Precursor Decomposition,Microstructure, and Porosity of Yttria Stabilized Zirconia Thin Films Prepared by Aerosol‐Assisted Chemical Vapor Deposition

Microstructures of yttria stabilized zirconia thin films deposited by aerosol assisted chemical vapor deposition (AA‐CVD) are correlated with the thermal decomposition behavior of the corresponding metal precursors, zirconium and yttrium 2,4‐pentanedionate. Process conditions of AA‐CVD are investigated with the aim of producing dense and compact YSZ thin films for applications as gas‐tight electrolyte. Based on systematic cross sectional scanning transmission electron microscopy (STEM) investigations and conductivity measurements, the development of percolating nanoporosity is observed in samples prepared at temperatures between 350 °C and 600 °C at standard solution throughput. Compact columnar thin films with bulk conductivity are obtained at 600 °C by reducing the metal content of the precursor solution and at 450 °C by reducing the solution throughput.     

Low‐Temperature Micro‐Solid Oxide Fuel Cells with Partially Amorphous La0.6Sr0.4CoO3‐δ Cathodes

Partially amorphous La_0.6Sr_0.4CoO_3‐δ (LSC) thin‐film cathodes are fabricated using pulsed laser deposition and are integrated in free‐standing micro‐solid oxide fuel cells (micro‐SOFC) with a 3YSZ electrolyte and a Pt anode. A low degree of crystallinity of the LSC layers is achieved by taking advantage of the miniaturization of the cells, which permits low‐temperature operation (300–450 °C). Thermomechanically stable micro‐SOFC are obtained with strongly buckled electrolyte membranes. The nanoporous columnar microstructure of the LSC layers provides a large surface area for oxygen incorporation and is also believed to reduce the amount of stress at the cathode/electrolyte interface. With a high rate of failure‐free micro‐SOFC membranes, it is possible to avoid gas cross‐over and open‐circuit voltages of 1.06 V are attained. First power densities as high as 200–262 mW cm^?2 at 400–450 °C are achieved. The area‐specific resistance of the oxygen reduction reaction is lower than 0.3 Ω cm² at 400 °C around the peak power density. These outstanding findings demonstrate that partially amorphous oxides are promising electrode candidates for the next‐generation of solid oxide fuel cells working at low‐temperatures.     

Low‐Cost Hollow Mesoporous Polymer Spheres and All‐Solid‐State Lithium,Sodium Batteries

A practical, low‐cost synthesis of hollow mesoporous organic polymer (HMOP) spheres is reported. The electrochemical properties of Li⁺/Na⁺‐electrolyte membranes with these spheres substituting for oxide filler particles in poly(ethylene oxide) (PEO)‐filler composite are explored. The electrolyte membranes are mechanically robust, thermally stable to over 250 °C, and block dendrites from a metallic‐lithium/sodium anode. The Li⁺/Na⁺ transfer impedance across the lithium/sodium–electrolyte interface is initially acceptable at 65 °C and scavenging of impurities by the porous‐spheres filler lowers this impedance relative to that with Al₂O₃. All‐solid‐state Li/LiFePO₄ and Na/NaTi₂(PO4)₃ cells give stable discharge capacity of ≈130 and 80 mAh g^?1, respectively, at 0.5 C and 65 °C for 100 cycles.     

Low‐Operating Temperature,High‐Rate and Durable Solid‐State Sodium‐Ion Battery Based on Polymer Electrolyte and Prussian Blue Cathode

A solid‐state polymer electrolyte (PFSA‐Na membrane) for solid‐state sodium‐ion batteries (SSIBs) to overcome severe safety issues caused by traditional liquid electrolytes is explored. The PFSA‐Na membranes, synthesized by an environmentally and economically friendly method, display high ionic conductivity, excellent thermal stability, and outstanding mechanical flexibility in a wide temperature range. SSIBs based on the PFSA‐Na membranes and Prussian blue cathode exhibit a superior rate performance of 87.5 mA h g^?1 at 8 C and a durable cycling life of up to 1100 cycles at 1 C with only a slight capacity decay of ≈0.014% per cycle. Furthermore, due to the intrinsic advantages of the PFSA‐Na membranes, the cyclic performance of the proposed SSIBs is more stable than that of its liquid counterpart even at the rather low temperature of ?35 °C.     

Multiblock Copolymers with Highly Sulfonated Blocks Containing Di‐ and Tetrasulfonated Arylene Sulfone Segments for Proton Exchange Membrane Fuel Cell Applications

Multiblock copoly(arylene ether sulfone)s with different block lengths and ionic contents are tailored for durable and proton‐conducting electrolyte membranes. Two series of fully aromatic copolymers are prepared by coupling reactions between non‐sulfonated hydrophobic precursor blocks and highly sulfonated hydrophilic precursor blocks containing either fully disulfonated diarylsulfone or fully tetrasulfonated tetraaryldisulfone segments. The sulfonic acid groups are exclusively introduced in ortho positions to the sulfone bridges to impede desulfonation reactions and give the blocks ion exchange capacities (IECs) of 4.1 and 4.6 meq. g^?1, respectively. Solvent cast block copolymer membranes show well‐connected hydrophilic nanophase domains for proton transport and high decomposition temperatures above 310 °C under air. Despite higher IEC values, membranes containing tetrasulfonated tetraaryldisulfone segments display a markedly lower water uptake than the corresponding ones with disulfonated diarylsulfone segments when immersed in water at 100 °C, presumably because of the much higher chain stiffness and glass transition temperature of the former segments. The former membranes have proton conductivities in level of a perfluorosulfonic acid membrane (NRE212) under fully humidified conditions. A membrane with an IEC of 1.83 meq. g^?1 reaches above 6 mS cm^?1 under 30% relative humidity at 80 °C, to be compared with 10 mS cm^?1 for NRE212 under the same conditions.     

3D Printing Quasi‐Solid‐State Asymmetric Micro‐Supercapacitors with Ultrahigh Areal Energy Density

A 3D printing approach is first developed to fabricate quasi‐solid‐state asymmetric micro‐supercapacitors to simultaneously realize the efficient patterning and ultrahigh areal energy density. Typically, cathode, anode, and electrolyte inks with high viscosities and shear‐thinning rheological behaviors are first prepared and 3D printed individually on the substrates. The 3D printed asymmetric micro‐supercapacitor with interdigitated electrodes exhibits excellent structural integrity, a large areal mass loading of 3.1 mg cm^?2, and a wide electrochemical potential window of 1.6 V. Consequently, this 3D printed asymmetric micro‐supercapacitor displays an ultrahigh areal capacitance of 207.9 mF cm^?2. More importantly, an areal energy density of 73.9 µWh cm^?2 is obtained, superior to most reported interdigitated micro‐supercapacitors. It is believed that the efficient 3D printing strategy can be used to construct various asymmetric micro‐supercapacitors to promote the integration in on‐chip energy storage systems.     

Stable Seamless Interfaces and Rapid Ionic Conductivity of Ca–CeO2/LiTFSI/PEO Composite Electrolyte for High‐Rate and High‐Voltage All‐Solid‐State Battery

Stable and seamless interfaces among solid components in all‐solid‐state batteries (ASSBs) are crucial for high ionic conductivity and high rate performance. This can be achieved by the combination of functional inorganic material and flexible polymer solid electrolyte. In this work, a flexible all‐solid‐state composite electrolyte is synthesized based on oxygen‐vacancy‐rich Ca‐doped CeO₂ (Ca–CeO₂) nanotube, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI), and poly(ethylene oxide) (PEO), namely Ca–CeO₂/LiTFSI/PEO. Ca–CeO₂ nanotubes play a key role in enhancing the ionic conductivity and mechanical strength while the PEO offers flexibility and assures the stable seamless contact between the solid electrolyte and the electrodes in ASSBs. The as‐prepared electrolyte exhibits high ionic conductivity of 1.3 × 10^?4 S cm^?1 at 60 °C, a high lithium ion transference number of 0.453, and high‐voltage stability. More importantly, various electrochemical characterizations and density functional theory (DFT) calculations reveal that Ca–CeO₂ helps dissociate LiTFSI, produce free Li ions, and therefore enhance ionic conductivity. The ASSBs based on the as‐prepared Ca–CeO₂/LiTFSI/PEO composite electrolyte deliver high‐rate capability and high‐voltage stability.     

Ultrathin YSZ Coating on Pt Cathode for High Thermal Stability and Enhanced Oxygen Reduction Reaction Activity

A simple, yet effective approach of stabilizing the nanostructure of porous metal‐based electrodes and thus, extending the life of microsolid oxide fuel cells is demonstrated. In an effort to avoid thermal agglomeration of metal electrodes, an ultrathin yttria‐stabilized zirconia (YSZ) is coated on the porous metal (Pt) cathode by the atomic layer deposition, a scalable, and potentially high‐throughput deposition technique. A very thin YSZ coating is found to maintain the morphology of its underlying nanoporous Pt during high temperature operations (500 °C). More interestingly, the YSZ coating is also found to improve oxygen reduction reaction activity by ≈2.5 times. This improvement is attributed to an enhanced triple phase area, especially in the vicinity of the Pt–electrolyte interface; cross‐sectional electron microscopy images indicate that the initially uniform ultrathin YSZ layer becomes a partially agglomerated coating, a favorable structure for a maximized reaction area and fluent oxygen access to the Pt–electrolyte interface.     

Physically Stable Polymer‐Membrane Electrolytes for Highly Efficient Solid‐State Dye‐Sensitized Solar Cells with Long‐Term Stability

A 3D polymer‐network‐membrane (3D‐PNM) electrolyte is described for highly stable, solid‐state dye‐sensitized solar cells (DSCs) with excellent power‐conversion efficiency (PCE). The 3D‐PNM electrolyte is prepared by using one‐pot in situ cross‐linking polymerization on the surface of dye‐sensitized TiO₂ particles in the presence of redox species. This method allows the direct connection of the 3D‐PNM to the surface of the TiO₂ particles as well as the in situ preparation of the electrolyte gel during device assembly. There are two junction areas (liquid and solid‐state junctions) in the DSCs that employ conventional polymer electrolytes, and the major interface is at the liquid‐state junction. The solid‐state junction is dominant in the DSCs that employ the 3D‐PNM electrolyte, which exhibit almost constant performance during aging at 65 °C for over 700 h (17.0 to 17.2 mA cm^–2). The best cell performance gives a PCE of 9.1%; this is slightly better than the performance of a DSC that employs a liquid electrolyte.     

High‐Performance Silver Cathode Surface Treated with Scandia‐Stabilized Zirconia Nanoparticles for Intermediate Temperature Solid Oxide Fuel Cells

This work introduces a novel silver composite cathode with a surface coating of scandia‐stabilized zirconia (ScSZ) nanoparticles for application in intermediate temperature solid oxide fuel cells (IT‐SOFCs). The ScSZ coating is expected to maximize the triple boundary area of the Ag electrode, ScSZ electrolyte, and oxygen gas, where the oxygen reduction reaction occurs. The coating also protects the porous Ag against thermal agglomeration during fuel cell operation. The ScSZ nanoparticles are prepared by sputtering scandium‐zirconium alloy followed by thermal oxidation on Ag mesh. The performance of the solid oxide fuel cells with a gadolinia‐doped ceria electrolyte support is evaluated. At temperatures <500 °C, our optimized Ag‐ScSZ cathode outperforms the bare Ag cathode and even the platinum cathode, which has been believed to be the best material for this purpose. The highest cell peak power with the Ag‐ScSZ cathode is close to 60 mW cm^?2 at 450 °C, while bare Ag and optimized Pt cathodes produce 38.3 and 49.4 mW cm^?2, respectively. Long‐term current measurement also confirms that the Ag‐ScSZ cathode is thermally stable, with less degradation than bare Ag or Pt.     

Rational Design of Hierarchical “Ceramic‐in‐Polymer” and “Polymer‐in‐Ceramic” Electrolytes for Dendrite‐Free Solid‐State Batteries

Solid polymer electrolytes as one of the promising solid‐state electrolytes have received extensive attention due to their excellent flexibility. However, the issues of lithium (Li) dendrite growth still hinder their practical applications in solid‐state batteries (SSBs). Herein, composite electrolytes from “ceramic‐in‐polymer” (CIP) to “polymer‐in‐ceramic” (PIC) with different sizes of garnet particles are investigated for their effectiveness in dendrite suppression. While the CIP electrolyte with 20 vol% 200 nm Li_6.4La₃Zr_1.4Ta_0.6O₁₂ (LLZTO) particles (CIP‐200 nm) exhibits the highest ionic conductivity of 1.6 × 10^?4 S cm^?1 at 30 °C and excellent flexibility, the PIC electrolyte with 80 vol% 5 µm LLZTO (PIC‐5 µm) shows the highest tensile strength of 12.7 MPa. A sandwich‐type composite electrolyte (SCE) with hierarchical garnet particles (a PIC‐5 µm interlayer sandwiched between two CIP‐200 nm thin layers) is constructed to simultaneously achieve dendrite suppression and excellent interfacial contact with Li metal. The SCE enables highly stable Li plating/stripping cycling for over 400 h at 0.2 mA cm^?2 at 30 °C. The LiFePO₄/SCE/Li cells also demonstrate excellent cycle performance at room temperature. Fabricating sandwich‐type composite electrolytes with hierarchical filler designs can be an effective strategy to achieve dendrite‐free SSBs with high performance and high safety at room temperature.     

Click‐Functionalized Ru(II) Complexes for Dye‐Sensitized Solar Cells

Three heteroleptic ruthenium complexes incorporating new ancillary ligands synthesized by sequential connection of different alkyl functionalities with triazole as a linker are prepared using click chemistry. These sensitizers exhibit low‐energy metal‐to‐ligand charge transfer bands centered at 540 nm with molar extinction coefficients of up to 1.54 × 10⁴ L mol^?1 cm^?1. The devices using these sensitizers in conjunction with a volatile electrolyte show high photovoltaic conversion efficiencies of 8.7 to 9.9% under standard AM 1.5G sunlight (100 mW cm^?2) conditions. Using an ionic liquid electrolyte, the cells show not only a good power‐conversion efficiency of up to 7.1%, but also promising long‐term stability under full sunlight intensity at 60 °C. The difference in the photovoltaic parameters during the ageing process is investigated by employing transient photoelectrical measurements.     

Advanced Electrolytes for Fast‐Charging High‐Voltage Lithium‐Ion Batteries in Wide‐Temperature Range

LiNi_xMn_yCo_1?x?yO₂ (NMC) cathode materials with Ni ≥ 0.8 have attracted great interest for high energy‐density lithium‐ion batteries (LIBs) but their practical applications under high charge voltages (e.g., 4.4 V and above) still face significant challenges due to severe capacity fading by the unstable cathode/electrolyte interface. Here, an advanced electrolyte is developed that has a high oxidation potential over 4.9 V and enables NMC811‐based LIBs to achieve excellent cycling stability in 2.5–4.4 V at room temperature and 60 °C, good rate capabilities under fast charging and discharging up to 3C rate (1C = 2.8 mA cm^?2), and superior low‐temperature discharge performance down to ?30 °C with a capacity retention of 85.6% at C/5 rate. It is also demonstrated that the electrode/electrolyte interfaces, not the electrolyte conductivity and viscosity, govern the LIB performance. This work sheds light on a very promising strategy to develop new electrolytes for fast‐charging high‐energy LIBs in a wide‐temperature range.     

A Lithium Amide‐Borohydride Solid‐State Electrolyte with Lithium‐Ion Conductivities Comparable to Liquid Electrolytes

High ionic conductivity of up to 6.4 × 10^?3 S cm^?1 near room temperature (40 °C) in lithium amide‐borohydrides is reported, comparable to values of liquid organic electrolytes commonly employed in lithium‐ion batteries. Density functional theory is applied coupled with X‐ray diffraction, calorimetry, and nuclear magnetic resonance experiments to shed light on the conduction mechanism. A Li₄Ti₅O₁₂ half‐cell battery incorporating the lithium amide‐borohydride electrolyte exhibits good rate performance up to 3.5 mA cm^?2 (5 C) and stable cycling over 400 cycles at 1 C at 40 °C, indicating high bulk and interfacial stability. The results demonstrate the potential of lithium amide‐borohydrides as solid‐state electrolytes for high‐power lithium‐ion batteries.     

Ultrathin,Flexible Polymer Electrolyte for Cost‐Effective Fabrication of All‐Solid‐State Lithium Metal Batteries

All‐solid‐state batteries are promising candidates for the next‐generation safer batteries. However, a number of obstacles have limited the practical application of all‐solid‐state Li batteries (ASSLBs), such as moderate ionic conductivity at room temperature. Here, unlike most of the previous approaches, superior performances of ASSLBs are achieved by greatly reducing the thickness of the solid‐state electrolyte (SSE), where ionic conductivity is no longer a limiting factor. The ultrathin SSE (7.5 µm) is developed by integrating the low‐cost polyethylene separator with polyethylene oxide (PEO)/Li‐salt (PPL). The ultrathin PPL shortens Li⁺ diffusion time and distance within the electrolyte, and provides sufficient Li⁺ conductance for batteries to operate at room temperature. The robust yet flexible polyethylene offers mechanical support for the soft PEO/Li‐salt, effectively preventing short‐circuits even under mechanical deformation. Various ASSLBs with PPL electrolyte show superior electrochemical performance. An initial capacity of 135 mAh g^?1 at room temperature and the high‐rate capacity up to 10 C at 60 °C can be achieved in LiFePO₄/PPL/Li batteries. The high‐energy‐density sulfur cathode and MoS₂ anode employing PPL electrolyte also realize remarkable performance. Moreover, the ASSLB can be assembled by a facile process, which can be easily scaled up to mass production.     

Ionic Liquid–Sulfolane Composite Electrolytes for High‐Performance and Stable Dye‐Sensitized Solar Cells

Ionic liquid electrolytes are prepared using sulfolane as a plasticizer for eutectic melts to realize highly stable and efficiently performing dye‐sensitized solar cells (DSCs) in hot climate conditions. Variations in the viscosity of the formulations with sulfolane content are measured and performance in DSCs is investigated using the ruthenium dye C106 as a sensitizer. A power conversion efficiency (PCE) of 8.2% is achieved under standard reporting conditions. Apart from lowering the viscosity, the addition of sulfolane induces a negative shift of the TiO₂ conduction band edge. Strikingly the device performance increases to 8.4% at 50 °C due to higher short circuit photocurrent and fill factor, over‐compensating the loss in open circuit voltage with increasing temperature. The PCE increases also upon decreasing the light intensity of the solar simulator, reaching up to 9% at 50 mW cm^?2. Devices based on these new electrolyte formulations show excellent stability during light soaking for 2320 h under full sunlight at 60 °C and also during a 1065 h long heat stress at 80 °C in the dark. A detailed investigation provides important information about the factors affecting the principal photovoltaic parameters during the aging process and the first results from a series of outdoor measurements are reported.     

Cyclic Aminosilane‐Based Additive Ensuring Stable Electrode–Electrolyte Interfaces in Li‐Ion Batteries

Ni‐rich cathodes are considered feasible candidates for high‐energy‐density Li‐ion batteries (LIBs). However, the structural degradation of Ni‐rich cathodes on the micro‐ and nanoscale leads to severe capacity fading, thereby impeding their practical use in LIBs. Here, it is reported that 3‐(trimethylsilyl)‐2‐oxazolidinone (TMS‐ON) as a multifunctional additive promotes the dissociation of LiPF₆, prevents the hydrolysis of ion‐paired LiPF₆ (which produces undesired acidic compounds including HF), and scavenges HF in the electrolyte. Further, the presence of 0.5 wt% TMS‐ON helps maintain a stable solid–electrolyte interphase (SEI) at Ni‐rich LiNi_0.7Co_0.15Mn_0.15O₂ (NCM) cathodes, thus mitigating the irreversible phase transformation from layered to rock‐salt structures and enabling the long‐term stability of the SEI at the graphite anode with low interfacial resistance. Notably, NCM/graphite full cells with TMS‐ON, which exhibit an excellent discharge capacity retention of 80.4%, deliver a discharge capacity of 154.7 mAh g^?1 after 400 cycles at 45 °C.     

A Room‐Temperature Molten Hydrate Electrolyte for Rechargeable Zinc–Air Batteries

Aqueous Zn‐based batteries are attracting extensive interest because of their economic feasibility and potentially high energy density. However, poor rechargeability of Zn anode in conventional electrolytes resulting from dendrite formation and self‐corrosion hinders their practical implementation. Herein, a Zn molten hydrate composed of inorganic Zn salt and water is demonstrated as an advantageous electrolyte for solving these issues. In this electrolyte, dendrite‐free Zn deposition/dissolution reaction with a high Coulombic efficiency (≈99%) as well as long‐term stability, free from CO₂ poisoning are realized. The resultant Zn–air cell exhibits a reversible capacity of 1000 mAh g_(catalyst)^?1 over 100 cycles at 30 °C. Combined with the intrinsic safety associated with aqueous chemistry and cost benefit of the raw material, the present Zn–air battery makes a strong candidate for large‐scale energy storage.     

A Flexible Dual‐Ion Battery Based on PVDF‐HFP‐Modified Gel Polymer Electrolyte with Excellent Cycling Performance and Superior Rate Capability

Dual‐ion batteries (DIBs) have attracted increasing attention owing to their merits of high working voltage, low cost, and especially environmental friendliness. However, the cycling stability of most DIBs is still unsatisfying due to the decomposition of conventional liquid carbonate electrolytes under high working voltages. Exploration of gel polymer electrolytes (GPEs) with good electrochemical stability at high voltage is a possible strategy to optimize their cycling stability. A high‐performance flexible DIB based on a poly(vinylidene fluoride‐hexafluoro propylene) GPE codoped with poly(ethylene oxide) and graphene oxide via weak bond interactions is herein reported for the first time. The prepared polymer electrolyte shows a 3D porous network with significantly improved ionic conductivity up to 2.1 × 10^?3 S cm^?1, which is favorable for fast ionic transportation of both cations and anions. As a result, this DIB exhibits excellent cycling stability with a capacity retention of 92% after 2000 cycles at a high current rate of 5C (1C is corresponding to 100 mA g^?1), which is among the best performances of DIBs. Moreover, good flexibility and thermal stability (up to 90 °C) are also achieved for this battery, indicating its potential applications for high‐performance flexible energy storage devices.     

Atmospheric‐Pressure Chemical Vapor Deposition of Iron Pyrite Thin Films

Iron pyrite (cubic FeS₂) is a promising candidate absorber material for earth‐abundant thin‐film solar cells. In this report, single‐phase, large‐grain, and uniform polycrystalline pyrite thin films are fabricated on glass and molybdenum‐coated glass substrates by atmospheric‐pressure chemical vapor deposition (AP‐CVD) using the reaction of iron(III) acetylacetonate and tert‐butyl disulfide in argon at 300 °C, followed by sulfur annealing at 500–550 °C to convert marcasite impurities to pyrite. The pyrite‐marcasite phase composition depends strongly on the concentration of sodium in the growth substrate and the sulfur partial pressure during annealing. Phase and elemental composition of the films are characterized by X‐ray diffraction, Raman spectroscopy, Auger electron spectroscopy, secondary ion mass spectrometry, Rutherford backscattering spectrometry, and X‐ray photoelectron spectroscopy. The in‐plane electrical properties are surprisingly insensitive to phase and elemental impurities, with all films showing p‐type, thermally activated transport with a small activation energy (≈30 meV), a room‐ temperature resistivity of ≈1 Ω cm, and low mobility. These ubiquitous electrical properties may result from robust surface effects. These CVD pyrite thin films are well suited to fundamental electrical studies and the fabrication of pyrite photovoltaic device stacks.