近化学计量比钽酸锂晶体-生长技术和成分测试方法

近化学计量比钽酸锂晶体的各种优越的物理性质已经吸引了众多研究者们的兴趣.常规提拉法生长的钽酸锂是一种非化学计量比的晶体,晶体中存在大量的本征缺陷,限制了其在高性能器件的应用.研究者们都在努力寻找一种能生长大尺寸高质量晶体的方法,并利用晶体的各种性质制造相应的功能器件.本文综述主要介绍了同成分钽酸锂晶体的缺陷结构和未掺杂和掺镁近化学计量比钽酸锂晶体的生长技术及成分测试方法.     

Strong dependency of lithium diffusion on mechanical constraints in high-capacity Li-ion battery electrodes

The effect of external constraints on Li diffusion in high-capacity Li-ion battery electrodes is investigated us- ing a coupled finite deformation theory. It is found that thin- film electrodes on rigid substrates experience much slower diffusion rates compared with free-standing films with the same material properties and geometric dimensions. More importantly, the study reveals that mechanical driving forces tend to retard diffusion in highly-constrained thin films when lithiation-induced softening is considered, in contrast to the fact that mechanical driving forces always enhance diffusion when deformation is fully elastic. The results provide further proof that nano-particles are a better design option for next-generation alloy-based electrodes compared with thin films.     

过充保护添加剂氰基功能化2, 5-二叔丁基对苯二酚的合成及其在锂离子电池中的应用

设计合成了单氰基功能化的2, 5-二叔丁基-1-（β-氰基乙氧基）-4-甲氧基苯（RS-MCN）和双氰基功能化的2, 5-二叔丁基-1, 4-（β-氰基乙氧基）苯（RS-DCN）,并用作氧化还原过充添加剂开展了其在锂离子电子中的应用研究。通过丙烯氰和2, 5-二叔丁基对苯二酚的迈克尔加成反应可高效合成RS-MCN和RS-DCN,氰乙基取代后的过充保护添加剂分子的可逆氧化还原电位分别为4.02、4.08 V（vs Li/Li⁺）;并且单氰基取代的RS-MCN在商业碳酸酯电解液1 mol·L^-1 LiPF6/EC+DEC+EMC（1：1：1,体积比）中的溶解度可高达0.3 mol·L^-1。RSMCN和RS-DCN对LiFePO₄/Li电池的过充保护性能和电极相容性也进行了深入的研究,实验结果表明：RSMCN具有更好的过充保护性能和电极相容性,其5 V截止电压过充保护时间可超过1200 h,100%过充保护大于90周循环;0.3 mol·L^-1 RS-MCN的添加能使100%过充的LiFePO₄/Li电池在2.5C倍率条件下正常循环,其放电比容量达153.5 mAh·g^-1。此外,RS-MCN的添加对LiFePO₄/Li电池在2.5-3.8 V条件下的循环性能有明显改善,添加有RS-MCN的电池在60周的循环后容量保持率高达94.4%,而商业电解液的电池在60周循环后的容量保持率降至84.3%。因此,氰基功能化RS-MCN是一类具有潜在应用前景的过充保护添加剂。     

Novel electrospun SnO2@carbon nanofibers as high performance anodes for lithium‐ion batteries

SnO₂@carbon (SnO₂@C) nanofibers (NFs) have been prepared by electrospinning method and evaluated as anodes in lithium‐ion battery half cells. XRD were carried out to provide further information about the structure of the as‐prepared NFs, and all the peaks can be readily indexed to the rutile phase SnO₂ (JCPDS No. 41–1445). Electrochemical characterization by galvanostatic charge‐discharge tests shows that the NF anodes have first discharge capacities of 1375.5 mA h g⁻¹ at 80 mA g⁻¹current density. This excellent Li‐ion storage capability of SnO₂ NFs is probably resulting from protection of amorphous carbon and the synergy arising from that the ultrafine SnO₂ particles embedded in the carbon nanofiber (CNF) matrix: the nanometer‐sized SnO₂@C NFs can provide not only negligible diffusion times of ions thus faster phase transitions but also enough space to buffer the volume changes during the lithium insertion and extraction reactions. The highly dispersed NFs are expected to be applied as attractive anodes for lithium‐ion batteries.     

Mesoporous cobalt oxide for largely improved lithium storage properties

We report the microstructure,application for lithium-ion batteries of mesoporous Co3O4 prepared by modified KIT-6 template method.The sample was characterized by XRD,TEM,HRTEM and nitrogen adsorption.Their electrochemical behaviors as electrode reactants for lithium ion batteries were evaluated by cyclic voltammograms and static charge-discharge.A direct comparison of electrochemical behaviors between mesoporous nanostructure and bulk reflects interesting "nanostructure effect",which is reasonably discussed in terms of how the 3D nanostructures of Co3O4 materials function in tuning their electrochemistry.The results demonstrate that further improvement of electrochemical performance in transition metal-oxide-based anode materials can be realized via the design of multiporous nanostructured materials.     

Molecular Ionics in Supramolecular Assemblies with Channel Structures Containing Lithium Ions

A novel trilithium compound, Li₃[B(C₆H₄O₂){O(CH₂CH₂O)₃CH₃}₂][N(SO₂CF₃)₂]₂ ( 1 ‐2.0), with solid‐state ionic conductivity was synthesized. The crystal structure of 1 ‐2.0 consists of the one‐dimensional ionic conduction paths. The paths were afforded as a result of the self‐assembled stacking of the component molecules of 1 ‐2.0 with channel structures containing lithium ions. In this supramolecule, one lithium ion holds the component molecules in specific positions to construct a supramolecular structure with thermally stable ionic conduction paths and the others behave as carrier ions exhibiting selective lithium‐ion conductivity. Owing to the existence of both roles for the lithium ions, this electrolyte shows selective lithium‐ion conductivity.