固体氧化物燃料电池Ruddlesden-Popper型氧化物阳极的研究进展

Ruddlesden-Popper(RP)型钙钛矿氧化物具有独特的理化性质,被认为是一种极具潜力的固体氧化物燃料电池(SOFCs)阳极材料,但是多数现有RP型钙钛矿存在不耐还原、催化氧化活性或稳定性不足等问题。在简要介绍RP型氧化物的基础上,总结出其结构可调和性质特异的内在机理,基于材料微观结构的维度、离子取代位点、制备工艺特性等系统地介绍了近年其作为SOFCs阳极的研究进展,并对制备RP型材料使用的相转变法及提升催化活性的原位析出进行了梳理与探讨,重点分析了RP型钙钛矿氧化物用于SOFCs阳极的设计理念和目前仍然存在的问题。最后指出利用异价离子取代、理论实践结合、充分利用氧非计量比是开发耐还原且具有高催化活性和稳定性的新型RP阳极的重要策略。

Rational Design of Ruddlesden-Popper Perovskite Ferrites as Air Electrode for Highly Active and Durable Reversible Protonic Ceramic Cells

Reversible protonic ceramic cells(RePCCs)hold promise for efficient energy storage,but their practicality is hindered by a lack of high-performance air electrode materials.Ruddlesden-Popper perovskite Sr_(3)Fe_(2)O_(7−δ)(SF)exhibits superior proton uptake and rapid ionic conduction,boosting activity.However,excessive proton uptake during RePCC operation degrades SF’s crystal structure,impacting durability.This study introduces a novel A/B-sites co-substitution strategy for modifying air electrodes,incorporating Sr-deficiency and Nb-substitution to create Sr_(2.8)Fe_(1.8)Nb_(0.2)O_(7−δ)(D-SFN).Nb stabilizes SF’s crystal,curbing excessive phase formation,and Sr-deficiency boosts oxygen vacancy concentration,optimizing oxygen transport.The D-SFN electrode demonstrates outstanding activity and durability,achieving a peak power density of 596 mW cm^(−2)in fuel cell mode and a current density of−1.19 A cm^(−2)in electrolysis mode at 1.3 V,650℃,with excellent cycling durability.This approach holds the potential for advancing robust and efficient air electrodes in RePCCs for renewable energy storage.

Boosting MA-based two-dimensional Ruddlesden-Popper perovskite solar cells by incorporating a binary spacer

Two-dimensional Ruddlesden-Popper(2DRP)perovskite exhibits excellent stability in perovskite solar cells(PSCs)due to introducing hydrophobic long-chain organic spacers.However,the poor charge transporting property of bulky organic cation spacers limits the performance of 2DRP PSCs.Inspired by the Asite cation alloying strategy in 3D perovskites,2DRP perovskites with a binary spacer can promote charge transporting compared to the unary spacer counterparts.Herein,the superior MA-based 2DRP perovskite films with a binary spacer,including 3-guanidinopropanoic acid(GPA)and 4-fluorophenethylamine(FPEA)are realized.These films(GPA_(0.85)FPEA_(0.15))_(2)MA_(4)Pb_5I_(16)show good morphology,large grain size,decreased trap state density,and preferential orientation of the as-prepared film.Accordingly,the present 2DRP-based PSC with the binary spacer achieves a remarkable efficiency of 18.37%with a V_(OC)of1.15 V,a J_(SC)of 20.13 mA cm^(-2),and an FF of 79.23%.To our knowledge,the PCE value should be the highest for binary spacer MA-based 2DRP(n≤5)PSCs to date.Importantly,owing to the hydrophobic fluorine group of FPEA and the enhanced interlayer interaction by FPEA,the unencapsulated 2DRP PSCs based on binary spacers exhibit much excellent humidity stability and thermal stability than the unary spacer counterparts.

Tuning synergy between nickel and iron in Ruddlesden-Popper perovskites through controllable crystal dimensionalities towards enhanced oxygenevolving activity and stability

Ni-Fe-based oxides are among the most promising catalysts developed to date for the bottleneck oxygen evolution reaction(OER)in water electrolysis.However,understanding and mastering the synergy of Ni and Fe remain challenging.Herein,we report that the synergy between Ni and Fe can be tailored by crystal dimensionality of Ni,Fe-contained Ruddlesden-Popper(RP)-type perovskites(La_(0.125)Sr_(0.875))n+1(Ni_(0.25)Fe_(0.75))nO3n+1(n=1,2,3),where the material with n=3 shows the best OER performance in alkaline media.Soft X-ray absorption spectroscopy spectra before and after OER reveal that the material with n=3 shows enhanced Ni/Fe-O covalency to boost the electron transfer as compared to those with n=1 and n=2.Further experimental investigations demonstrate that the Fe ion is the active site and the Ni ion is the stable site in this system,where such unique synergy reaches the optimum at n=3.Besides,as n increases,the proportion of unstable rock-salt layers accordingly decreases and the leaching of ions(especially Sr^(2+))into the electrolyte is suppressed,which induces a decrease in the leaching of active Fe ions,ultimately leading to enhanced stability.This work provides a new avenue for rational catalyst design through the dimensional strategy.

Photodetector based on Ruddlesden-Popper perovskite microwires with broader band detection

Recently,the two-dimensional(2D)form of Ruddlesden-Popper perovskite(RPP)has been widely studied.However,the synthesis of one-dimensional(1D)RPP is rarely reported.Here,we fabricated a photodetector based on RPP microwires(RPP-MWs)and compared it with a 2D-RPP photodetector.The results show that the RPP-MWs photodetector possesses a wider photoresponse range and higher responsivities of 233 A/W in the visible band and 30 A/W in the near-infrared(NIR)band.The analyses show that the synthesized RPP-MWs have a multi-layer,heterogeneous core-shell structure.This structure gives RPP-MWs a unique band structure,as well as abundant trap states and defect levels,which enable them to acquire better photoresponse performance.This configuration of RPP-MWs provides a new idea for the design and application of novel heterostructures.

高压固相反应法合成具有理想Ruddlesden-Popper结构的Ca_4Mn_3O_(10)层状化合物

采用高压下的固相反应方法 ,成功地合成了具有空间群I4 mmm的理想三层结构化合物Ca4Mn3 O10 。用电子显微学方法对此结构进行了研究 ,并提出了近似的结构模型。基于提出的模型 ,进行了电子衍射图和高分辨像的模拟 ,并与实验结果进行了比较。

Ruddlesden-Popper结构杂化非本征铁电体及其多铁性

杂化非本征铁电性是指在具有钙钛矿结构单元的金属氧化物中由氧八面体面内旋转和面外倾侧耦合诱导出的二阶铁电序,其有望在室温强磁电耦合多铁性材料中获得重要应用,并将极大地拓展铁电体物理学的内涵和外延.本文在阐述杂化非本征铁电性物理起源及其内禀电控磁性的基础上,总结了有关Ruddlesden-Popper结构杂化非本征铁电体及多铁性的主要研究进展与面临的挑战,并展望了发展方向.

n=2 Ruddlesden-Popper Sr_(3)B_(2)Se_(7)(B=Zr,Hf)非常规铁电性的第一性原理研究

近年来,层状钙钛矿材料中存在的非常规铁电性为新型铁电体设计提供了新的途径.基于第一性原理,本文系统研究了具有Ruddlesden-Popper (RP)(n=2)结构的Sr_(3)B_(2)Se_(7) (B=Zr, Hf)化合物的基态结构、电子结构和非常规铁电性.研究表明, Sr_(3)B_(2)Se_(7) (B=Zr, Hf)基态均为具有A2_(1)am极性相的直接带隙半导体;其非常规铁电性来源于BSe_6八面体的两种旋转模式的耦合.而且,因具有较强的铁电极化值与可见光吸收带隙, Sr_(3)B_(2)Se_(7) (B=Zr, Hf)有望成为新一代铁电光伏材料.

紫外可见漫反射光谱和Tauc plot方法分析无机Ruddlesden-Popper钙钛矿带隙

半导体在当今社会中扮演着举足轻重的作用,在大学物理实验教学中,让学生能够深入理解半导体的带隙性质和测量方法有着重要的意义。紫外可见漫反射光谱方法是一种简便易行的确定半导体的带隙以及能带结构的方法。本文使用紫外-可见漫反射光谱以及Tauc Plot方法确定Ruddlesden-Popper半导体钙钛矿Sr_(n+1)Ti_(n)O_(3n+1)(n=1,2,3,∞)的带隙,并讨论了Tauc plot公式在透射和反射情形下的应用。

二维Ruddlesden-Popper相钙钛矿太阳能电池研究进展

目前,影响钙钛矿太阳能电池发展的主要因素是弱稳定性和低光电转换效率。Ruddlesden-Popper(RP)相二维(2D)钙钛矿材料具有结晶度高、吸收光谱宽和稳定性良好等特性,已经成为光伏领域研究的热点。RP相2D钙钛矿中有机分子层间通过范德瓦尔斯力可以形成稳定的2D结构,进而克服稳定性问题。截至目前,研究者已经获得了超过18%的光电转换效率。文中对RP相钙钛矿的结构特点进行阐述,对RP相钙钛矿薄膜的典型制备方法进行归纳,总结了不同A′位有机阳离子在提高RP相钙钛矿太阳能电池的效率和稳定性方面的应用现状,最后对RP相钙钛矿在PSCs中未来可探究方面进行展望。本研究能够为深入理解和提升PSCs性能提供理论支持和实验依据。

Controlled crystal orientation of two-dimensional Ruddlesden-Popper halide perovskite films for solar cells

Metal halide perovskite solar cells have attracted considerable attention because of their high-power conversion efficiency and costeffective solution-processable fabrication;however,they exhibit poor structural stability.Two-dimensional(2D)Ruddlesden-Popper(RP)perovskites could address the aforementioned issue and present excellent stability because of their hydrophobic organic spacer cations.However,the crystallographic orientation of 2D crystals should be perpendicular to the bottom substrates for charges to transport fast and be collected in solar cells.Moreover,controlling the crystallographic orientation of the 2D RP perovskites prepared by the solution process is difficult.Herein,we reviewed the progress of recent research regarding 2D RP perovskite films with the focus on the crystallographic orientation mechanism and orientation controlling methods.Furthermore,the current issues and prospects of 2D RP perovskites in the photovoltaic field were discussed to elucidate their development and application in the future.

Mixed B-site ruddlesden-popper phase Sr_(2)(Ru_(x)Ir_(1-x))O_(4) enables enhanced activity for oxygen evolution reaction

Development of high performance electrocatalysts for oxygen evolution reaction (OER) in acidic media remains a challenge for direct water splitting using an electrolyzer.Recently,Ruddlesden-Popper phase Sr_(2)IrO_(4)was discovered to be an efficient OER catalyst because of its unique structure,which consists of layers of both rock salt and perovskite phases simultaneously.In this study,we prepared a series of B-site mixed,Ruddlesden-Popper phase of Sr_(2)(Ru_(x)Ir_(1-x))O_(4) and examined their electrocatalytic properties for OER in acidic media.Through partial substitution of Ru in the B-site of Ruddlesden-Popper phase materials,we achieved much enhanced OER performance for this series of Sr_(2)(Ru_(x)Ir_(1-x))O_(4)electrocatalysts,among which Sr_(2)(Ru_(0.5)Ir_(0.5))O_(4)exhibited the best catalytic activity with a current density of 8.06 m A/cm^(2) at 1.55 V and a Tafel slope of 47 m V/dec.This current density is three times higher than that of Sr_(2)Ir O_(4).The B-site mixed Sr_(2)(Ru_(0.5)Ir_(0.5))O_(4)retained good stability in acidic conditions for>24 h at 10 m A/cm^(2).A range of techniques were used to characterize the crystal and electronic structures of the Sr_(2)(Ru_(x)Ir_(1-x))O_(4)samples.Our data indicate that the improved OER performance can be correlated to the formation of high level of hydroxyl groups and the enhanced overlap between Ir/Ru 4d and O_(2)p orbitals,revealing a new way for the design of efficient OER electrocatalysts by regulating their composition and electronic structures.

Phenylformamidinium-enabled quasi-2D Ruddlesden-Popper perovskite solar cells with improved stability

Two-dimensional(2D)/quasi-2D perovskite solar cells(PSCs)incorporating organic spacer cations exhibit appealing ambient stability in comparison with their 3D analogs.Most reported organic spacer cations are based on ammonium,whereas formamidinium(FA^(+))has been seldom applied despite that FA has been extensively used in high-efficiency 3D PSCs.Herein,a novel FA-based organic spacer cation,4-chloro-phenylformamidinium(CPFA^(+)),is applied in quasi-2D Ruddlesden-Popper(RP)PSCs for the first time,and methylammonium chloride(MACl)is employed to promote crystal growth and orientation of perovskite film,resulting in high power conversion efficiency(PCE)with improved stability.Upon incorporating CPFA+organic spacer cation and MACl additive,high-quality quasi-2D CPFA_(2)MA_(n-1)Pb_(n)(I_(0.857)Cl_(0.143))_(3n+1)(n=9)perovskite film forms,exhibiting improved crystal orientation,reduced trap state density,prolonged carrier lifetime and optimized energy level alignment.Consequently,the CPFA_(2)MA_(n-1)Pb_(n)(I_(0.857)Cl_(0.143))_(3n+1)(n=9)quasi-2D RP PSC devices deliver a highest PCE of 14.78%.Moreover,the un-encapsulated CPFA-based quasi-2D RP PSC devices maintain~80%of its original PCE after exceeding 2000 h storage under ambient condition,whereas the 3D MAPb I3counterparts retain only~45%of its original PCE.Thus,the ambient stability of quasi-2D RP PSC devices is improved obviously relative to its 3D MAPb I3counterpart.

Hybrid improper ferroelectricity and phase transition behavior of Li_(2)Nd_(2)Ti_(3)O_(10)ceramics with A-site ordered triple-layer Ruddlesden-Popper structure

Hybrid improper ferroelectricity has been extensively reported through theoretical prediction and experimental investigation in the oxides with Ruddlesden-Popper(R-P)structures.However,the experimentally reported ferroelectric materials based on triple-layer R-P structures are rare,and the weak ferroelectricity impedes its practical application.In the present work,the single-phase Li_(2)Nd_(2)Ti_(3)O_(10)ceramics with A-site cation ordered triple-layer R-P structure was obtained by spark plasma sintering technique,and the crystal structure of P2_(1)ab symmetry was revealed by neutron powder diffraction and transmission electron microscope analysis.Furthermore,the switchable ferroelectricity in Li_(2)Nd_(2)Ti_(3)O_(10)ceramics has been observed at room temperature,and the saturated polarization-electric field hysteresis loop was obtained with P_(r)=0.4μC/cm^(2)under the electric field of 250 kV/cm.The phase transition behavior of Li_(2)Nd_(2)Ti_(3)O_(10)oxides was revealed by the temperature-dependence Raman and dielectric spectra combined with the piezoelectric property.

New two-layer Ruddlesden-Popper cathode materials for protonic ceramics fuel cells

New two-layer Ruddlesden-Popper(RP)oxide La_(0.25)Sr_(2.75)FeNiO_(7-δ)(LSFN)in the combination of Sr_(3)Fe_(2)O_(7-δ) and La_(3)Ni_(2)O_(7-δ) was successfully synthesized and studied as the potential active single-phase and composite cathode for protonic ceramics fuel cells(PCFCs).LSFN with the tetragonal symmetrical structure(IMmmm)is confinned,and the co-existence of Fe^(3+)/Fe^(4+) and Ni^(3+)/Ni^(2+) couples is demonstrated by X-ray photoelectron spectrometer(XPS)analysis.The LSFN conductivity is apparently enhanced after Ni doping in Fe-site,and nearly three times those of Sr_(3)Fe_(2)O_(7-δ),which is directly related to the carrier concentration and conductor mechanism.Importantly,anode supported PCFCs using LSFN-BaZr_(0.1)Ce_(0.7)Y_(0.2)O_(3-δ)(LSFN-BZCY)composite cathode achieved high power density(426 mW·cm^(-2) at 650℃)and low electrode interface polarization resistance(0.26Ω·cm^(2)).Besides,distribution of relaxation time(DRT)function technology was further used to analyse the electrode polarization processes.The observed three peaks(Pl,P2,and P3)separated by DRT shifted to the high frequency region with the decreasing temperature,suggesting that the charge transfer at the electrode-electrolyte interfaces becomes more difficult at reduced temperatures.Preliminary results demonstrate that new two-layer RP phase LSFN can be a promising cathode candidate for PCFCs.

Ruddlesden-Popper phase A2BO4 oxides:Recent studies on structure,electrical,dielectric,and optical properties

In the last two decades,structure and properties of Ruddlesden–Popper phase(RP)A2BO4 oxides with K2NiF4 structure,have been widely investigated.But to the best of our knowledge,no review article is available in the literature on recent studies on these oxides.Therefore,in this article,recent studies on structure,electrical,dielectric,and optical properties of these oxides have been reviewed.Special attention is put on to highlight the effect of doping and oxygen stoichiometry on the structure and properties of these oxides.Further,important applications of these oxides have also been mentioned in this article.

Robust Ruddlesden-Popper phase Sr_(3)Fe_(1.3)Mo_(0.5)Ni_(0.2)O_(7-δ)decorated with in-situ exsolved Ni nanoparticles as an efficient anode for hydrocarbon fueled solid oxide fuel cells

A highly efficient Ruddlesden-Popper structure anode material with a formula of Sr_(3)Fe_(1.3)Mo_(0.5)Ni_(0.2)O_(7-δ)(RP-SFMN)has been developed for hydrocarbon fueled solid oxide fuel cells(HF-SOFC)application.It is demonstrated that a nanostructured RP-SFMN anode decorated with in-situ exsolved Ni nanoparticles(Ni@RP-SFMN)has been successfully prepared by annealing the anode in reducing atmosphere similar to the operating conditions.The phase compositions,valence states,morphologies,and electrocatalytic activities of RP-SFMN material have been characterized in detail.In addition,the in-situ exsolution mechanism of the metallic Ni phase from the parent oxide is clearly explained by using density function theory calculation.The peak output power density at 800℃ is significantly enhanced from 0.163 to 0.409 W/cm^(2)while the electrode polarization resistance is effectively lowered from 0.96 to 0.30Ωcm^(2)by the substitution of B-site Fe by Ni,which is attributed to the improved electrocatalytic activities induced by the in-situ exsolved Ni nanocatalysts.Moreover,the single cell with RP-SFMN anode exhibits good stability in 3%H_(2)O humidified H_(2)and syngas for 110 and 60 h at 800℃,respectively.Our findings indicate that RP-SFMN is a greatly promising anode candidate of HF-SOFCs due to its good electrochemical performance and stability during the operation.

Efficient and stable Ruddlesden-Popper layered tin-based perovskite solar cells enabled by ionic liquid-bulky spacers

The crucial component,bulky spacers,in two-dimensional Ruddlesden-Popper(2 DRP)layered tin(Sn)perovskites are highly limited by halide ammonium salts,leading to the insufficient control of complex crystallization process due to the limited interaction between bulky spacers and 2 DRP perovskite frameworks.Here,we report an ionic liquid-bulky spacer,butylammounium acetate(BAAc O),for constructing efficient and stable 2 DRP Sn-based perovskite solar cells(PSCs).In contrast to the traditional halide ammonium bulky spacer,butylammounium iodide(BAI),the Ac O^(-)-functional group in BAAc O has a strong interaction with formamidine ions(FA^(+))and Sn2+.The inter-component interaction allows the formation of controllable intermediates for the favorable growth of smooth,dense,and highly oriented perovskite films.A PSC with power conversion efficiency of 10.36%(7.16%for BAI)is achieved,which is the highest report,along with improved stability with~90%retained after~600 h storage in N_(2) atmosphere without any encapsulation.

Room-temperature ferroelectricity in A-site ordered Ruddlesden-Popper Li_(2)CaTa_(2)O_(7) ceramics

In the present work,the crystal structure,ferroelectric and dielectric properties of the dense single-phase Li_(2)CaTa_(2)O_(7) ceramics with A-site ordered double-layer Ruddlesden-Popper structures have been investigated by the experiments and first-principles calculations.A polar Pna21 phase was determined by the Rietveld refinement against the X-ray diffraction pattern at room temperature,and it was confirmed by its lowest calculated energy and rigid phonon modes.The ferroelectricity was found by observing the ferroelectric hysteresis loop at room temperature,and its remanent polarization was similar to the value calculated from the Berry phase and Born effective charge approaches.The ferroelectricity is a nonconventional proper one since its polarization is induced from the displacement of oxygen anions instead of tantalum cations based on the individual atomic polarization.A first-order transition from an antiferroelectric to paraelectric phase around 900 K was found by the DSC and variable-temperature dielectric measurements.From the present work,the room-temperature ferroelectricity is experimental confirmed in the present ceramics,inspiring the search for new ferroelectricity in the ceramics with A-site ordered Ruddlesden-Popper structures.

溴掺杂对2D-RP钙钛矿薄膜及电池器件性能的影响

近年来,二维Ruddlesden-Popper型钙钛矿(2D-RP)因其独特的光电性质以及良好的环境稳定性而受到研究者的青睐。其组分调控灵活度高,可以通过元素或有机基团的替换、掺杂对材料的光电特性进行优化,进而带来器件性能的提升。研究中,我们将溴元素引入基于环己甲胺(CMA)的2D-RP钙钛矿晶体,形成溴碘混合体系。实验表明,该体系薄膜具有优良的光学特性,适量的溴掺杂可以改善薄膜的结晶度、降低薄膜内部缺陷态密度、增强载流子传输。最终,基于溴掺杂的器件光电转化效率(PCE)达到了14.01%,其开路电压(V_(oc))达到1.18 V,短路电流密度(J_(sc))达到17.04 mA/cm^(2),填充因子(FF)达到69.62%。