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.

Transmission Spectral Characteristics of Photonic Crystals Milled in Annealed Proton-Exchange LiNbO_3 Waveguide

Transmission spectra of triangular lattice photonic crystals milled in the top surface of an annealed proton- exchange waveguide are numerically simulated. The effects of the finite depth, conical shape, trapezoidal shape and hybrid shape of holes are theoretically analyzed. Due to the difficulty of milling high aspect-ratio cylindrical holes in lithium niobate （LiNbO3 ）, a compromised solution is proposed to improve the overlap between shallow holes and the waveguide mode, and useful transmission spectra with strong contrast and sharp band edges are achieved.

Machine learning and Bayesian optimization for performance prediction of proton-exchange membrane fuel cells

Proton-exchange membrane fuel cells (PEMFCs) are critical components of zero-emission electro-hydrogen generators. Accurate performance prediction is vital to the optimal operation management and preventive maintenance of these generators. Polarization curve remains one of the most important features representing the performance of PEMFCs in terms of efficiency and durability. However, predicting the polarization curve is not trivial as PEMFCs involve complex electrochemical reactions that feature multiple nonlinear relationships between the operating variables as inputs and the voltage as outputs. Herein, we present an artificial-intelligence-based approach for predicting the PEMFCs’ performance. In that way, we propose first an explainable solution for selecting the relevant features based on kernel principal component analysis and mutual information. Then, we develop a machine learning approach based on XGBRegressor and Bayesian optimization to explore the complex features and predict the PEMFCs’ performance. The performance and the robustness of the proposed machine learning based prediction approach is tested and validated through a real industrial dataset including 10 PEMFCs. Furthermore, several comparison studies with XGBRegressor and the two popular machine learning-based methods in predicting PEMFC performance, such as artificial neural network (ANN) and support vector machine regressor (SVR) are also conducted. The obtained results show that the proposed approach is more robust and outperforms the two conventional methods and the XGBRegressor for all the considered PEMFCs. Indeed, according to the coefficient of determination criterion, the proposed model gains an improvement of 6.35%, 6.8%, and 4.8% compared with ANN, SVR, and XGBRegressor respectively.

The Characterisitic of Proton-Exchanged LiNbO_3 Waveguide Formed by Different Proton Source

Benzoic acid as a source of proton is widely used in the technology of manufacture of proton exchanged ( PE) waveguide .But the diffusing speed of proton is too fast to make the waveguide stable in the pure benzoic acid. The characteristic of waveguide is improved with mixture of benzoic acid and lithium benzoate .

Ultrafine ordered L1_(2)-Pt-Co-Mn ternary intermetallic nanoparticles as high-performance oxygen-reduction electrocatalysts for practical fuel cells

The long-range periodically ordered atomic structures in intermetallic nanoparticles(INPs)can significantly enhance both the electrocatalytic activity and electrochemical stability toward the oxygen reduction reaction(ORR)compared to the disordered atomic structures in ordinary solid-solution alloy NPs.Accordingly,through a facile and scalable synthetic method,a series of carbon-supported ultrafine Pt_3Co_(x)Mn_(1-x)ternary INPs are prepared in this work,which possess the"skin-like"ultrathin Pt shells,the ordered L1_(2) atomic structure,and the high-even dispersion on supports(L1_(2)-Pt_3Co_(x)Mn_(1-x)/~SPt INPs/C).Electrochemical results present that the composition-optimized L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C exhibits the highest electrocata lytic activity among the series,which are also much better than those of the pristine ultrafine Pt/C.Besides,it also has a greatly enhanced electrochemical stability.In addition,the effects of annealing temperature and time are further investigated.More importantly,such superior ORR electrocatalytic performance of L1_(2)-Pt_3Co_(0.7)Mn_(0.3)/~SPt INPs/C are also well demonstrated in practical fuel cells.Physicochemical characterization analyses further reveal the major origins of the greatly enhanced ORR electrocata lytic performance:the Pt-Co-Mn alloy-induced geometric and ligand effects as well as the extremely high L1_(2) atomic-ordering degree.This work not only successfully develops a highly active and stable ordered ternary intermetallic ORR electrocatalyst,but also elucidates the corresponding"structure-function"relationship,which can be further applied in designing other intermetallic(electro)catalysts.

CO_(2) electrolysis to formic acid for carbon neutralization

To avoid carbonate precipitation for CO_(2) electrolysis,developing CO_(2) conversion in an acid electrolyte is viewed as an ultimately challenging technology.In Nature,Xia et al.recently explored a proton-exchange membrane system for reducing CO_(2) to formic acid with a Pb±Pb SO_(4) composite catalyst derived from waste lead-acid batteries based on the lattice carbon activation mechanism.Up to 93%Faradaic efficiency was realized when formic acid was produced by this technology.

Progress on the mechanisms of Ru-based electrocatalysts for the oxygen evolution reaction in acidic media

Water electrolysis using proton-exchange membranes is one of the most promising technologies for carbon-neutral and sustainable energy production.Generally,the overall efficiency of water splitting is limited by the oxygen evolution reaction(OER).Nevertheless,a trade-off between activity and stability exists for most electrocatalytic materials in strong acids and oxidizing media,and the development of efficient and stable catalytic materials has been an important focus of research.In this view,gaining in-depth insights into the OER system,particularly the interactions between reaction intermediates and active sites,is significantly important.To this end,this review introduces the fundamentals of the OER over Ru-based materials,including the conventional adsorbate evolution mechanism,lattice oxygen oxidation mechanism,and oxide path mechanism.Moreover,the up-to-date progress of representative modifications for improving OER performance is further discussed with reference to specific mechanisms,such as tuning of geometric,electronic structures,incorporation of proton acceptors,and optimization of metal-oxygen covalency.Finally,some valuable insights into the challenges and opportunities for OER electrocatalysts are provided with the aim to promote the development of next-generation catalysts with high activity and excellent stability.

Co_3O_4 nanoparticles assembled on polypyrrole/graphene oxide for electrochemical reduction of oxygen in alkaline media

The development of highly efficient catalysts for cathodes remains an important objective of fuel cell research. Here, we report Co3O4 nanoparticles assembled on a polypyrrole/graphene oxide electrocatalyst （Co3O4/Ppy/GO） as an efficient catalyst for the oxygen reduction reaction （ORR） in alkaline media. The catalyst was prepared via the hydrothermal reaction of Co2＋ ions with Ppy-modified GO. The GO, Ppy/GO, and Co3O4/Ppy/GO were characterized using scanning electron microscopy, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The incorporation of Ppy into GO nanosheets resulted in the formation of a nitrogen-modified GO po-rous structure, which acted as an efficient electron-transport network for the ORR. With further anchoring of Co3O4 on Ppy/GO, the as-prepared Co3O4/Ppy/GO exhibited excellent ORR activity and followed a four-electron route mechanism for the ORR in alkaline solution. An onset potential of -0.10 V vs. a saturated calomel electrode and a diffusion limiting current density of 2.30 mA/cm^2 were achieved for the Co3O4/Ppy/GO catalyst heated at 800 ℃; these values are comparable to those for noble-metal-based Pt/C catalysts. Our work demonstrates that Co3O4/Ppy/GO is highly active for the ORR. Notably, the Ppy coupling effects between Co3O4 and GO provide a new route for the preparation of efficient non-precious electrocatalysts with hierarchical porous structures for fuel cell applications.

Novel Au nanoparticles-inlaid titanium paper for PEM water electrolysis with enhanced interfacial electrical conductivity

Proton-exchange membrane water electrolysis(PEM WE)is a particularly promising technology for renewable hydrogen produc-tion.However,the excessive passivation of the gas diffusion layer(GDL)will seriously affect the high surface-contact resistance and result in energy losses.Thus,a mechanism for improving the conductivity and interface stability of the GDL is an urgent issue.In this work,we have prepared a hydrophilic and corrosion resistant conductive composite protective coating.The polydopamine(PDA)film on the Ti surface,which was obtained via the solution oxidation method,ensured that neither micropores nor pinholes existed in the final hybrid coatings.In-situ reduced gold nanoparticles(AuNPs)improved the conductivity to achieve the desired interfacial contact resistance and further enhanced the corrosion resistance.The surface composition of the treated samples was investigated using scanning electron microscopy(SEM),transmis-sion electron microscopy(TEM),X-ray diffraction(XRD),and Fourier transform infrared spectroscopy(FTIR).The results indicated that the optimized reaction conditions included a pH value of 3 of HAuCl_(4) solution with PDA deposition(48 h)on papers and revealed the lowest con-tact resistance(0.5 mΩ·cm^(2))and corrosion resistance(0.001μA·cm^(−2))in a 0.5 M H_(2)SO_(4)+2 ppm F−solution(1.7 V vs.RHE)among all the modified specimens,where RHE represents reversible hydrogen electrode.These findings indicated that the Au-PDA coating is very appropriate for the modification of Ti GDLs in PEM WE systems.

SYNTHESIS AND PROPERTIES OF SULFONATED POLY(ARYLENE ETHER) CONTAINING TRIPHENYL METHANE MOIETIES FROM ISOCYNATE MASKED BISPHENOL

A novel sulfonated poly（arylene ether） containing triphenylmethane moieties was synthesized by the sulfonation of a designed parent polymer using chlorosulfonic acid as sulfonation agent. The sulfonation took place at the para position of the pendant phenyl rings because of the specially designed parent polymer. The position and degree of sulfonation were characterized by ^1H-NMR and elemental analysis. The sulfonated polymers are highly soluble in common organic solvents, such as dimethylsulfoxide, N,N＇-dimethylacetamide, dimethylformamide, ethylene glycol monomethyl ether, and can be readily cast into tough and smooth films from solutions. The films showed good thermal and hydrolysis stabilities. Moreover, Fenton＇s reagent test revealed that the films exhibited superior stability to oxidation. The proton conductivities of the films were comparable with Nation 117 under same conditions. The membrane electrode assembly （MEA） prepared with the asmade film （706 EW, 100 μm dry thickness） shows better cell performance than Nation 115-MEA in the whole current density range.

In situ protonation in a locally flexible porous coordination polymer for enhancing proton-carrier loading and proton conductivity

Designing efficient proton-conductive materials is crucial in fuel cells.Yet,it remains a substantial challenge because of the issues in proton mobility,proton-carrier amount,and orientation of proton host materials.Herein,we report an in-situ protonation strategy to produce a locally flexible porous coordination polymer(PCP)to enhance the proton-carrier loading and proton conductivity.The local dipole flipping of the ligand allows effective proton exchange with low activation energy,promoting interpore proton transport through the pore apertures and pore walls.The protonation induces substantial charges to the frameworks and enhances the interaction with proton carriers,thereby increasing the loading of the proton carriers.By this design strategy,the resulting PCP exhibits enhanced phosphoric acid loading and extraordinary proton conductivities under both aqueous and anhydrous conditions compared to its isoreticular analog that features rigidity without proton-exchange capability.Our work provides a new avenue for designing proton-conductive materials that combine structural dynamics with performance merits.

Integrating single Ni site and PtNi alloy on two-dimensional porous carbon nanosheet for efficient catalysis in fuel cell

The performance of catalyst depends on the intrinsic activity of active sites and the structural characteristics of the support.Here,we simultaneously integrate single nickel(Ni)sites and platinum-nickel(PtNi)alloy nanoparticles(NPs)on a two-dimensional(2D)porous carbon nanosheet,demonstrating remarkable catalytic performance in the oxygen reduction reaction(ORR).The single Ni sites can activate the oxygen molecules into key oxygen-containing intermediate that is further efficiently transferred to the adjacent PtNi alloy NPs and rapidly reduced to H_(2)O,which establishes a relay catalysis between active sites.The porous structure on the carbon nanosheet support promotes the transfer of active intermediates between these active sites,which assists the relay catalysis by improving mass diffusion.Remarkably,the obtained catalyst demonstrates a half-wave potential of up to 0.942 V,a high mass activity of 0.54 A·mgPt^(−1),and negligible decay of activity after 30,000 cycles,which are all superior to the commercial Pt/C catalysts with comparable loading of Pt.The theoretical calculation results reveal that the obtained catalyst with defect structure of carbon support presents enhanced relay catalytic effect of PtNi alloy NPs and single Ni sites,ultimately realizing improved catalytic performance.This work provides valuable inspiration for developing low platinum loading catalyst,integrating single atoms and alloy with outstanding performance in fuel cell.

Modeling and Simulation of Hydrogen Energy Storage System for Power-to-gas and Gas-to-power Systems

By collecting and organizing historical data and typical model characteristics,hydrogen energy storage system(HESS)-based power-to-gas(P2G)and gas-to-power systems are developed using Simulink.The energy transfer mechanisms and numerical modeling methods of the proposed systems are studied in detail.The proposed integrated HESS model covers the following system components:alkaline electrolyzer(AE),highpressure hydrogen storage tank with compressor(CM&H_(2) tank),and proton-exchange membrane fuel cell(PEMFC)stack.The unit models in the HESS are established based on typical U-I curves and equivalent circuit models,which are used to analyze the operating characteristics and charging/discharging behaviors of a typical AE,an ideal CM&H_(2) tank,and a PEMFC stack.The validities of these models are simulated and verified in the MicroGrid system,which is equipped with a wind power generation system,a photovoltaic power generation system,and an auxiliary battery energy storage system(BESS)unit.Simulation results in MATLAB/Simulink show that electrolyzer stack,fuel cell stack and system integration model can operate in different cases.By testing the simulation results of the HESS under different working conditions,the hydrogen production flow,stack voltage,state of charge(SOC)of the BESS,state of hydrogen pressure(SOHP)of the HESS,and HESS energy flow paths are analyzed.The simulation results are consistent with expectations,showing that the integrated HESS model can effectively absorb wind and photovoltaic power.As the wind and photovoltaic power generations increase,the HESS current increases,thereby increasing the amount of hydrogen production to absorb the surplus power.The results show that the HESS responds faster than the traditional BESS in the microgrid,providing a solid theoretical foundation for later wind-photovoltaic-HESS-BESS integration.

Hydrogen-assisted scalable preparation of ultrathin Pt shells onto surfactant-free and uniform Pd nanoparticles for highly efficient oxygen reduction reaction in practical fuel cells

Concentrating active Pt atoms in the outer layers of electrocatalysts is a very effective approach to greatly reduce the Pt loading without compromising the electrocatalytic performance and the total electrochemically active surface area(ECSA)for the oxygen reduction reaction(ORR)in hydrogen-based proton-exchange membrane fuel cells.Accordingly,a facile,low-cost,and hydrogen-assisted two-step method is developed in this work,to massively prepare carbon-supported uniform,small-sized,and surfactant-free Pd nanoparticles(NPs)with ultrathin~3-atomic-layer Pt shells(Pd@Pt_(3L) NPs/C).Comprehensive physicochemical characterizations,electrochemical analyses,fuel cell tests,and density functional theory calculations reveal that,benefiting from the ultrathin Pt-shell nanostructure as well as the resulting ligand and geometric effects,Pd@Pt_(3L) NPs/C exhibits not only significantly enhanced ECSA,electrocatalytic activity,and noble-metal(NM)utilization compared to commercial Pt/C,showing 81.24 m^(2)/gPt,0.710 mA/cm^(2),and 352/577 mA/mgNM/Pt in ECSA,area-,and NM-/Pt-mass-specific activity,respectively;but also a much better electrochemical stability during the 10,000-cycle accelerated degradation test.More importantly,the corresponding 25-cm^(2) H2-air/O_(2) fuel cell with the low cathodic Pt loading of~0.152 mgPt/cm^(2)geo achieves the high power density of 0.962/1.261 W/cm^(2)geo at the current density of only 1,600 mA/cm^(2)geo,which is much higher than that for the commercial Pt/C.This work not only develops a high-performance and practical Pt-based ORR electrocatalyst,but also provides a scalable preparation method for fabricating the ultrathin Pt-shell nanostructure,which can be further expanded to other metal shells for other energy-conversion applications.

Synthesis and Characterization of Novel Sulfonated Polyimides from 4,6-Bis（4-aminophenoxy）-naphthalene-2-sulfonic Acid

A novel sulfonated diamine monomer, 4,6-bis（4-arninophenoxy）-naphthalene-2-sulfonic acid（BAPNS）, was synthesized. A series of sulfonated polyimide copolymers was prepared from BAPNS, 1,4,5,8-naphthalenetetracarboxylic dianhydride（NTDA） and nonsulfonated diamine 4,4＇-diaminodiphenyl ether（ODA）. Flexible, transparent, and mechanically strong membranes were obtained. The novel sulfonated polyimide（SPI） membranes show higher conductivity, for example, SPI-100 shows a conductivity of 0.0698 S/cm at 80℃（SPI-X： Xrefers to molar fraction of BAPNS）. The membranes exhibit the permeability of methanol from 2.18×10^-7 cm2/s to 2.57×10^-7 cm2/s, which is much lower than that of Nafion（2.00×10 6 cm^2/s）. The copolymers were thermally stable up to 330℃. The sulfonated polyimide copolymers also show reasonable mechanical strength; for example, the maximum tensile strength at break of the sulfonated polyimide copolymer with 100%（molar fraction） BAPNS is 1.35 GPa under high moisture condi- tions. The optimum concentration of BAPNS was found to be 100%（molar fraction） from the view point of proton conductivity, methanol permeability, and membrane stability.