finally,we present a prospective evaluation of the developments in the electrode ionomer for fabricating CL,offering valuable insights for designing and synthesizing more efficient electrode ionomer materials.By addressing these facets,this review contributes to a comprehensive understanding of the role and potential of electrode ionomers for enhancing PEMFC performance.

Gel-state polybenzimidazole proton exchange membranes with flexible alkyl sulfonic acid side chains for a wider operating temperature range(25–240 ℃)

High-temperature proton exchange membrane fuel cells(HT-PEMFC) possess distinct technical advantages of high output power, simplified water/heat management, increased tolerance to fuel impurities and diverse fuel sources, within the temperature range of 120–200 ℃. However, for practical automobile applications, it was crucial to broaden their low-temperature operating window and enable cold start-up capability. Herein, gel-state phosphoric acid(PA) doped sulfonated polybenzimidazole(PBI) proton exchange membranes(PEMs) were designed and synthesized via PPA sol-gel process and in-situ sultone ring-opening reactions with various proton transport pathways based on absorbed PA, flexible alkyl chain connected sulfonic acid groups and imidazole sites. The effects of flexible alkyl sulfonic acid side chain length and content on PA doping level, proton conductivity, and membrane stability under different temperature and relative humidity(RH) were thoroughly investigated. The prepared gel-state membranes contained a self-assembled lamellar and porous structure that facilitated the absorption of a large amount of PA with rapid proton transporting mechanisms. At room temperature, the optimized membrane exhibited a proton conductivity of 0.069 S cm^(-1), which was further increased to 0.162 and 0.358 S cm^(-1)at 80 and 200 ℃, respectively, without additional humidification. The most significant contribution of this work was demonstrating the feasibility of gel-state sulfonated PBI membranes in expanding HT-PEMFC application opportunities over a wider operating range of 25 to 240 ℃.

Rational Design of Electrode–Electrolyte Interphase and Electrolytes for Rechargeable Proton Batteries

Rechargeable proton batteries have been regarded as a promising technology for next-generation energy storage devices,due to the smallest size,lightest weight,ultrafast diffusion kinetics and negligible cost of proton as charge carriers.Nevertheless,a proton battery possessing both high energy and power density is yet achieved.In addition,poor cycling stability is another major challenge making the lifespan of proton batteries unsatisfactory.These issues have motivated extensive research into electrode materials.Nonetheless,the design of electrode–electrolyte interphase and electrolytes is underdeveloped for solving the challenges.In this review,we summarize the development of interphase and electrolytes for proton batteries and elaborate on their importance in enhancing the energy density,power density and battery lifespan.The fundamental understanding of interphase is reviewed with respect to the desolvation process,interfacial reaction kinetics,solvent-electrode interactions,and analysis techniques.We categorize the currently used electrolytes according to their physicochemical properties and analyze their electrochemical potential window,solvent(e.g.,water)activities,ionic conductivity,thermal stability,and safety.Finally,we offer our views on the challenges and opportunities toward the future research for both interphase and electrolytes for achieving high-performance proton batteries for energy storage.

GPU-based cross-platform Monte Carlo proton dose calculation engine in the framework of Taichi

In recent years,graphics processing units(GPUs)have been applied to accelerate Monte Carlo(MC)simulations for proton dose calculation in radiotherapy.Nonetheless,current GPU platforms,such as Compute Unified Device Architecture(CUDA)and Open Computing Language(OpenCL),suffer from cross-platform limitation or relatively high programming barrier.However,the Taichi toolkit,which was developed to overcome these difficulties,has been successfully applied to high-performance numerical computations.Based on the class II condensed history simulation scheme with various proton-nucleus interactions,we developed a GPU-accelerated MC engine for proton transport using the Taichi toolkit.Dose distributions in homogeneous and heterogeneous geometries were calculated for 110,160,and 200 MeV protons and were compared with those obtained by full MC simulations using TOPAS.The gamma passing rates were greater than 0.99 and 0.95 with criteria of 2 mm,2%and 1 mm,1%,respectively,in all the benchmark tests.Moreover,the calculation speed was at least 5800 times faster than that of TOPAS,and the number of lines of code was approximately 10 times less than those of CUDA or OpenCL.Our study provides a highly accurate,efficient,and easy-to-use proton dose calculation engine for fast prototyping,beamlet calculation,and education purposes.

Promoting Proton Migration Kinetics by Ni^(2+)Regulating Enables Improved Aqueous Zn-MnO_(2) Batteries

The energy storage behaviors of MnO_(2) for aqueous Zn-MnO_(2) batteries mainly depend on the Zn^(2+)/H^(+)intercalation but are limited by poor ion/electron migration dynamics and stability.Herein,a strategy is proposed that promoting proton migration kinetics ameliorates H^(+)storage activity by introducing Ni^(2+)intoγ-MnO_(2)(Ni-MnO_(2)).Ni^(2+)can lower the diffusion barrier of H^(+)and selectively induce the ion intercalation,thereby alleviating the electrostatic interaction with the lattice.Moreover,Ni^(2+)enables the adjacent[MnO6]octahedrons to have better electron conductivity.The Ni-MnO_(2) exhibits superior rate performance(nearly four times specific capacity compared with MnO_(2))and ultra-long-cycle stability(100%of capacity retention after 11000 cycles at 3.0 A g^(-1)).The calculation indicates that the Ni-MnO_(2) allows H^(+)migrate rapidly along the one-dimensional tunnel due to reduction of the activation energy caused by Ni^(2+)regulating,thus achieving excellent reaction kinetics.This work brings great potential for the development of high-performance aqueous Zn-MnO_(2) batteries.

Pore-Scale Investigation of Coupled Two-Phase and Reactive Transport in the Cathode Electrode of Proton Exchange Membrane Fuel Cells

A three-dimensional multicomponent multiphase lattice Boltzmann model(LBM)is established to model the coupled two-phase and reactive transport phenomena in the cathode electrode of proton exchange membrane fuel cells.The gas diff usion layer(GDL)and microporous layer(MPL)are stochastically reconstructed with the inside dynamic distribution of oxygen and liquid water resolved,and the catalyst layer is simplifi ed as a superthin layer to address the electrochemical reaction,which provides a clear description of the fl ooding eff ect on mass transport and performance.Diff erent kinds of electrodes are reconstructed to determine the optimum porosity and structure design of the GDL and MPL by comparing the transport resistance and per-formance under the fl ooding condition.The simulation results show that gradient porosity GDL helps to increase the reactive area and average concentration under fl ooding.The presence of the MPL ensures the oxygen transport space and reaction area because liquid water cannot transport through micropores.Moreover,the MPL helps in the uniform distribution of oxygen for an effi cient in-plane transport capacity.Crack and perforation structures can accelerate the water transport in the assembly.The systematic perforation design yields the best performance under fl ooding by separating the transport of liquid water and oxygen.

Design of 50 MeV proton microbeam based on cyclotron accelerator

High-energy proton microbeam facilities are powerful tools in space science,biology and cancer therapy studies.The primary limitations of the 50 MeV proton microbeam system are the poor beam quality provided by the cyclotron and the problem of intense scattering in the slit position.Here,we present an optical design for a cyclotron-based 50 MeV high-energy proton microbeam system with a micron-sized resolution.The microbeam system,which has an Oxford triplet lens configuration,has relatively small spherical aberrations and is insensitive to changes in the beam divergence angle and momentum spread.In addition,the energy filtration included in the system can reduce the beam momentum spread from 1 to 0.02%.The effects of lens parasitic aberrations and the lens fringe field on the beam spot resolution are also discussed.In addition,owing to the severe scattering of 50 MeV protons in slit materials,a slit system model based on the Geant4 toolkit enables the quantitative analysis of scattered protons and secondary particles.For the slit system settings under a 10-micron final beam spot,very few scattered protons can enter the quadrupole lens system and affect the focusing performance of the microbeam system,but the secondary radiation of neutrons and gamma rays generated at the collimation system should be considered for the 50 MeV proton microbeam.These data demonstrate that a 50 MeV proton microbeam system with a micron-sized beam spot based on a cyclotron is feasible.

SAPT:a synchrotron-based proton therapy facility in Shanghai

Because of its excellent dose distribution,proton therapy is becoming increasingly popular in the medical application of cancer treatment.A synchrotron-based proton therapy facility was designed and constructed in Shanghai.The synchrotron,beam delivery system,and other technical systems were commissioned and reached their expected performances.After a clinical trial of 47 patients was finished,the proton therapy facility obtained a registration certificate from the National Medical Products Administration.The characteristics of the accelerator and treatment systems are described in this article.

A theoretical study of fragmentation dynamics of water dimer by proton impact

To investigate the collision processes of proton with the water dimer(H_(2)O)_(2)at 50 e V,the time-dependent density functional theory coupled with molecular dynamics nonadiabatically is applied.Six specific collision orientations with various impact parameters are considered.The reaction channels,the mass distribution and the fragmentation mass spectrum are explored.Among all launched samples,the probability of the channel of non-charge transfer scattering and charge transfer scattering is about 80%,hinting that the probability of fragmentation is about 20%.The reaction channel of proton exchange process 2 is taken as an example to exhibit the detailed microscopic dynamics of the collision process by inspecting the positions,the respective distance,the number of loss of electrons and the evolution of the electron density.The study of the mass distribution and the fragmentation mass spectrum shows that among all possible fragments,the fragment with mass 36 has the highest relative abundance of 65%.The relative abundances of fragments with masses 1,35,and 34are 20%,13%,and 1.5%,respectively.For the total electron capture cross section,the present calculations agree with the available measurements and calculations over the energy range from 50 e V to 12 ke V.

Metal-oxoacid-mediated oxyhydroxide with proton acceptor to break adsorption energy scaling relation for efficient oxygen evolution

Metal oxyhydroxides(MOOH)generated from irreversible reconstructions of transition metal compounds are intrinsic active species for oxygen evolution reaction,whose activities are still constrained by sluggish deprotonation kinetics and inherent adsorption energy scaling relations.Herein,we construct a tunable proton acceptor(TPA)on oxyhydroxides by in-situ reconstruction of metal oxoacids such as NiC2O4to accelerate deprotonation and break adsorption energy scaling relations during OER.The modified C_(2)O_(4)^(2-)as a TPA can easily extract H of*OH(forming*HC2O4intermediate)and then promote deprotonation by the transmitted hydrogen bond with*OOH along conjugated(H...)O=C-O(-H)chain.As a result,Ni OOH-C2O4shows non-concerted proton-electron transfer and improved deprotonation rate,and delivers a good OER activity(270 mV@10 mA cm-2).The conjugate acidity coefficient(pKa)of the modified oxoacid group can be a descriptor for TPA selection.This TPA strategy can be universally applied to Co-,Fe-,and Ni-based oxyhydroxides to facilitate OER efficiency.