Effects of operating conditions on the performance degradation and anode microstructure evolution of anode-supported solid oxide fuel cells

Performance degradation shortens the life of solid oxide fuel cells in practical applications.Revealing the degradation mechanism is crucial for the continuous improvement of cell durability.In this work,the effects of cell operating conditions on the terminal voltage and anode microstructure of a Ni-yttria-stabilized zirconia anode-supported single cell were investigated.The microstructure of the anode active area near the electrolyte was characterized by laser optical microscopy and focused ion beam-scanning electron microscopy.Ni depletion at the anode/electrolyte interface region was observed after 100 h discharge tests.In addition,the long-term stability of the single cell was evaluated at 700℃for 3000 h.After an initial decline,the anode-supported single cell exhibits good durability with a voltage decay rate of 0.72%/kh and an electrode polarization resistance decay rate of 0.17%/kh.The main performance loss of the cell originates from the initial degradation.

Realizing high-performance Na_(3)V_(2)(PO_(4))_(2)O_(2)F cathode for sodium-ion batteries via Nb-doping

Na_(3)V_(2)(PO_(4))_(2)O_(2)F(NVPOF)has received considerable interest as a promising cathode material for sodium-ion batteries because of its high working voltage and good structural/thermal stability.However,the sluggish electrode reaction resulting from its low intrinsic electronic conductivity significantly restricts its electrochemical performance and thus its practical application.Herein,Nb-doped Na_(3)V_(2-x)Nb_(x)(PO_(4))_(2)O_(2)F/graphene(rGO)composites(x=0,0.05,0.1)were prepared using a solvothermal method followed by calcination.Compared to the un-doped NVPOF/r GO,doping V-site with high-valence Nb element(Nb^(5+))(Na_(3)V_(1.95)Nb_(0.05)(PO_(4))_(2)O_(2)F/r GO(NVN05POF/rGO))can result in the generated V4^(+)/V3^(+)mixed-valence,ensuring the lower bandgap and thus the increased intrinsic electronic conductivity.Besides,the expanded lattice space favors the Na^(+)migration.With the structure feature where NVN05POF particles are attached to the rGO sheets,the electrode reaction kinetics is further accelerated owing to the well-constructed electron conductive network.As a consequence,the as-prepared NVN05POF/r GO sample exhibits a high specific capacity of~72 m Ah·g^(-1)at 10C(capacity retention of 65.2%(vs.0.5C))and excellent long-term cycling stability with the capacity fading rate of~0.099%per cycle in 500 cycles at 5C.

Editorial for special issue on renewable energy conversion,utilization and storage

1.Foreword In light of the rapid depletion of fossil energy resources and the escalating environmental pollution crisis,there has been a significant surge in research focused on the development of technologies and materials for renewable energy conversion,utilization,and storage.This research area has gained paramount importance in addressing the pressing challenges of our time.

Sb-Cu alloy cathode with a novel lithiation mechanism of ternary intermetallic formation: Enabling high energy density and superior rate capability of liquid metal battery

Antimony(Sb) is an attractive cathode for liquid metal batteries(LMBs) because of its high theoretical voltage and low cost.The main obstacles associated with the Sb-based cathodes are unsatisfactory energy density and poor rate-capability.Herein,we propose a novel Sb_(64)Cu_(36)cathode that effectively tackles these issues.The Sb_(64)Cu_(36)(melting point:525℃) cathode presents a novel lithiation mechanism involving sequentially the generation of Li_(2)CuSb,the formation of Li_(3)Sb,and the conversion reaction of Li_(2)CuSb to Li_(3)Sb and Cu.The generated intermetallic compounds show a unique microstructure of the upper floated Li_(2)CuSb layer and the below cross-linked structure with interpenetrated Li_(2)CuSb and Li_(3)Sb phases.Compared with Li_(3)Sb,the lower Li migration energy barrier(0.188 eV) of Li_(2)CuSb significantly facilitates the lithium diffusion across the intermediate compounds and accelerates the reaction kinetics.Consequently,the Li‖Sb_(64)Cu_(36)cell delivers a more excellent electrochemical performance(energy density:353 W h kg^(-1)at 0.4 A cm^(-2);rate capability:0.59 V at 2.0 A cm^(-2)),and a much lower energy storage cost of only 38.45 $ kW h^(-1)than other previously reported Sb-based LMBs.This work provides a novel cathode design concept for the development of high-performance LMBs in applications for large-scale energy storage.

A review on the critical challenges and progress of SiO_(x)-based anodes for lithium-ion batteries

With the advantages of abundant resources,high specific capacity,and relatively stable cycling performance,silicon suboxides(SiO_(x) ,x<2)have been recently suggested as promising anodes for next-generation lithium-ion batteries(LIBs).SiO_(x) exhibits superior storage capability because of the presence of silicon and smaller volume change upon charge/discharge than Si owing to the buffering effect of the initial lithiation products of inert lithium oxide and lithium silicates,enabling a stable cycle life of electrodes.However,significant improvements such as overcoming issues related to volume changes in cycling and initial irreversible capacity loss and enhancing the ionic and electronic charge transport in poorly conducting SiO_(x) electrodes,are still needed to achieve the satisfactory performance required for commercial applications.This review summarizes recent progress on the cycling performance and initial coulombic efficiency of SiO_(x) .Advances in the design of particle morphology and composite composition,prelithiation and prereduction methods,and usage of electrolyte additives and optimized electrode binders are discussed.Perspectives on the promising research directions that might lead to further improvement of the electrochemical properties of SiO_(x) -based anodes are noted.This paper can serve as a basis for the research and development of high-energy-density LIBs.

Electrochemical properties of spinel LiMn_2O_4 and LiAl_(0.1)Mn_(1.9)O_(3.9)F_(0.1) synthesized by solid-state reaction

Two types of spinel cathode powders, LiMn2O4 and LiAl0.1Mn1.9O3.9F0.1, were synthesized by solid-state reaction, X-ray diffraction （XRD） patterns of the prepared samples were identified as the spinel structure with a space group of Fd 3^- m. The cubic lattice parameter was determined from least-squares fitting of the XRD data. The LiAl0.1Mn1.9O3.9F0.1 sample showed a little lower initial capacity, but better cycling performance than the LiMn2O4 sample at both room temperature and an elevated temperature. The Vanderbilt method was used to test the electrochemical conductivity of the LiMn2O4 samples. The electrochemical impedance spectroscopy （EIS） method was employed to investigate the electrochemical properties of these spinel LiMn2O4 samples.

Sandwich-like structure C/SiO_(x)@graphene anode material with high electrochemical performance for lithium ion batteries

Silicon suboxide(SiO_(x),0<x<2)is recognized as one of the next-generation anode materials for high-energy-density lithium ion batteries(LIBs)due to its high theoretical specific capacity and abundant resource.However,the severe mechanical instability arising from large volume variation upon charge/discharge cycles frustrates its electrochemical performance.Here we propose a well-designed sandwich-like structure with sandwiched SiO_(x) nanoparticles between graphene sheets and amorphous carbon-coating layer so as to improve the structural stability of SiO_(x) anode materials during cycling.Graphene sheets and carbon layer together construct a three-dimensional conductive network around SiO_(x) particles,which not only improves the electrode reactions kinetics,but also homogenizes local current density and thus volume variation on SiO_(x) surface.Moreover,Si-O-C bonds between SiO_(x) and graphene endow the strong particle adhesion on graphene sheets,which prevents SiO_(x) peeling from graphene sheets.Owing to the synergetic effects of the structural advantages,the C/SiO_(x)@graphene material exhib-its an excellent cyclic performance such as 890 mAh/g at 0.1 C rate and 73.7%capacity retention after 100 cycles.In addition,it also delivers superior rate capability with a capacity recovery of 886 mAh/g(93.7%recovery rate)after 35 cycles of ascending steps at current range of 0.1-5 C and finally back to 0.1 C.This study provides a novel strategy to improve the structural stability of high-capacity anode materials for lithium/sodium ion batteries.

Semi-interpenetrating-network all-solid-state polymer electrolyte with liquid crystal constructing efficient ion transport channels for flexible solid lithium-metal batteries

The development of the solid-state polymer electrolytes (SPEs) for Li-ion batteries (LIBs) can effectively address the hidden safety issues of commercially used liquid electrolytes.Nevertheless,the unsatisfactory room temperature ion conductivity and inferior mechanical strength for linear PEO-based SPEs are still the immense obstacles impeding the further applications of SPEs for large-scale commercialization.Herein,we fabricate a series of semi-interpenetrating-network (semi-IPN) polymer electrolytes based on a novel liquid crystal (C6M LC) and poly(ethylene glycol) diglycidyl ether (PEGDE) via UV-irradiation at the first time.The LCs not only highly improve the mechanical properties of electrolyte membranes via the construction of network structure with PEGDE,but also create stable ion transport channels for ion conduction.As a result,a free-standing flexible SPE shows outstanding ionic conductivity(5.93×10^(-5) S cm^(-1) at 30℃),a very wide electrochemical stability window of 5.5 V,and excellent thermal stability at thermal decomposition temperatures above 360℃ as well as the capacity of suppressing lithium dendrite growth.Moreover,the LiFePO_(4)/Li battery assembled with the semi-IPN electrolyte membranes exhibits good cycle performance and admirable reversible specific capacity.This work highlights the obvious advantages of LCs applied to the electrolyte for the advanced solid lithium battery.

Effect of sintering time on the electrochemical properties of spinel LiMn_2O_4 synthesized by solid-state reaction

LiMn2O4 powder as a cathode materials for rechargeable lithium-ion batteries was prepared by solid-state reaction from LitCO3 and electrolytic MnOz at different sintering periods （2, 6, 18, and 32 h）. X-ray diffraction （XRD） patterns of the prepared samples are identified as the spinel structure with a space group of Fd3 m. The lattice parameters almost remain the same as the sintering periods increase. The sample with a sintering period of 32 h shows good cycling performance at both low and nigh current densities, and also elevated temperature. It is believed that the excellent electrochemical behavior of this sample results from its good crystallinity and large grain size compared with other samples. Different electrochemical measurements were conducted to investigate the electrochemical properties of spinel LiMn204. 2008 University of Science and Technology Beijing. All rights reserved.

Rational structure design to realize high-performance SiOx@C anode material for lithium ion batteries

Silicon suboxide(SiOx)is considered to be one of the most promising materials for next-generation anode due to its high energy density.For its preparation,the wet-chemistry method is a cost-effective and readily scalable route,while the so-derived SiOx usually shows lower capacity compared with that prepared by high temperature-vacuum evaporation route.Herein,we present an elaborate particle structure design to realize the wet-chemistry preparation of a high-performance SiOx/C nanocomposite.Dandelion-like highly porous SiOx particle coated with conformal carbon layer is designed and prepared.The highly-porous SiOx skeleton provides plenty specific surface for intimate contact with carbon layer to allow a deep reduction of SiOx to a low O/Si ratio at relatively low temperature(700℃),enabling a high specific capacity.The abundant mesoscale voids effectively accommodate the volume variation of SiOx skeleton,ensuring the high structural stability of SiOx@C during lithiation/delithiation process.Meanwhile,the three-dimensional(3D)conformal carbon layer provides a fast electron/ion transportation,allowing an enhanced electrodereaction kinetics.Owing to the optimized O/Si ratio and well-engineered structure,the prepared SiOx@C electrode delivers an ultra-high capacity(1,115.8 mAh·g^-1 at 0.1 A·g^-1 after 200 cycles)and ultra-long lifespan(635 mAh·g^-1 at 2 A·g^-l after 1,000 cycles).To the best of our knowledge,the achieved combination of ultra-high specific capacity and ultra-long cycling life is unprecedented.

High-performance oxygen permeation membranes:Cobalt-free Ba_(0.975)La_(0.025)Fe_(1-x)Cu_(x)O_(3)-δceramics

A new group of cobalt-free perovskite oxides,Ba_(0.975)La_(0.025)Fe_(1-x)Cu_(x)O_(3-δ)(BLFC,x=0.05-0.15),was designed,characterized and applied as oxygen permeation membranes.It was found that BLFC oxides with Cu doping range of 0.075-0.15 maintain cubic perovskite phase in a wide range of temperatures.More Cu introduced at the B-site results in a gradual increase of the electrical conductivity,which is attributed to the denser overlapping of electron clouds of CueO bonds.With increasing Cu content,the oxygen vacancy concentration increases and the oxygen ion migration energy decreases,leading to the highest oxygen permeation flux of 1.59 mL cm^(-2)min^(-1)recorded for Ba_(0.975)La_(0.025)Fe_(0.9)Cu_(0.1)O_(3-δ)1mm thick membrane at 950℃.However,the oxygen permeability decreases with further Cu doping,which may be correspond to a presence of defect association.Ba_(0.975)La_(0.025)Fe_(0.9)Cu_(0.10)O_(3-δ)membrane with 0.7mm thickness delivers stable oxygen permeation flux of 1.57 mL cm^(-2)min^(-1)for 200 h at 900℃.All of the obtained results indicate that the developed BLFC with optimized Cu content(i.e.x=0.1)is a very promising material for usage in oxygen separation applications.