钙熔盐电解石墨阳极破损机理及防护研究

通过扫描电镜和电子探针分析钙熔盐电解中破损石墨阳极的结构和杂质,探索了其破损机理,认为主要是由于孔隙存在导致氧化和孔隙吸附电解质,电解质因水解、脱水等过程使其周围的石墨阳极颗粒受应力不平衡而发生破损.通过实验研制出适合于钙熔盐电解过程用的石墨阳极具有抗氧化性能的涂层,并对涂层进行了XRD,SEM分析和氧化失重实验.实验表明该涂层在680～750℃下成硼玻璃态,能渗透到石墨阳极孔隙中,涂层表面致密无裂纹且附着力强,因而具有较好的抗氧化能力.该涂层是一种适合钙熔盐电解的、性能优良的石墨阳极涂层.     

Ti基IrO2＋Ta2O5阳极在H2SO4溶液中的电解时效行为

研究了450 ℃制备所得Ti/70％IrO2 30％Ta2O5（摩尔分数）高寿命阳极在H2SO4溶液电解过程中电极的物理、化学及电化学性能的时效行为.结果发现，整个电解过程可分为“活化”、“稳定”及“失效”三个阶段.在“活化”及“稳定”区内主要发生电极表面活性氧化物的溶解，涂层中IrO2金红石相的（110）、（101）晶面择优取向随电解时间延长而减弱，而（002）晶面择优增强.但是在“失效区”内，各晶面的择优程度却不随电解时间的变化而变化，这表明在“失效区”内氧化物的损失机制发生了变化.电化学阻抗谱测试表明，电极的析氧电化学反应电阻随电解时间的延长发生缓慢而连续的上升，而整个电极的物理阻抗在“失效区”内却发生突升现象.X射线衍射分析（XRD）表明，随电解时间的延长TiO2金红石相的衍射强度增大，达“失效区”时衍射强度发生突升.根据实验现象特别是“失效区”内阳极的时效行为提出高寿命Ti基氧化物涂层阳极的失效机制.     

添加铈对铅钙合金在硫酸溶液中电化学性能的影响

为了改善铅钙合金的耐腐蚀性能和提高铅蓄电池的循环寿命, 应用交流阻抗, 阳极极化曲线, 交流伏安, 恒流腐蚀等方法研究了在铅钙锡铝合金中添加铈对合金电化学性能的影响. 研究结果表明: 铈能提高合金的耐腐蚀能力, 添加铈使合金腐蚀膜的阻抗明显降低, 有利于缓解早期容量损失(PCL-1)现象, 实验电池的循环寿命也明显延长. 因此掺铈铅钙合金是一种性能优良的阀控式铅酸电池正极板栅合金材料.     

铱钽钛金属氧化物阳极的电化学特性

采用热分解方法在钛基体上制备铱钽钛金属氧化物阳极 ,用扫描电镜对阳极涂层显微形貌进行分析 ,通过强化电解寿命试验、开路电位测试、消耗率试验及循环伏安曲线研究了金属氧化物阳极的电化学性能 .SEM分析结果表明铱钽钛金属氧化物阳极涂层呈现多孔多裂纹形貌结构 .随阳极涂层组成不同 ,涂层显微形貌表现出很大差异 ,这种差异直接影响阳极电化学性能 .电化学性能试验结果表明铱钽钛金属氧化物阳极在酸性介质和海水中具有良好的电化学稳定性和电化学活性 .此外 ,铱钽钛金属氧化物阳极在海水中的消耗率很低 ,属于不溶性的阳极材料 ,作为外加电流阴极保护用辅助阳极具有广泛的应用前景 .     

Gd_(0.2)Ce_(0.8)O_2包覆固体氧化物燃料电池Ni-ScSZ复合阳极制备及性能表征

应用双层流延法制备Ni-ScSZ阳极支撑体-ScSZ电解质复合膜素坯,经共烧结得到复合膜.以硝酸铈和硝酸钆为原料,柠檬酸作燃料,由燃烧合成法制备Gd0.2Ce0.8O2(GDC)包覆的Ni-ScSZ阳极.X-射线衍射(XRD)和电子显微镜(TEM和SEM)分析显示,Ni-ScSZ阳极颗粒表面的包覆层是由直径小于100 nm的GDC微粒构成,并与Ni-ScSZ阳极颗粒紧密烧结在一起.实验表明,2.0%(by mass)GDC包覆的Ni-ScSZ阳极具有较佳的性能,以其组装的单电池在850℃用H2或CH4作燃料的最大功率密度分别是825和848 mW/cm2,而由无包覆的Ni-ScSZ作阳极的单电池,功率密度分别是584和586 mW/cm2.由两种阳极材料组装的单电池,分别在700℃于CH4气氛下作长时间发电实验,发现2.0%(by mass)GDC包覆的Ni-ScSZ阳极比Ni-ScSZ阳极具有较好的抗碳沉积性能.     

海水电解Ru-Ti-Ir-Sn氧化物阳极涂层研究

应用热分解法制备不同组分的Ru-Ti-Ir-Sn氧化物阳极涂层,并由SEM、EDX、强化电解寿命、电流效率、抗Mn2+污染、极化曲线和循环伏安等实验方法研究该Ru-Ti-Ir-Sn氧化物阳极涂层的物理性能和电化学性能.结果表明,优化配方的Ru-Ti-Ir-Sn氧化物阳极涂层对电解海水具有较好的综合性能.     

氯离子对硫化矿发电浸出过程影响的机理研究

采用双电池体系综合考虑了Cl-对硫化矿的FeCl3浸出过程的影响.研究结果表明,Cl-对所研究各硫化矿发电浸出的影响效果类似:阳极电解液中Cl-直接参与硫化矿发电浸出过程.发电输出功率随着Cl-浓度的增加而增加,但是浓度增大到一定程度时,其影响作用减弱.本研究对各矿物提出了相应的反应机理,建立了各体系发电浸出速率与[Cl-]的动力学关系,对镍精矿、铜精矿、闪锌矿及方铅矿体系分别为:模型与实验结果吻合.     

热处理对化学沉积Ni-Fe-P合金性能的影响

采用DSC和XRD研究了化学镀Ni-Fe-P合金的晶化行为和结构.结果表明,镀态合金呈非晶结构, 367.6 ℃下热处理出现亚稳态Ni5P2(P3)和Fe-Ni(Im3m), 499.2 ℃下热处理进一步晶化为稳定的Ni3P(I-4)和FeNi3(Pm3m).采用磁性能实验和在w=3.5％氯化钠溶液浸泡实验以及阳极极化实验研究了热处理对镀层磁性能和耐腐蚀性的影响.结果表明,该镀层在镀态时几乎没有磁性,随着退火温度的升高,磁性能不断提高. 400 ℃以后,镀层的饱和磁化强度和矫顽力随着退火温度升高而急剧上升.浸泡实验和阳极极化实验结果均表明镀态镀层比经热处理后的镀层在w=3.5％氯化钠溶液中具有更好的耐腐蚀性,但是它们的阳极极化行为不同.     

稀土元素镧对锌阳极带电化学性能的影响

研究了镧的加入对牺牲锌阳极带电化学性能的影响。结果表明，稀土元素镧对锌阳极带的电位和电流效率影响很小，实验结果符合相关标准。证明在纯锌中添加微量稀土元素镧改善锌阳极带机械性能，同时保持必要的电化学性能的工艺方法是有效、可行的。     

阳极氧化法制备阀金属氧化物纳米管的机理及影响因素

阳极氧化法不仅能够简便地制备出阀金属氧化物纳米管,而且通过调节各种参数可以调控所制备纳米管的形貌.阳极氧化法制备的纳米管具有优异的化学/物理性能,在众多领域都得到了广泛应用.本文综述了阳极氧化法制备纳米管膜的基本过程以及三种常见的模型,并以三种具有代表性的阀金属(Al、Ti、Zr)为例,分别介绍了它们形成多孔膜反应过程和常用的制备过程,同时也介绍了其他阀金属及其合金的制备方案.最后,结合对Al、Ti、Zr的实验过程,讨论、分析了电压大小、电解液种类、电解液浓度、反应时间等控制因素对阳极氧化法制备纳米管膜形貌的影响,对制备形貌规整的多孔膜,提高多孔膜在实际应用中的性能具有一定的意义.     

Amide-Functionalized Porous Carbonaceous Anode Materials for Lithium-Ion Batteries

Porous carbonaceous anode materials have received considerable attention as an alternative anode material, however, there is a critical bottleneck as it suffers from a large irreversible specific capacity loss over several initial cycles owing to undesired surface reactions. In order to suppress undesired surface reactions of porous carbonaceous anode material, here, we suggest a simple and convenient two-step surface modification approach that allows the embedding of an amide functional group on the surface of a porous carbonaceous anode, which effectively improves the surface stability. In this approach, the porous carbonaceous anode material is firstly activated by means of strong acid treatment comprising a combination of H₂SO₄ and HNO₃, and it is subjected to further modification by means of an amide coupling reaction. Our additional systematic analyses confirm that the acid functional group effectively transforms into the amide functional group. The resulting amide-functionalized porous carbon exhibits an improved electrochemical performance: the initial discharge specific capacity is greatly reduced to less than 2,620 mA h g⁻¹ and charge specific capacity is well still remained, indicating stabling cycling performance of the cell.     

Engineering of Silicon Core-Shell Structures for Li-ion Anodes

The amount of silicon in anode materials for Li-ion batteries is still limited by the huge volume changes during charge-discharge cycles. Such changes lead to the loss of electrical contacts, as well as mechanical and surface electrolyte interphase (SEI) instabilities, strongly reducing the cycle life. Core-shell structures have attracted a vast research interest due to the possibility of modifying some properties with a judicious choice of the shell. It is, for example, possible to improve the electronic conductivity and ionic diffusion, or buffer volume variations. This review gives a comprehensive overview of the recent developments and the different strategies used for the design, synthesis and electrochemical performance of silicon-based core-shells. It is based on a selection of the main types of silicon coatings reported in the literature, including carbon, inorganic, organic and double-layer coatings, Finally, a summary of the advantages and drawbacks of these different types of core-shells as anode materials for Li-ion batteries and some insightful suggestions in regards to their use are provided.     

Electrochemical performances of lithium ion batteries from hydrothermally synthesized LiFePO4 and carbon spherules

Hydrothermally synthesized LiFePO₄ cathode and carbon spherules anode materials were investigated by full-cells for the first time. The assembled half-cells suggest that electrode materials prepared hydrothermally have excellent electrochemical properties. Despite having a capacity loss during the formation process, the assembled LiFePO₄/CS full-cells still exhibit an excellent cycling performance with stable coulombic efficiency at 100% and less than 9% capacity fading after 260 cycles, which suggest that hydrothermally fabricated electrode materials have a potential application in EVs and stationary energy storage.     

镓酸镧基中温-SOFC的新型阳极NiO-La0.3Ce0.7O2-δ研究

采用共沉淀法制备了NiO-La0.3Ce0.7O2-δ(LDC30)新型阳极材料, 通过对其配方与性能的研究, 探索获得中温SOFC高性能阳极材料的新途径.     

Prelithiation Reagents and Strategies on High Energy Lithium-Ion Batteries

Lithium-ion batteries (LIBs) have been widely employed in energy-storage applications owing to the relatively higher energy density and longer cycling life. However, they still need further improvement especially on the energy density to satisfy the increasing demands on the market. In this respect, the irreversible capacity loss (ICL) in the initial cycle is a critical challenge due to the lithium loss during the formation of solid electrolyte interphase (SEI) layer on the anode surface. The strategy of prelithiation was then proposed to compensate for the ICL in the anode and recover the energy density. Here, various methods of the prelithiation are summarized and classified according to the basic working mechanism. Further, considering the critical importance and promising progress of prelithiation in both fundamental research and real applications, this Review article is intended to discuss the considerations involved in the selection of prelithiation reagents/strategies and the electrochemical performance in full-cells. Moreover, insights are provided regarding the practical application prospects and the challenges that still need to be addressed.     

High Power- and Energy-Density Supercapacitors through the Chlorine Respiration Mechanism

Supercapacitor represents an important electrical energy storage technology with high-power performance and superior cyclability. However, currently commercialized supercapacitors still suffer limited energy densities. Here we report an unprecedentedly respiring supercapacitor with chlorine gas iteratively re-inspires in porous carbon materials, that improves the energy density by orders of magnitude. Both electrochemical results and theoretical calculations show that porous carbon with pore size around 3 nm delivers the best chlorine evolution and adsorption performance. The respiring supercapacitor with multi-wall carbon nanotube as the cathode and NaTi₂(PO₄)₃ as the anode can store specific energy of 33 Wh kg⁻¹ with negligible capacity loss over 30 000 cycles. The energy density can be further improved to 53 Wh kg⁻¹ by replacing NaTi₂(PO₄)₃ with zinc anode. Furthermore, thanks to the extraordinary reaction kinetics of chlorine gas, this respiring supercapacitor performs an extremely high-power density of 50 000 W kg⁻¹.     

Nafion/Titanium Dioxide‐Coated Lithium Anode for Stable Lithium–Sulfur Batteries

Lithium–sulfur (Li–S) batteries have shown great potential as high energy‐storage devices. However, the stability of the Li metal anode is still a major concern. This is due to the formation of lithium dendrites and severe side reactions with polysulfide intermediates. We herein develop an anode protection method by coating a Nafion/TiO₂ composite layer on the Li anode to solve these problems. In this architecture, Nafion suppresses the growth of Li dendrites, protects the Li anode, and prevents side reactions between polysulfides and the Li anode. Moreover, doped TiO₂ further improves the ionic conductivity and mechanical properties of the Nafion membrane. Li–S batteries with a Nafion/TiO₂‐coated Li anode exhibit better cycling stability (776 mA h g^?1 after 100 cycles at 0.2 C, 1 C=1672 mA g^?1) and higher rate performance (787 mA h g^?1 at 2 C) than those with a pristine Li anode. This work provides an alternative way to construct stable Li anodes for high‐performance Li–S batteries.     

Research Progress toward Room Temperature Sodium Sulfur Batteries: A Review

Lithium metal batteries have achieved large-scale application, but still have limitations such as poor safety performance and high cost, and limited lithium resources limit the production of lithium batteries. The construction of these devices is also hampered by limited lithium supplies. Therefore, it is particularly important to find alternative metals for lithium replacement. Sodium has the properties of rich in content, low cost and ability to provide high voltage, which makes it an ideal substitute for lithium. Sulfur-based materials have attributes of high energy density, high theoretical specific capacity and are easily oxidized. They may be used as cathodes matched with sodium anodes to form a sodium-sulfur battery. Traditional sodium-sulfur batteries are used at a temperature of about 300 °C. In order to solve problems associated with flammability, explosiveness and energy loss caused by high-temperature use conditions, most research is now focused on the development of room temperature sodium-sulfur batteries. Regardless of safety performance or energy storage performance, room temperature sodium-sulfur batteries have great potential as next-generation secondary batteries. This article summarizes the working principle and existing problems for room temperature sodium-sulfur battery, and summarizes the methods necessary to solve key scientific problems to improve the comprehensive energy storage performance of sodium-sulfur battery from four aspects: cathode, anode, electrolyte and separator.     

Building Polymeric Framework Layer for Stable Solid Electrolyte Interphase on Natural Graphite Anode

The overall electrochemical performance of natural graphite is intimately associated with the solid electrolyte interphase (SEI) layer developed on its surface. To suppress the interfacial electrolyte decomposition reactions and the high irreversible capacity loss relating to the SEI formation on a natural graphite (NG) surface, we propose a new design of the artificial SEI by the functional molecular cross-linking framework layer, which was synthesized by grafting acrylic acid (AA) and N,N′−methylenebisacrylamide (MBAA) via an in situ polymerization reaction. The functional polymeric framework constructs a robust covalent bonding onto the NG surface with —COOH and facilitates Li⁺ conduction owing to the effect of the —CONH group, contributing to forming an SEI layer of excellent stability, flexibility, and compactness. From all the benefits, the initial coulombic efficiency, rate performance, and cycling performance of the graphite anode are remarkably improved. In addition, the full cell using the LiNi_0.5Co_0.2Mn_0.3O₂ cathode against the modified NG anode exhibits much-prolonged cycle life with a capacity retention of 82.75% after 500 cycles, significantly higher than the cell using the pristine NG anode. The mechanisms relating to the artificial SEI growth on the graphite surface were analyzed. This strategy provides an efficient and feasible approach to the surface optimization for the NG anode in LIBs.     

Electrospun Sb2Se3@C nanofibers with excellent lithium storage properties

Antimony-based materials have become promising anodes within lithium-ion batteries(LIBs)due to their low cost and the high theoretical capacity.However,there is a potential to further enhance the electrochemical performance of such antimony-based materials.Herein,Sb2Se3@C nanofibers(Sb2Se3@CNFs)are designed and obtained via a novel electrospinning method.Upon electrochemically testing as an anode within LIBs,the Sb2Se3@CNFs(annealed at 600℃)delivers a remarkably good cycling performance of 625 mAh/g at 100 mA/g after 100 cycles.Moreover,it still remains at 490 mAh/g after 500 cycles with an applied current density of 1.0 A/g.The excellent performance of the Sb2 Se3@CNFs can be attributed to the fact that the N-doped C matrices not only remit the volume expansion of materials,but also enhance the electrical and ionic conductivity thusly increasing the lithium-ion diffusion.The obtained Sb2Se3@CNFs are promising anode for LIBs in the future.