钴基双金属氧化物的制备及其在电化学储能领域的应用

钴基双金属氧化物MCo₂O₄（M=Ni、Zn、Mn等）既继承了单一钴金属氧化物（Co₃O₄、CoO等）高比容量的优点,又引入了新的改性金属元素用于改善其导电性差、倍率性能不佳等缺点,是一种潜在的新型电化学储能材料。本文分类介绍了NiCo₂O₄、ZnCo₂O₄、MnCo₂O₄等钴基双金属氧化物及其复合物的现有研究（包括制备方法、形貌结构、颗粒尺寸及其电化学性能）,阐述了改性手段的可能性机理,并对钴基双金属氧化物后续研究提出了一些看法。     

钴基双金属氧化物的制备及其在电化学储能领域的应用

钴基双金属氧化物MCo_2O_4(M=Ni、Zn、Mn等)既继承了单一钴金属氧化物(Co_3O_4、Co O等)高比容量的优点,又引入了新的改性金属元素用于改善其导电性差、倍率性能不佳等缺点,是一种潜在的新型电化学储能材料。本文分类介绍了NiCo_2O_4、ZnCo_2O_4、MnCo_2O_4等钴基双金属氧化物及其复合物的现有研究(包括制备方法、形貌结构、颗粒尺寸及其电化学性能),阐述了改性手段的可能性机理,并对钴基双金属氧化物后续研究提出了一些看法。     

Ni0.8Co0.15Al0.05C2O4@Graphene的合成及电化学性能研究

过渡金属氧化物/石墨烯复合材料具有优异的电化学性能被广泛应用在锂离子电池中。本文以硫酸镍、硫酸钴、硫酸铝、草酸为原料按一定的物质的量比配制成溶液,在120°C的条件下水热反应12小时,得到多元过渡金属氧化物前驱体Ni_0.8Co_0.15Al_0.05C₂O₄(NCA-C₂O₄);该前驱体经聚烯丙基胺盐酸盐修饰后,与氧化石墨烯进行复合并还原得到石墨烯包覆的多元过渡金属氧化物/石墨烯负极材料Ni_0.8Co_0.15Al_0.05C₂O₄@Graphene(NCA-C₂O₄@G)。对材料的结构、形貌和电化学性质进行了表征。扫描电镜测试结果显示样品粒度均一,具有两端不规则长方体形貌。电化学性能测试结果表明：石墨烯包覆后的NCA-C₂O₄@G充放电容量高于前驱体NCA-C₂O₄,NCA-C₂O₄@G复合材料在0.1C电流密度 (1C=1000 mAh/g)下首次放电比容量为1956 mA h/g;经过0.1C、0.2C、0.5C、1C、2C高倍率循环后,当测试电流密度恢复至100 mA/g时,复合材料比容量可迅速回升至720 mA h/g,并在随后50次循环中比容量保持稳定,显示出良好的循环稳定性和倍率性能。     

静电纺丝法制备的钴酸镍微米带的磁性以及电化学性能

通过直接退火静电纺丝前驱样品以及调节升温速率最终得到了钴酸镍(NiCo₂O₄)微米带. 通过X射线衍射、扫描电镜、振动样品磁强计以及电化学工作站等分析手段对钴酸镍微米带的晶体结构、形貌、磁学性能以及电化学性能进行了研究. 结果显示, 以1℃·min^-1的升温速率得到的NiCo₂O₄微米带属于立方尖晶石结构, 高温处理后仍能保持一维结构. 室温磁化结果显示制备的NiCo₂O₄微米带具有超顺磁性, 在10 kOe时磁化强度为6.35 emu·g^-1. 此外, 电化学测试结果显示, NiCo₂O₄微米带的电容特性是典型的赝电容, 并且比电容随着放电电流密度的增加而减小.     

表面化学侵蚀改性富锂层状正极材料Li[Li0.2Mn0.54Ni0.13Co0.13]O2

采用3种不同pH值的去离子水,NH₄NO₃和H₂C₂O₄溶液对富锂层状正极材料Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂进行表面化学侵蚀改性,旨在改善其整体电化学性能。ICP结果表明pH值对材料中Li的析出具有显著影响。X射线衍射（XRD）表明表面化学侵蚀对材料的结构有影响。拉曼光谱（Raman spectroscopy）表明材料表面结构发生了变化。H₂C₂O₄溶液侵蚀过的样品的首次效率有了极大提高,但同时中值电压和循环性能显著恶化。NH₄NO₃溶液侵蚀过的样品的首次效率从63%提高到了85%,1C倍率下的放电比容量从149 mAh·g^-1提高到194 mAh·g^-1,同时保持了温和的中值电压变化曲线。通过高分辨透射电镜（HRTEM）,X射线光电子能谱（XPS）和电化学阻抗谱（EIS）对改性机理进行了研究。     

表面化学侵蚀改性富锂层状正极材料Li[Li0.2Mn0.54Ni0.13Co0.13]O2

采用3种不同pH值的去离子水,NH₄NO₃和H₂C₂O₄溶液对富锂层状正极材料Li[Li_0.2Mn_0.54Ni_0.13Co_0.13]O₂进行表面化学侵蚀改性,旨在改善其整体电化学性能。ICP结果表明pH值对材料中Li的析出具有显著影响。X射线衍射（XRD）表明表面化学侵蚀对材料的结构有影响。拉曼光谱（Raman spectroscopy）表明材料表面结构发生了变化。H₂C₂O₄溶液侵蚀过的样品的首次效率有了极大提高,但同时中值电压和循环性能显著恶化。NH₄NO₃溶液侵蚀过的样品的首次效率从63%提高到了85%,1C倍率下的放电比容量从149 mAh·g^-1提高到194 mAh·g^-1,同时保持了温和的中值电压变化曲线。通过高分辨透射电镜（HRTEM）,X射线光电子能谱（XPS）和电化学阻抗谱（EIS）对改性机理进行了研究。     

ZnFe2O4/CNFs钛网基对电极膜厚对染料敏化太阳能电池性能的影响

通过静电纺丝和简单的一步水热法合成了碳纳米纤维（CNFs）负载的ZnFe₂O₄纳米颗粒（ZnFe₂O₄/CNFs）,并将其刮涂在钛网基底上作为染料敏化太阳能电池（DSSCs）的对电极进行组装测试,电池表现出优异的电化学性能。我们着重研究了不同膜厚对电极对DSSCs光电性能的影响。经过反复测试结果表明,当ZnFe₂O₄/CNFs复合电极材料膜厚为12 μm时存在最高的光电转换效率8.60%。     

LaF3表面修饰LiMn2O4的合成方法及电化学性能的研究

通过高温固相法制得尖晶石LiMn₂O₄,然后在通过简单易行的无水乙醇蒸干法包覆LaF₃来修饰LiMn₂O₄。利用XRD,SEM来表征LaF₃修饰的LiMn₂O₄的结构和形貌特征,并通过电化学测试研究LaF₃修饰LiMn₂O₄的高温和常温下的电化学性能,另外结合电化学阻抗谱（EIS）和循环伏安（CV）考察表面修饰的锰酸锂的循环阻抗和循环可逆性。结果显示：经LaF₃修饰过的LiMn₂O₄仍具有尖晶石结构,并且具有良好的电学性能。其中,以3wt%的修饰效果最好,常温循环100次和高温循环50次的循环保持率分别是91%和90%;而且,EIS和CV分别表明经LaF₃修饰的LiMn₂O₄的电荷传递阻抗明显减小,其循环可逆性也明显提高。     

水相锌二次电池正极材料V2O5/C的电化学性能研究

采用溶胶－凝胶法合成了一种V₂O₅/C复合材料.扫描电镜（SEM）和红外光谱（FTIR）分析表明,这是一种外层V₂O₅胶体包覆内层乙炔分子的多孔复合材料.以V₂O₅/C作正极,锌片为负极,Zn(ClO₄)₂溶液为电解质组成水相锌二次电池,采用循环伏安（CV）和电化学阻抗谱（EIS）等方法研究发现:V₂O₅:C质量比为1:1时电极具有最好的电化学性能,电池开路电压达1.64 V; Zn^2＋能分别在1.01 V和1.26 V处分步嵌入V₂O₅/C结构中A、B两种位置,其嵌入电流密度峰值最高可达70 mA•g^－1,并且具有较好的循环充放电性能;在一定放电深度下,V₂O₅/C电极反应速率受Zn^2＋的扩散过程控制.     

铝基化合物改性富锂锰三元正极材料的高温性能

通过多相复合分别制备了Al₂O₃、AlF₃、AlPO₄改性的富锂锰三元正极材料(Li_1.2Ni_0.133Co_0.133Mn_0.533O₂,LR)。采用X射线光电子能谱、透射电镜和电化学交流阻抗等对复合材料的成分结构、高温下的电化学性能及作用机理进行了研究。结果表明：Al₂O₃改性的Li_1.2Ni_0.133Co_0.133Mn_0.533O₂(LRO)性能最佳,包覆层薄且均匀;在50℃高温下,LRO的200圈平均放电比容量为189.5mAh·g^-1,容量保持率为81.5%,比原材料分别提高61.5 mAh·g^-1、49.8%;100圈循环后的电荷转移电阻为443.1 Ω,仅为原材料一半,表现出较优的电化学性能。     

Recent advances of transition metal oxalate-based micro- and nanomaterials for electrochemical energy storage: a review

A key challenge in the development of electrochemical energy storage (EES) is the design and engineering of electrode materials for electrochemical reactions. Transition metal oxalates (TMOxs) have been widely used in various EES applications due to their low cost, simple synthesis, and excellent electrochemical performance. In this review, the recent advances in the design and engineering of transition metal oxalate-based micro- and nanomaterials for EES are summarized. Specifically, the survey will focus on three types of micro- and nano-scale TMOxs (monometallic, bimetallic, and trimetallic TMOxs), their composites (TMOx-metal oxide, TMOx-hydroxide, TMOx-GO, and TMOx-MOFs composites), and derivatives, including transition metal oxides (TiO₂, V₂O₅, Mn_xO_y, Co₃O₄, NiO, CuO, and Nb₂O₅), multi-transition metal oxides (MCo₂O₄ (M = Ni, Cu, and Zn), NiMn₂O₄, and N_xO_y-M_xO_y), transition metal sulfide (NiS₂), and carbon materials (ordinary carbon, GO and their composites), within the context of their intrinsic structure and corresponding electrochemical performance. A range of experimental variables will be carefully analyzed, such as sample synthesis, crystal structure, and electrochemical reaction mechanism. The applications of these materials as EES electrodes are then featured for supercapacitors (SCs) and lithium-ion batteries (LIBs). We conclude the review with a perspective of future research prospects and challenges.     

Synthesis of Co3O4/CoOOH via electrochemical dispersion using a pulse alternating current method for lithium-ion batteries and supercapacitors

We report a convenient, low-cost and ecofriendly approach for the fabrication of a Co₃O₄/CoOOH electrode material intended for lithium ion batteries (LIBs) and supercapacitors (SCs) using the electrochemical dispersion of the cobalt foil through the pulse alternating current (PAC) method. The synthesized material is a Co₃O₄/CoOOH composite (with about 10–15 wt% CoOOH) in the form of nanosheets with a length of approximately 200 nm and a thickness of 10–20 nm. It is found to exhibit high reversible discharge specific capacities and good cycling behavior while tested as the anode material in LIBs. Measuring the reversible capacitance at high (2C) and low (C/20) cycling rates gives the values of 610 mAh g⁻¹ and 1030 mAh g⁻¹, respectively. The specimen possesses excellent performance as the electrode for SCs with the retention of capacitance up to 98% at the current density increasing from 0.5 to 10 A g⁻¹. After 1000 cycles at a current density of 10 A g⁻¹ the electrode maintains about 90% of its initial capacitance which evidences the long cycle life. Hence, electrochemically prepared Co₃O₄/CoOOH seems to be a promising candidate for high-performance LIBs and SCs applications.     

锂离子电池片状四氧化三钴负极的合成及改性

采用液相沉淀法结合低温固相热解法合成了锂离子电池片状Co3O4负极.通过X射线粉体衍射(XRD)、Brunauer-Emmett-Teller(BET)比表面积分析、扫描电子显微镜(SEM)及恒电流充放电等表征手段,发现该Co3O4为立方相,结晶完整且无杂质,由直径为1.5-3.0μm、厚度约为100-300 nm的不规则片状颗粒组成,比表面积约为30.5 m2·g-1;其比容量高且容量保持率好,在0.1C倍率下,首次放电容量高达1444.5 mAh·g-1,50次循环后充电容量仍大于1100.0 mAh·g-1;但在高倍率(1C)下,50次循环后充电容量保持率仅为75.3%,倍率性能一般.故采用碳纳米管(CNTs)掺杂改性,结果表明:在1C倍率下,70次循环后复合材料充电容量保持率为96.3%;在2C倍率下,50次循环后充电容量保持率仍高达97.0%,倍率性能显著提升.     

Recent Advances of ZnCo2O4-based Anode Materials for Li-ion Batteries

ZnCo₂O₄ has been attracted wide research attention as a promising anode material for lithium-ion batteries (LIBs) in recent years based on its high theoretical specific capacity, low toxicity as well as stable chemical properties. However, the further large-scale application of pristine ZnCo₂O₄ anode have been impeded because of its undesirable Li⁺ ion conductivity, low electronic conductivity, and finite stability of electrolytes at high potentials. Recently, optimizing the micro/nano structure, modification with carbonaceous materials, incorporation with metal oxides and constructing a binder-free structure on conductive substrate for ZnCo₂O₄-based materials have been verified as promising effective routes for solving the above problems. In this review, the recent advances in underlying reaction mechanisms, synthetic methods and strategies for improving the performance of ZnCo₂O₄ anodes are comprehensively summarized. The factors affecting the electrochemical properties of ZnCo₂O₄-based materials are mainly discussed, and paths to promote the specific capacity and cyclic stability are proposed. Finally, several insights into the future developments, challenges, and prospects of ZnCo₂O₄-based anode materials of LIBs are proposed.     

Calcination-Free Synthesis of Well-Dispersed and Sub-10 nm Spinel Ferrite Nanoparticles as High-Performance Anode Materials for Lithium-Ion Batteries: A Case Study of CoFe2O4

Spinel ferrites are promising anode materials for lithium-ion batteries (LIBs) owing to their high theoretical specific capacities. However, their practical application is impeded by inherent low conductivity and severe volume expansion, which can be surpassed by increasing the surface-to-volume ratio of nanoparticles. Currently, most methods produce spinel ferrite nanoparticles with large size and severe aggregation, degrading their electrochemical performance. In this study, a low-temperature aminolytic route was designed to synthesize sub-10 nm CoFe₂O₄ nanoparticles with good dispersion through carefully exploiting the reaction of acetates and oleylamine. The performance of CoFe₂O₄ nanoparticles obtained by a traditional co-precipitation method was also investigated for comparison. This work demonstrates that CoFe₂O₄ nanoparticles synthesized by the aminolytic route are promising as anode materials for LIBs. Besides, this method can be extended to design other spinel ferrites for energy storage devices with superior performance by simply changing the starting material, such as MnFe₂O₄, MgFe₂O₄, ZnFe₂O₄, and so on.     

The synergic effects of Ca and Sm co-doping on the crystal structure and electrochemical performances of Li4-xCaxTi5-xSmxO12 anode material

Li₄Ti₅O₁₂ as the well-known “zero strain” anode material for lithium ion batteries (LIBs) suffers from low intrinsic ionic and electronic conductivity. The strategy of lattice doping has been widely taken to relieve the intrinsic issues. But the roles of the dopants are poorly understood. Herein, we propose to modulate the crystal structure and improve the electrochemical performance of Li₄Ti₅O₁₂ by substituting Li and Ti with Ca and Sm, respectively. The roles of Ca and Sm on the crystal structure and electrochemical performances have been comprehensively investigated by means of X-ray diffraction (XRD), neutron diffraction (ND) and electrochemical analysis. The Rietveld refinement of ND data indicate that Ca and Sm prefer to take 8a site (tetrahedral site) and 16d site (octahedral site), respectively. Li_3.98Ca_0.02Ti_4.98Sm_0.02O₁₂ has the longer Li1-O bond and shorter Ti-O bond length which reduces Li⁺ migration barrier as well as enhances the structure stability. Ca-Sm co-doping also alleviates the electrode polarization and enhances the reversibility of oxidation and reduction. In compared to bare Li₄Ti₅O₁₂ and Li_3.95Ca_0.05Ti_4.95Sm_0.05O₁₂, Li_3.98Ca_0.02Ti_4.98Sm_0.02O₁₂ electrode shows the lower charge transfer resistance, higher Li⁺ diffusion coefficient, better rate capability and cycling performance. The proposed insights on the roles of dopants are also instructive to design high performance electrode materials by lattice doping.     

Recent progress on lithium-ion batteries with high electrochemical performance

Lithium-ion batteries(LIBs) have been widely used in many fields such as portable electronics and electric vehicles since their successful commercialization in the 1990 s. However, the electrochemical performance of current commercial LIBs still needs to be further improved to meet the continuously increasing demands for energy storage applications. Recently, tremendous research efforts have been made in developing next-generation LIBs with enhanced electrochemical performance. In this review, we mainly focus on the recent progress of LIBs with high electrochemical performance from four aspects, including cathode materials, anode materials, electrolyte, and separators. We discuss not only the commercial electrode materials(LiCoO_2,LiFePO_4, LiMn_2O_4, LiNi_xMn_yCo_zO_2, LiNi_xCo_yAl_zO_2, and graphite) but also other promising next-generation materials such as Li-, Mn-rich layered oxides, organic cathode materials, Si, and Li metal. For each type of materials, we highlight their problems and corresponding strategies to enhance their electrochemical performance. Nowadays, one of the key challenges to construct high-performance LIBs is how to develop cathode materials with high capacity and working voltage. This review provides an overview and future perspectives to develop next-generation LIBs with high electrochemical performance.     

Multilayered structure of N-carbonenvelopediron oxide/graphene nanocomposites as an improved anode for Li-ion battery

Transition metal oxides with high capacity are considered a promising electrode material for lithium-ion batteries (LIBs). Nevertheless, the huge volume expansion and poor conductivity severely hamper their practical application. In this work, a carbon riveting method is reported to address the above issues by designing multilayered N-doped carbon (N-carbon) enveloped Fe₃O₄/graphene nanosheets. When evaluated as a negative electrode, the N-carbon/Fe₃O₄/graphene nanocomposites demonstrate greatly enhanced electrochemical properties compared with Fe₃O₄/graphene. The N-carbon/Fe₃O₄/graphene presents a superior reversible capacity (807 mAh/g) over Fe₃O₄/graphene (540 mAh/g). Furthermore, it affords a considerable capacity of 550 mAh/g at 1 A/g over 700 cycles, indicating superb cycling stability. The structure-property correlation studies reveal that the carbon riveting layer is essential for enhancing the lithium diffusion kinetics. The good electrochemical properties and effective structure design make the carbon riveting strategy quite general and reliable to manipulate high performance electrodes for future LIBs.     

A Core–Shell Fe/Fe2O3 Nanowire as a High‐Performance Anode Material for Lithium‐Ion Batteries

The preparation of novel one‐dimensional core–shell Fe/Fe₂O₃ nanowires as anodes for high‐performance lithium‐ion batteries (LIBs) is reported. The nanowires are prepared in a facile synthetic process in aqueous solution under ambient conditions with subsequent annealing treatment that could tune the capacity for lithium storage. When this hybrid is used as an anode material for LIBs, the outer Fe₂O₃ shell can act as an electrochemically active material to store and release lithium ions, whereas the highly conductive and inactive Fe core functions as nothing more than an efficient electrical conducting pathway and a remarkable buffer to tolerate volume changes of the electrode materials during the insertion and extraction of lithium ions. The core–shell Fe/Fe₂O₃ nanowire maintains an excellent reversible capacity of over 767 mA h g^?1 at 500 mA g^?1 after 200 cycles with a high average Coulombic efficiency of 98.6 %. Even at 2000 mA g^?1, a stable capacity as high as 538 mA h g^?1 could be obtained. The unique composition and nanostructure of this electrode material contribute to this enhanced electrochemical performance. Due to the ease of large‐scale fabrication and superior electrochemical performance, these hybrid nanowires are promising anode materials for the next generation of high‐performance LIBs.