Cathode materials for solid oxide fuel cells: a review

The composition and microstructure of cathode materials has a large impact on the performance of solid oxide fuel cells (SOFCs). Rational design of materials composition through controlled oxygen nonstoichiometry and defect aspects can enhance the ionic and electronic conductivities as well as the catalytic properties for oxygen reduction in the cathode. Cell performance can be further improved through microstructure optimization to extend the triple-phase boundaries. A major degradation mechanism in SOFCs is poisoning of the cathode by chromium species when chromium-containing alloys are used as the interconnect material. This article reviews recent developments in SOFC cathodes with a principal emphasis on the choice of materials. In addition, the reaction mechanism of oxygen reduction is also addressed. The development of Cr-tolerant cathodes for intermediate temperature solid oxide fuel cells, and a possible mechanism of Cr deposition at cathodes are briefly reviewed as well. Finally, this review will be concluded with some perspectives on the future of research directions in this area.     

Formation of copper–polymer nanocomposite upon copper electrodeposition in the presence of poly(<Emphasis Type="Italic">N</Emphasis>-vinylpyrrolidone)

The composition and structure of products formed on a cathode upon electrodeposition of copper from copper sulfate–poly(N-vinylpyrrolidone) mixed solutions have been studied. These products have been shown to be nanocomposites consisting of copper nanoparticles and the polymer. It has been suggested that the composite is formed by a pseudotemplate mechanism via noncovalent interaction between macromolecules and copper particles growing on the cathode. The interaction is accompanied by deceleration of subsequent growth of particles because of their screening by the polymer. This decreases the sizes of copper particles in the reaction product and the rate of metal reduction. The sonication of the reaction system yields a nanocomposite sol containing nanoparticles of copper(I) oxide. The oxide results from rapid oxidation of copper metal particles that have passed to the sol with copper(II) ions.     

A Redox‐Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity

Metal–organic framework cathodes usually exhibit low capacity and poor electrochemical performance for Li‐ion storage owing to intrinsic low conductivity and inferior redox activity. Now a redox‐active 2D copper–benzoquinoid (Cu‐THQ) MOF has been synthesized by a simple solvothermal method. The abundant porosity and intrinsic redox character endow the 2D Cu‐THQ MOF with promising electrochemical activity. Superior performance is achieved as a Li‐ion battery cathode with a high reversible capacity (387 mA h g^?1), large specific energy density (775 Wh kg^?1), and good cycling stability. The reaction mechanism is unveiled by comprehensive spectroscopic techniques: a three‐electron redox reaction per coordination unit and one‐electron redox reaction per copper ion mechanism is demonstrated. This elucidatory understanding sheds new light on future rational design of high‐performance MOF‐based cathode materials for efficient energy storage and conversion.     

Advances in the Cathode Materials for Lithium Rechargeable Batteries

The accelerating development of technologies requires a significant energy consumption, and consequently the demand for advanced energy storage devices is increasing at a high rate. In the last two decades, lithium‐ion batteries have been the most robust technology, supplying high energy and power density. Improving cathode materials is one of the ways to satisfy the need for even better batteries. Therefore developing new types of positive electrode materials by increasing cell voltage and capacity with stability is the best way towards the next‐generation Li rechargeable batteries. To achieve this goal, understanding the principles of the materials and recognizing the problems confronting the state‐of‐the‐art cathode materials are essential prerequisites. This Review presents various high‐energy cathode materials which can be used to build next‐generation lithium‐ion batteries. It includes nickel and lithium‐rich layered oxide materials, high voltage spinel oxides, polyanion, cation disordered rock‐salt oxides and conversion materials. Particular emphasis is given to the general reaction and degradation mechanisms during the operation as well as the main challenges and strategies to overcome the drawbacks of these materials.     

新型纳米结构V10O24·12H2O的制备及结构表征

以V2O5粉末为原料, 在常压下制备新型纳米结构V10O24·12H2O材料, 并分析了其反应机制. 利用XRD, TEM, TG-DSC, FTIR和XPS对其结构和形貌等进行了表征. 结果表明, V10O24·12H2O的层间距d(002)≈1.43 nm; 微观形貌为球形, 球径40~60 nm; 有V4+和V5+两种化学状态; IR峰的变化主要由晶格膨胀和V4+引起; 存在吸附水、层间水及结晶水.     

层状LiMnO_2正极材料的研究进展

层状LiMnO2 化合物的研究是目前锂离子电池正极材料锂锰氧化物研究工作的新热点 ,本文综述了近年来国内外LiMnO2 化合物的研究进展 ,主要阐述了具有层状和扭曲层状结构的m LiMnO2和o LiMnO2 的结构、电性能、合成和改性方法等方面的研究状况 ,重点介绍了离子交换法合成层状LiMnO2 的原因和机理。探索新的合成方法和掺杂其它金属离子改性以提高循环性能是今后LiMnO2 的研究趋势。     

不同含钴阴极在YSZ薄膜电解质固体氧化物燃料电池中的性能

固体氧化物燃料电池阴极材料的阻抗对固体氧化物燃料电池的性能有较大影响.我们通过XRD、对称电池以及单电池性能测试等方法比较系统地研究了4种最为常用的含钴阴极材料直接用于钇稳定化氧化锆（YSZ）电解质薄膜与通过引入SDC夹层后用于YSZ电解质薄膜后的性能.我们发现,不同的含钴阴极材料与YSZ材料之间都不同程度地发生相反应,在应用于YSZ电解质薄膜上时,相反应大大降低了含钴阴极材料的性能,在使用了SDC夹层后,单电池的功率输出显著提高.     

氧化镁表面辐射接枝聚合反应机理研究

氧化镁表面辐射接枝聚合反应机理研究蒋波＊黄光琳（四川联合大学原子核科学技术研究所成都６１００６４）（四川联合大学化学系成都）关键词氧化镁，反应机理，辐射接枝，甲基丙烯酸甲酯１９９６－０５－２１收稿，１９９６－０８－２６修回辐射诱发有机单体在固体表面聚...     

三元锂离子电池容量衰减机理研究进展

三元锂离子电池主要是指使用镍钴锰酸锂(NCM)或镍钴铝酸锂(NCA)作为正极材料的锂离子电池,三元锂离子电池广泛应用于电动汽车、3C电子产品、储能等领域。然而,三元锂离子电池的循环寿命已成为其进一步发展的最大障碍,因此了解三元锂离子电池的容量衰退机理具有重要意义。三元锂离子电池的衰退机理主要包括五个方面:晶体结构的改变和相变、活性材料的损失、电解质的分解和消耗、可脱嵌锂离子的损耗以及固体电解质界面的形成。本文总结了近年来相关方面的研究进展,以期更全面地总结三元锂离子电池的容量衰减机理,并对三元锂离子电池的应用前景进行了展望。     

锂离子电池锂锰氧化物高压嵌锂材料的结构和电化学性能研究

利 用 Ｘ Ｒ Ｄ、 Ｉ Ｃ Ｐ、 Ｔ Ｇ Ａ 、 Ｄ Ｔ Ａ 及 恒 流 充 放 电 等 方 法 研 究 分 析 了 一 种 特 殊 天 然 结 构 Ｍｎ Ｏ２（ Ｎ Ｍ Ｄ） 材料的结 构、组成 以及电 化学嵌锂 特性． Ｘ Ｒ Ｄ 分析 表明,该样 品材料 是由钠水 锰矿以及水羟 锰矿复 合结构组 成的 Ｍｎ Ｏ２ 纳米 纤 维． 充放 电 循环 结果 显 示,其 前 期循 环容 量 可高 达 １５０ｍ Ａｈ／ ｇ 左 右,但性 能尚不够 稳定． 本文采 用一种 水热法高 压嵌锂处 理,可将 Ｎ Ｍ Ｄ 样品 转变为 具有３ ×３ 大隧道结 构的钡 镁锰矿（ Ｔｏｄｏｒｏｋｉｔｅ） 型锂 锰氧 化 物,既 增 强了 Ｌｉ ＋ 嵌 入 隧道 或 层间 结 构 的循环稳定 性． 并 显著提 高锂锰氧 化物电 极材料性 能的 稳定 性,以 充放 电电 流密 度 为０ ．８ ｍ Ａ／ｃ ｍ ２ ,经过１８０ 次 循环后 其比容量 仍具有 １１０ ｍ Ａｈ／ ｇ ． 该类 大隧道结 构锂锰 氧化物可 作为一 种３ Ｖ 的锂离子电极 材料．     

Thermal Behavior Investigation of LiNi1/3Co1/3Mn1/3O2-Based Li-ion Battery under Overcharged Test

Thermal behavior of its components such as separator, electrolyte, cathode, anode, and each binder were investigated by differential scanning calorimetry and thermal gravimetric (DSC/TG) to explain thermal runaway mechanism of Li‐ion battery under overcharged test. DSC results indicated the decomposition reaction temperature of SEI (solid electrolyte interface) layer in anode was at about 126°C. It was found that heat generation in anode under normal charged state increased obviously with the increasing of charged voltage. When the battery was overcharged to 4.6 V or 5.0 V, the onset temperature and heat generation of thermal reaction in anode changed a little, while those in cathode had large increase. It was proposed that thermal behavior in cathode mainly caused by the reaction of electrolyte with evolutional oxygen played a key role to thermal runaway for the studied Li‐ion battery under overcharged test.     

钒氧化物催化剂上NH3-SCR反应物的吸附-脱附

对于钒氧化物负载型催化剂在NH3-SCR过程中的反应机理和动力学已有较多研究。研究表明反应气体在催化剂表面的吸附-脱附过程对于SCR催化反应具有重要意义。本文概述了钒氧化物催化剂载体和表面物种在催化反应中的作用机理,以及H2O、SO2对NH3-SCR反应的影响,重点阐述了各种气相反应物的吸附形式以及反应作用机理。     

Electroreduction of tetra-coordinate phosphonium derivatives; one-pot transformation of triphenylphosphine oxide into triphenylphosphine

Electroreduction of triphenylphosphine dichloride in acetonitrile was performed successfully in an undivided cell fitted with an aluminium sacrificial anode and a platinum cathode, wherein Al³⁺, which was electrogenerated at the anode would react as a Lewis acid with triphenylphosphine dichloride to afford tetra-coordinate chlorotriphenylphosphonium species and subsequent two-electron reduction at the cathode would give triphenylphosphine. One-pot transformation of triphenylphosphine oxide to triphenylphosphine was achieved successfully by the treatment of triphenylphosphine oxide with oxalyl chloride and subsequent electroreduction. In a similar manner, some tetra-coordinate triphenylphosphonium species derived from triphenylphosphine oxide were reduced electrochemically to triphenylphosphine in moderate yields.     

Co-electrolysis of CO_2 and H_2O in high-temperature solid oxide electrolysis cells: Recent advance in cathodes

Co-electrolysis of CO_2 and H_2O using high-temperature solid oxide electrolysis cells(SOECs) into valuable chemicals has attracted great attentions recently due to the high conversion and energy efficiency,which provides opportunities of reducing CO_2 emission, mitigating global warming and storing intermittent renewable energies. A single SOEC typically consists of an ion conducting electrolyte, an anode and a cathode where the co-electrolysis reaction takes place. The high operating temperature and difficult activated carbon-oxygen double-bond of CO_2 put forward strict requirements for SOEC cathode. Great efforts are being devoted to develop suitable cathode materials with high catalytic activity and excellent long-term stability for CO_2/H_2O electro-reduction. The so far cathode material development is the key point of this review and alternative strategies of high-performance cathode material preparation is proposed. Understanding the mechanism of CO_2/H_2O electro-reduction is beneficial to highly active cathode design and optimization. Thus the possible reaction mechanism is also discussed. Especially, a method in combination with electrochemical impedance spectroscopy(EIS) measurement, distribution functions of relaxation times(DRT) calculation, complex nonlinear least square(CNLS) fitting and operando ambient pressure X-ray photoelectron spectroscopy(APXPS) characterization is introduced to correctly disclose the reaction mechanism of CO_2/H_2O co-electrolysis. Finally, different reaction modes of the CO_2/H_2O coelectrolysis in SOECs are summarized to offer new strategies to enhance the CO_2 conversion. Otherwise,developing SOECs operating at 300-600 °C can integrate the electrochemical reduction and the Fischer-Tropsch reaction to convert the CO_2/H_2O into more valuable chemicals, which will be a new research direction in the future.     

A Redox-Active 2D Metal–Organic Framework for Efficient Lithium Storage with Extraordinary High Capacity

Metal–organic framework cathodes usually exhibit low capacity and poor electrochemical performance for Li-ion storage owing to intrinsic low conductivity and inferior redox activity. Now a redox-active 2D copper–benzoquinoid (Cu-THQ) MOF has been synthesized by a simple solvothermal method. The abundant porosity and intrinsic redox character endow the 2D Cu-THQ MOF with promising electrochemical activity. Superior performance is achieved as a Li-ion battery cathode with a high reversible capacity (387 mA h g⁻¹), large specific energy density (775 Wh kg⁻¹), and good cycling stability. The reaction mechanism is unveiled by comprehensive spectroscopic techniques: a three-electron redox reaction per coordination unit and one-electron redox reaction per copper ion mechanism is demonstrated. This elucidatory understanding sheds new light on future rational design of high-performance MOF-based cathode materials for efficient energy storage and conversion.     

固体氧化物燃料电池Cr毒化La0.8Sr0.2MnO3-δ(LSM)阴极机理

从电化学阻抗谱和阴极极化等方面对Cr毒化La0.8Sr0.2MnO3-δ(LSM)阴极机理进行了研究.     

Cobalt oxyhydroxide/graphene oxide nanocomposite for amelioration of electrochemical performance of lithium/sulfur batteries

Cobalt oxyhydroxide combination with graphene oxide (CoOOH@GO) as a novel conductive matrix is developed for high performance lithium/sulfur batteries. Enhancement retention of polysulfide species into matrix of cobalt oxyhydroxide anchored on graphene oxide flakes by strong chemical binding of carbon-sulfur is demonstrated. Sulfur incorporated in the sheet-like morphology of CoOOH@GO delivers high initial discharge specific capacity of 1190.85 mAh/g, which raises 260 mAh/g with respect to graphene oxide/sulfur (GO/S) as a cathode material. Furthermore, CoOOH@GO/S maintains the average coulombic efficiency of 96 % after 300 cycles at 1 C rate with capacity retention of about 61 %. Good current rate capability of CoOOH@GO/S cathode reveals that the resulting composite is open platform for electrolyte diffusion and fast ion transportation leading to the improved electrochemical performance of lithium/sulfur batteries.     

LiNbO_3-coated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2 cathode with high discharge capacity and rate performance for all-solid-state lithium battery

In order to obtain high power density, energy density and safe energy storage lithium ion batteries(LIB)to meet growing demand for electronic products, oxide cathodes have been widely explored in all-solidstate lithium batteries(ASSLB) using sulfide solid electrolyte. However, the electrochemical performances are still not satisfactory, due to the high interfacial resistance caused by severe interfacial instability between sulfide solid electrolyte and oxide cathode, especially Ni-rich oxide cathodes, in charge-discharge process. Ni-rich LiNi_(0.8)Co_(0.1)Mn_(0.1)O_2(NCM811) material at present is one of the most key cathode candidates to achieve the high energy density up to 300 Wh kg~(-1) in liquid LIB, but rarely investigated in ASSLB using sulfide electrolyte. To design the stable interface between NCM811 and sulfide electrolyte should be extremely necessary. In this work, in view of our previous work, LiNbO_3 coating with about 1 wt%content is adopted to improve the interfacial stability and the electrochemical performances of NCM811 cathode in ASSLB using Li_(10)GeP_2S_(12) solid electrolyte. Consequently, LiNbO_3-coated NCM811 cathode displays the higher discharge capacity and rate performance than the reported oxide electrodes in ASSLB using sulfide solid electrolyte to our knowledge.     

The electrochemical behaviour of zircaloy-4 electrodes in acid iodide solution

Potentiostatic as well as potentiodynamic measurements have been made in order to elucidate the role played by iodide ion in the electroformation and growth of a ZrO₂ film at Zircaloy-4 electrodes. The results show that at potential values close to the corrosion potential, iodide can be adsorbed at the oxide covered electrode with further formation of zirconium-iodide species. As a consequence of this process a partial inhibition in oxide growth is produced. A dissolution-precipitation mechanism which is consistent with the experimental potentiodynamic parameters is proposed for the overall process in which iodide is involved.     

Redox switching and oxygen evolution at oxidized metal and metal oxide electrodes: iron in base

Outstanding issues regarding the film formation, redox switching characteristics and the oxygen evolution reaction (OER) electrocatalytic behaviour of multicycled iron oxyhydroxide films in aqueous alkaline solution have been revisited. The oxide is grown using a repetitive potential multicycling technique, and the mechanism of the latter hydrous oxide formation process has been discussed. A duplex layer model of the oxide/solution interphase region is proposed. The acid/base behaviour of the hydrous oxide and the microdispersed nature of the latter material has been emphasised. The hydrous oxide is considered as a porous assembly of interlinked octahedrally coordinated anionic metal oxyhydroxide surfaquo complexes which form an open network structure. The latter contains considerable quantities of water molecules which facilitate hydroxide ion discharge at the metal site during active oxygen evolution, and also charge compensating cations. The dynamics of redox switching has been quantified via analysis of the cyclic voltammetry response as a function of potential sweep rate using the Laviron-Aoki electron hopping diffusion model by analogy with redox polymer modified electrodes. Steady state Tafel plot analysis has been used to elucidate the kinetics and mechanism of oxygen evolution. Tafel slope values of ca. 60 mV dec(-1) and ca. 120 mV dec(-1) are found at low and high overpotentials respectively, whereas the reaction order with respect to hydroxide ion activity changes from ca. 3/2 to ca. 1 as the potential is increased. These observations are rationalised in terms of a kinetic scheme involving Temkin adsorption and the rate determining formation of a physisorbed hydrogen peroxide intermediate on the oxide surface. The dual Tafel slope behaviour is ascribed to the potential dependence of the surface coverage of adsorbed intermediates.