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Metal-organic frameworks (MOFs) present diverse building blocks for high-performance materials across industries, yet their crystallization mechanisms remain incompletely understood due to gaps in nucleation and growth knowledge. In this study, MOF structural evolution is probed using in situ liquid phase transmission electron microscopy (TEM) and cryo-TEM, unveiling a blend of classical and nonclassical pathways involving liquid-liquid phase separation, particle attachment-coalescence, and surface layer deposition. Additionally, ultrafast high-temperature sintering (UHS) is employed to dope ultrasmall Cobalt nanoparticles (Co NPs) uniformly within nitrogen-doped hard carbon nanocages confirmed by 3D electron tomography. Lithium-sulfur battery tests demonstrate the nanocage-Co NP structure's exceptional capacity and cycling stability, attributed to Co NP catalytic effects due to its small size, uniform dispersion, and nanocage confinement. The findings propose a holistic framework for MOF crystallization understanding and Co NP tunability through ultrafast sintering, promising advancements in materials science and informing future MOF synthesis strategies and applications., (© 2024 The Author(s). Advanced Science published by Wiley‐VCH GmbH.)

Fluorinated-ethers are promising electrolyte solvents in lithium metal batteries, for their high antioxidant and excellent reductive stability on Li anode. However, fluorinated-ethers with high fluorination degree suffer from low ionic conductivity and narrow temperature adaptibility. Herein, we synthesize a mono-fluorinated linear ether of bis(2-fluoroethoxy) methane (BFME) with enhanced solvated ability. The -OCH 2 O- structure and fluoride substitution on the β-C position endows the BFME electrolyte with moderate affinity to Li + , thereby improving the ionic conductivity and decreasing the Li + -desolvation energy barrier at a wide temperature range of -60-60 °C. Additionally, the electrolyte with anion-participated solvation structure demonstrates high film-forming ability by forming LiF-rich interfacial film on the electrode surfaces, rendering the graphite anode with an initial Coulombic efficiency (CE) of 94.9 % and a Li plating/stripping CE of 99.8 % by Aurbach method. Consequently, the Graphite||LiFePO 4 pouch cells delivered 83.2 %, 92.5 % and 81.2 % capacity retention after 1250, 200 and 300 cycles at 25, -20 °C and 60 °C, respectively. Moreover, the Li||LFP pouch cell with 3 Ah capacity can operate for 65 cycles with 99 % capacity retention, verifying the effectiveness of the BFME electrolyte in stabilizing the interfaces and broadening the temperature adaptibility of lithium-ion and lithium metal batteries., (© 2024 Wiley-VCH GmbH.)

Lithium iron phosphate batteries, known for their durability, safety, and cost-efficiency, have become essential in new energy applications. However, their widespread use has highlighted the urgency of battery recycling. Inadequate management could lead to resource waste and environmental harm. Traditional recycling methods, like hydrometallurgy and pyrometallurgy, are complex and energy-intensive, resulting in high costs. To address these challenges, this study introduces a novel low-temperature liquid-phase method for regenerating lithium iron phosphate positive electrode materials. By using N 2 H 4 ·H 2 O as a reducing agent, missing Li + ions are replenished, and anti-site defects are reduced through annealing. This process restores nearly all missing Li + ions at 80 °C/6h. After high-temperature sintering at 700 °C/2h, the regenerated LiFePO 4 matches commercial LiFePO 4 in terms of anti-site defects and exhibits excellent performance with a 97 % capacity retention rate after 100 cycles at 1C. Compared to high-temperature techniques, this low-temperature liquid-phase method is simpler, safer, and more energy-efficient, offering a blueprint for reclaiming discarded LiFePO 4 and similar materials., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2024 Elsevier Ltd. All rights reserved.)

To enable high performance of all solid-state batteries, a catholyte should demonstrate high ionic conductivity, good compressibility and oxidative stability. Here, a LaCl 3 -based Na + superionic conductor (Na 1 - x Zr x La 1 - x Cl 4 ) with high ionic conductivity of 2.9 × 10 -4  S cm -1 (30 °C), good compressibility and high oxidative potential (3.80 V vs. Na 2 Sn) is prepared via solid state reaction combining mechanochemical method. X-ray diffraction reveals a hexagonal structure (P6 3 /m) of Na 1 - x Zr x La 1 - x Cl 4 , with Na + ions forming a one-dimensional diffusion channel along the c-axis. First-principle calculations combining with X-ray absorption fine structure characterization etc. reveal that the ionic conductivity of Na 1 - x Zr x La 1 - x Cl 4 is mainly determined by the size of Na + -channels and the Na + /La 3+ mixing in the one-dimensional diffusion channels. When applied as a catholyte, the NaCrO 2 ||Na 0.7 Zr 0.3 La 0.7 Cl 4 ||Na 3 PS 4 ||Na 2 Sn all-solid-state batteries demonstrate an initial capacity of 114 mA h g -1 and 88% retention after 70 cycles at 0.3 C. In addition, a high capacity of 94 mA h g -1 can be maintained at 1 C current density., (© 2024. The Author(s).)

Graphite anode suffers from great capacity loss and larger cell polarization under low-temperature conditions in lithium-ion batteries (LIBs), which are mainly caused by the high energy barrier for the Li + desolvation process and sluggish Li + transfer rate across the solid electrolyte interface (SEI). Regulating an electrolyte with an anion-dominated solvation structure could synchronously stabilize the interface and boost the reaction kinetics of the graphite anode. Herein, a highly ionic conductive electrolyte consisting of a fully methylated cyclic ether solvent of 2,2,4,4,5,5-hexamethyl-1,3-dioxolane (HMD) and fluoroethylene carbonate (FEC) cosolvent was designed. The high electron-donating effect and steric hindrance of -(CH 3 ) 2 in HMD endow the HMD-based electrolyte with high ionic conductivity but lower coordination numbers with Li + , and an anion-dominated solvation structure was formed. Such configuration can accelerate the desolvation process and induce the forming of a LiF-rich SEI film on the anode, avoiding the solvent coembedding into graphite and enhancing the ion migration rate under low temperatures. The assembled Li||graphite cell with the tame electrolyte outperformed the conventional carbonates-based cell, showing 93.8% capacity retention after 227 cycles for the DF-based cell compared to 64.7% after 150 cycles. It also exhibited a prolonged cycle life for 200 rounds with 81% capacity retention under -20 °C. Therefore, this work offers a valuable thought for solvent design and provides approaches to electrolyte design for low-temperature LIBs.

In situ polymerization to prepare quasi-solid electrolyte has attracted wide attentions for its advantage in achieving intimate electrode-electrolyte contact and the high process compatibility with current liquid batteries; however, gases can be generated during polymerization process and remained in the final electrolyte, severely impairing the electrolyte uniformity and electrochemical performance. In this work, an in situ polymerized poly(vinylene carbonate)-based quasi-solid electrolyte for high-voltage sodium metal batteries (SMBs) is demonstrated, which contains a novel multifunctional additive N-methyl-N-(trimethylsilyl)trifluoroacetamide (MSTFA). MSTFA as high-efficient plasticizer diminishes residual gases in electrolyte after polymerization; the softer and homogeneous electrolyte enables much faster ionic conduction. The HF/H 2 O scavenge effect of MSTFA mitigates the corrosion of free acid to cathode and interfacial passivating layers, enhancing the cycle stability under high voltage. As a result, the 4.4 V Na||Na 3 V 2 (PO 4 ) 2 F 3 cell employing the optimized electrolyte possesses an initial discharge capacity of 112.0 mAh g -1 and a capacity retention of 91.3% after 100 cycles at 0.5C, obviously better than those of its counterparts without MSTFA addition. This work gives a pioneering study on the gas residue phenomenon in in situ polymerized electrolytes, and introduces a novel multifunctional silane additive that effectively enhances electrochemical performance in high-voltage SMBs, showing practical application significance., (© 2023 Wiley-VCH GmbH.)

Lithium metal batteries (LMBs) are expected to upgrade their energy density to meet the growing battery market demand; however, intractable lithium dendrites and prominent electrode-electrolyte interface problems have been the stumbling block to their practical applications. Electrolytes play a crucial role in LMBs and are directly involved in the establishment of the electrode-electrolyte interface. In particular, low-concentration electrolytes (LCEs) can significantly save electrolyte costs, but the interface issue is more noteworthy. Here, multifunctional acetamide ( N -methyl- N -(trimethylsilyl)-trifluoroacetamide, MTA) and lithium nitrate (LiNO 3 ) additives were introduced together to enhance the performance of LMBs in LCEs. The MTA additive effectively removes the trace water and corrosive HF from the electrolyte, thus suppressing lithium salt decomposition and enhancing the stability of LCEs. Moreover, the MTA additive can construct an inorganic-rich interphase layer on the cathode/anode surface to protect the electrode. Especially, MTA can cooperate with LiNO 3 additive to suppress lithium dendrites and reduce interfacial impedance, thus effectively enhancing lithium metal anode stability. Benefiting from the introduction of MTA and LiNO 3 additives in the LCEs, the Li||NMC811 metal battery still has a capacity of 110 mA h g -1 after 500 cycles at room temperature, while the reference batteries have failed. The rate capacity and high temperature (50 °C) performance of the Li||NCM811 batteries have also been significantly improved. Significantly, this research explores a cost-effective method of using multifunctional additives to enhance LMBs' stability in LCEs.

In situ liquid phase transmission electron microscopy (TEM) and three-dimensional electron tomography are powerful tools for investigating the growth mechanism of MOFs and understanding the factors that influence their particle morphology. However, their combined application to the study of MOF etching dynamics is limited due to the challenges of the technique such as sample preparation, limited field of view, low electron density, and data analysis complexity. In this research, we present a study employing in situ liquid phase TEM to investigate the etching mechanism of colloidal zeolitic imidazolate framework (ZIF) nanoparticles. The etching process involves two distinct stages, resulting in the development of porous structures as well as partially and fully hollow morphologies. The etching process is induced by exposure to an acid solution, and both in situ and ex situ experiments demonstrate that the outer layer etches faster leading to overall volume shrinking (stage I) while the inner layer etches faster giving a hollow morphology (stage II), although both the outer layer and inner layer have been etched in the whole process. 3D electron tomography was used to quantify the properties of the hollow structures which show that the ZIF-67 crystal etching rate is larger than that of the ZIF-8 crystal at the same pH value. This study provides valuable insights into MOF particle morphology control and can lead to the development of novel MOF-based materials with tailored properties for various applications.

Si-based rechargeable lithium-ion batteries (LIBs) have generated interest as silicon has remarkably high theoretical specific capacity. It is projected that LIBs will meet the increasing need for extensive energy storage systems, electric vehicles, and portable electronics with high energy densities. However, the Si-based LIB has a substantial problem due to the volume cycle variations brought on by Si, which result in severe capacity loss. Making Si-based anodes-enabled high-performance LIBs that are easy to utilize requires an understanding of the fading mechanism. Due to its distinct advantage in morphological changes from microscale to nanoscale, even approaching atomic resolution, electron microscopy is one of the most popular methods. Based on operando electron microscopy characterization, the general comprehension of the fading mechanism and the morphology evolution of Si-based LIBs are debated in this review. The current advancements in compositional and structural interpretation for Si-based LIBs using advanced electron microscopy characterization methods are outlined. The future development trends in pertinent silicon materials characterization methods are also highlighted, along with numerous potential research avenues for Si-based LIBs design and characterization.

A novel and facile strategy for fabricating red phosphorus@nitrogen doped graphene/carbon nanotube aerogel (P@NGCA) is proposed as a free-standing anode for high energy sodium-ion batteries. Owing to an optimized structure of red P uniformly confined in porous NGCA with high conductivity and mechanical stability, the free-standing P@NGCA anode exhibits outstanding sodium storage performance with a high areal capacity of 3.3 mA h cm -2 and superior initial Coulombic efficiency of 80%.

A lithium metal anode and high nickel ternary cathode are considered viable candidates for high energy density lithium metal batteries (LMBs). However, unstable electrode-electrolyte interfaces and structure degradation of high nickel ternary cathode materials lead to serious capacity decay, consequently hindering their practical applications in LMBs. Herein, we introduced N , O -bis(trimethylsilyl) trifluoro acetamide (BTA) as a multifunctional additive for removing trace water and hydrofluoric acid (HF) from the electrolyte and inhibiting corrosive HF from disrupting the electrode-electrolyte interface layers. Furthermore, the BTA additive containing multiple functional groups (C-F, Si-O, Si-N, and C═N) promotes the formation of LiF-rich, Si- and N-containing solid electrolyte interfacial films on a lithium metal anode and LiNi 0.8 Mn 0.1 Co 0.1 O 2 (NMC811) cathode surfaces, thereby improving the electrode-electrolytes interfacial stability and mitigating the capacity decay caused by structural degradation of the layered cathode. Using the BTA additive had tremendous benefits through modification of both anode and cathode surface layers. This was demonstrated using a Li||NMC811 metal battery with the BTA electrolyte, which exhibits remarkable cycling and rate performances (122.9 mA h g -1 at 10 C) and delivers a discharge capacity of 162 mA h g -1 after 100 cycles at 45 °C. Likewise, this study establishes a cost-effective approach of using a single additive to improve the electrochemical performance of LMBs.

A novel design strategy for synthesizing hard carbon microspheres (HCMs) from a single source of sodium lignin sulfonate is proposed for a practical anode material of sodium-ion batteries. The HCM has an optimized microstructure, including an enlarged interlayer spacing and few defects, along with a low specific surface area. As an anode material of sodium-ion batteries, HCM is highly promising for practical applications because of its high capacity and reversibility.

Lithium-ion sulfur batteries as a new energy storage system with high capacity and enhanced safety have been emphasized, and their development has been summarized in this review. The lithium-ion sulfur battery applies elemental sulfur or lithium sulfide as the cathode and lithium-metal-free materials as the anode, which can be divided into two main types. One is anode-type, where elemental sulfur is applied as the cathode, and the anode provides lithium ions. The other one is cathode-type, where lithium sulfide as the cathode provides lithium ions, and lithium-metal-free materials (e.g., graphite, silicon/carbon) function as the anode. Recently, some new lithium-ion sulfur battery systems have also been proposed, and are discussed in this review as well. The lithium-ion sulfur batteries not only maintain the advantage of high energy density because of the high capacities of sulfur and lithium sulfide, but also exhibit the improved safety of the batteries due to a non-lithium-metal in the anode. This review paper aims to track the recent progress in the development of lithium-ion sulfur batteries and summarize the challenges and the approaches for improving their electrochemical performances, including the lithiation methods to prepare lithium-metal-free anodes in anode-type lithium-ion sulfur batteries and the lithium sulfide cathode modification approaches in cathode-type lithium-ion sulfur batteries. Furthermore, the challenges and perspectives for future research and commercial applications have also been enumerated.

Trace ethanol is applied as a cheap and effective electrolyte additive for reducing the activation voltage of Li2S cathodes in lithium-ion-sulfur batteries. Because Li2S can dissolve in ethanol, the solid-solid phase reaction in the first stage of the activation process converts into a liquid-solid phase reaction, which expedites the transport of electrons and lithium ions and reduces the activation voltage of Li2S. This strategy can be extended to other solvents that can dissolve Li2S.

Rapidly developed Na-ion batteries are highly attractive for grid energy storage. Nevertheless, the safety issues of Na-ion batteries are still a bottleneck for large-scale applications. Similar to Li-ion batteries (LIBs), the safety of Na-ion batteries is considered to be tightly associated with the electrolyte and electrode/electrolyte interphase. Although the knowledge obtained from LIBs is helpful, designing safe electrolytes and obtaining stable interphases in Na-ion batteries is still a huge challenge. Therefore, it is of significance to investigate the key factors and develop new strategies for the development of high-safety Na-ion batteries. This comprehensive review introduces the recent efforts from nonaqueous electrolytes and interphase aspects of Na-ion batteries, proposes their design strategies and requirements for improving safety characteristics, and discusses the potential issues for practical applications. The insight to formulate safe electrolytes and design the stable interphase for Na-ion batteries with high safety is intended to be provided herein., (© 2019 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

In this work, a ternary confined-functional sulfur composite with a Host-Sulfur-Container structure is designed and synthesized for high performance lithium sulfur batteries. The host in this unique architecture is porous carbon, which contains interconnected macropore tunnels and meso/micropores on the macropore tunnel walls. These hierarchical pores exhibit a synergistic effect to adsorb sulfur in their spaces and provide more nucleation sites to direct the uniform coating of sulfur. Moreover, the interconnected porous structure can facilitate electron transfer and also ensure high sulfur utilization. Furthermore, the poly(3,4-ethylenedioxythiophene) layer container improves the conductivity of the electrode, prevents the diffusion of dissolved polysulfide, and prevents volume expansion during the charge-discharge processes. As a result, the electrode with the poly(3,4-ethylenedioxythiophene)/sulfur/porous carbon composite and Host-Sulfur-Container architecture maintains a reversible capacity of 831.9 mA h g-1 after 200 cycles at a current density of 0.5 C and presents long-term cycling stability with 0.088% capacity decay per cycle over 500 cycles at 1 C. This indicates that the prepared Host-Sulfur-Container composite is a promising cathode material for lithium-sulfur batteries, and its hierarchical tunnel pore carbon host with meso/micropores inside shows great potential in the energy storage field.

The notorious lithium (Li) dendrites and the low Coulombic efficiency (CE) of Li anode are two major obstacles to the practical utilization of Li metal batteries (LMBs). Introducing a dendrite-suppressing additive into nonaqueous electrolytes is one of the facile and effective solutions to promote the commercialization of LMBs. Herein, Li difluorophosphate (LiPO 2 F 2, LiDFP) is used as an electrolyte additive to inhibit Li dendrite growth by forming a vigorous and stable solid electrolyte interphase film on metallic Li anode. Moreover, the Li CE can be largely improved from 84.6% of the conventional LiPF 6 -based electrolyte to 95.2% by the addition of an optimal concentration of LiDFP at 0.15 M. The optimal LiDFP-containing electrolyte can allow the Li||Li symmetric cells to cycle stably for more than 500 and 200 h at 0.5 and 1.0 mA cm -2 , respectively, much longer than the control electrolyte without LiDFP additive. Meanwhile, this LiDFP-containing electrolyte also plays an important role in enhancing the cycling stability of the Li||LiNi 1/3 Co 1/3 Mn 1/3 O 2 cells with a moderately high mass loading of 9.7 mg cm -2 . These results demonstrate that LiDFP has extensive application prospects as a dendrite-suppressing additive in advanced LMBs.

We prepare a totally nonflammable phosphate-based electrolyte composed of 5 mol L-1 (M) Li bis(fluorosulfonyl) imide (LiFSI) in a trimethyl phosphate (TMP) solvent. The concentrated 5 M LiFSI/TMP electrolyte shows good compatibility with graphite and no Al corrosion. More attractively, such a concentrated electrolyte can effectively suppress the growth of Li dendrites in Li metal batteries because of a stable LiF-rich SEI layer. Therefore, this highly concentrated electrolyte is promising for safe Li batteries.

Two-dimensional stable metallic 1T-MoSe 2 with expanded interlayer spacing of 10.0 Å in situ grown on SWCNTs film is fabricated via a one-step solvothermal method. Combined with X-ray absorption near-edge structures, our characterization reveals that such 1T-MoSe 2 and single-walled carbon nanotubes (abbreviated as 1T-MoSe 2 /SWCNTs) hybridized structure can provide strong electrical and chemical coupling between 1T-MoSe 2 nanosheets and SWCNT film in a form of C-O-Mo bonding, which significantly benefits a high-efficiency electron/ion transport pathway and structural stability, thus directly enabling high-performance lithium storage properties. In particular, as a flexible and binder-free Li-ion anode, the 1T-MoSe 2 /SWCNTs electrode exhibits excellent rate capacity, which delivers a capacity of 630 mAh/g at 3000 mA/g. Meanwhile, the strong C-O-Mo bonding of 1T-MoSe 2 /SWCNTs accommodates volume alteration during the repeated charge/discharge process, which gives rise to 89% capacity retention and a capacity of 971 mAh/g at 300 mA/g after 100 cycles. This synthetic route of a multifunctional MoSe 2 /SWCNTs hybrid might be extended to fabricate other 2D layer-based flexible and light electrodes for various applications such as electronics, optics, and catalysts.

Bulk doping, surface coating, and size reducing are three strategies for improving the electrochemical properties of Li4Ti5O12 (LTO). In this work, chromium (Cr)-modified LTO with a synergistic effect of bulk doping, surface coating, and size reducing is synthesized by a facile sol-gel method. X-ray diffraction (XRD) and Raman analysis prove that Cr dopes into the LTO bulk lattice, which effectively inhibits the generation of TiO2 impurities. Transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS) verifies the surface coating of Li2CrO4 on the LTO surface, which decreases impedance of the LTO electrode. More importantly, the size of LTO particles can be significantly reduced from submicroscale to nanoscale as a result of the protection of the Li2CrO4 surface layer and the suppression from Cr atoms on the long-range order in the LTO lattice. As anode material, Li4-xCr3xTi5-2xO12 (x = 0.1) delivers a reversible capacity of 141 mAh g(-1) at 10 °C, and over 155 mAh g(-1) at 1 °C after 1000 cycles. Therefore, the Cr-modified Li4Ti5O12 prepared via a sol-gel method has potential for applications in high-power, long-life lithium-ion batteries.

Ultrathin Li4Ti5O12 (LTO) nanosheets with ordered microstructures were prepared via a polyether-assisted hydrothermal process. Pluronic P123, a polyether, can impede the growth of Li2TiO3 in the precursor and also act as a structure-directing agent to facilitate the (Li1.81H0.19)Ti2O5·2H2O precursor to form the LTO nanosheets with the ordered microstructure. Moreover, the addition of P123 can suppress the stacking of LTO nanosheets during calcining of the precursor, and the thickness of the nanosheets can be controlled to be about 4 nm. The microstructure of the as-prepared ultrathin and ordered nanosheets is helpful for Li(+) or Na(+) diffusion and charge transfer through the particles. Therefore, the ultrathin P123-assisted LTO (P-LTO) nanosheets show a rate capability much higher than that of the LTO sample without P123 in a Li battery with over 130 mAh g(-1) of capacity remaining at the 64C rate. For intercalation of larger size Na(+) ions, the P-LTO still exhibits a capacity of 115 mAh g(-1) at a current rate of 10 C and a capacity retention of 96% after 400 cycles.

The effects of propylene carbonate (PC) content in CsPF6-containing electrolytes on the performances of graphite electrode in lithium half cells and in graphite∥LiNi0.80Co0.15Al0.05O2 (NCA) full cells are investigated. It is found that the performance of graphite electrode is significantly affected by PC content in the CsPF6-containing electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode can be attributed to the synergistic effects of the PC solvent and the Cs(+) additive. The synergistic effects of Cs(+) additive and appropriate amount of PC enable the formation of a robust, ultrathin, and compact solid electrolyte interphase (SEI) layer on the surface of graphite electrode, which is only permeable for desolvated Li(+) ions and allows fast Li(+) ion transport through it. Therefore, this SEI layer effectively suppresses the PC cointercalation and largely alleviates the Li dendrite formation on graphite electrode during lithiation even at relatively high current densities. The presence of low-melting-point PC solvent improves the sustainable operation of graphite∥NCA full cells under a wide temperature range. The fundamental findings also shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in various energy-storage devices.

Despite the potential advantages it brings, such as wider liquid range and lower cost, propylene carbonate (PC) is seldom used in lithium-ion batteries because of its sustained cointercalation into the graphene structure and the eventual graphite exfoliation. Here, we report that cesium cation (Cs(+)) directs the formation of solid electrolyte interphase on graphite anode in PC-rich electrolytes through its preferential solvation by ethylene carbonate (EC) and the subsequent higher reduction potential of the complex cation. Effective suppression of PC-decomposition and graphite-exfoliation is achieved by adjusting the EC/PC ratio in electrolytes to allow a reductive decomposition of Cs(+)-(EC)m (1 ≤ m ≤ 2) complex preceding that of Li(+)-(PC)n (3 ≤ n ≤ 5). Such Cs(+)-directed interphase is stable, ultrathin, and compact, leading to significant improvement in battery performances. In a broader context, the accurate tailoring of interphasial chemistry by introducing a new solvation center represents a fundamental breakthrough in manipulating interfacial reactions that once were elusive to control.

Composite Ni-YSZ fuel electrodes are able to operate only under strongly reducing conditions for the electrolysis of CO(2) in oxygen-ion conducting solid oxide electrolysers. In an atmosphere without a flow of reducing gas (i.e., carbon monoxide), a composite fuel electrode based on redox-reversible La(0.2)Sr(0.8)TiO(3+δ) (LSTO) provides a promising alternative. The Ti(3+) was approximately 0.3% in the oxidized LSTO (La(0.2)Sr(0.8)TiO(3.1)), whereas the Ti(3+) reached approximately 8.0% in the reduced sample (La(0.2)Sr(0.8)TiO(3.06)). The strong adsorption of atmospheric oxygen in the form of superoxide ions led to the absence of Ti(3+) either on the surface of oxidized LSTO or the reduced sample. Reduced LSTO showed typical metallic behaviour from 50 to 700 °C in wet H(2); and the electrical conductivity of LSTO reached approximately 30 S cm(-1) at 700 °C. The dependence of [Ti(3+)] concentration in LSTO on P(O(2)) was correlated to the applied potentials when the electrolysis of CO(2) was performed with the LSTO composite electrode. The electrochemical reduction of La(0.2)Sr(0.8)TiO(3+δ) was the main process but was still present up to 2 V at 700 °C during the electrolysis of CO(2); however, the electrolysis of CO(2) at the fuel electrode became dominant at high applied voltages. The current efficiency was approximately 36% for the electrolysis of CO(2) at 700 °C and a 2 V applied potential.