锂硫电池硫正极材料研究现状与展望

综述了锂硫电池硫正极材料的研究现状。针对锂硫电池目前存在的问题,展望了其发展趋势,并指出硫/有序多孔碳纳米复合材料对提升锂硫电池性能有重要研究价值;同时形成三维空间传导网络的导电添加剂和具有良好粘接性、导电性及电化学稳定性的粘结剂对锂硫电池性能提升也具有重要作用。     

In situ synthesis of SnO2/graphene nanocomposite and their application as anode material for lithium ion battery

SnO₂/graphene nanocomposite was prepared via an in situ chemical synthesis method. The nanocomposite was characterized by X-ray diffraction, filed emission scanning electron microscope and transmission electron microscope, which revealed that tiny SnO₂ nanoparticles could be homogeneously distributed on the graphene matrix. The electrochemical performance of the SnO₂/graphene nanocomposite as anode material was measured by galvanostatic charge/discharge cycling. The SnO₂/graphene nanocomposite showed a reversible capacity of 665 mAh/g after 50 cycles and an excellent cycling performance for lithium ion battery, which was ascribed to the three-dimensional architecture of SnO₂/graphene nanocomposite. These results suggest that SnO₂/graphene nanocomposite would be a promising anode material for lithium ion battery.     

Lithium batteries: a new tool in solid state chemistry

Lithium batteries are being intensively studied owing to the considerable challenge they represent for applications. From a fundamental point of view, the shape of the charge/discharge curves gives information on all the structural and physical properties modifications which occur during the intercalation/deintercalation process. Moreover, the electrochemical reaction is a way of synthesising metastable materials which cannot be obtained by classical methods. The ease of monitoring very accurately either the cell voltage (oxidation state of the material) or the number of electrons transferred (lithium content in the material) makes lithium batteries a new very convenient tool for the solid state chemist. Typical examples are presented.     

锂离子电池正极材料的研究进展

综述了近年来发展起来的一些锂离子电池正极材料 ,主要包括嵌锂的层状LixMO2 结构和尖晶石型LixM2 O4 结构的过渡金属氧化物 (M =Co、Ni、Mn、Cr等 )。重点介绍了锂钴氧化物、锂镍氧化物、锂锰氧化物的性能、制备、结构以及改性方法等 ,并对纳米电极材料和其它正极材料的发展情况作了简介     

3D Graphene Networks Encapsulated with Ultrathin SnS Nanosheets@Hollow Mesoporous Carbon Spheres Nanocomposite with Pseudocapacitance‐Enhanced Lithium and Sodium Storage Kinetics

The lithium and sodium storage performances of SnS anode often undergo rapid capacity decay and poor rate capability owing to its huge volume fluctuation and structural instability upon the repeated charge/discharge processes. Herein, a novel and versatile method is described for in situ synthesis of ultrathin SnS nanosheets inside and outside hollow mesoporous carbon spheres crosslinked reduced graphene oxide networks. Thus, 3D honeycomb‐like network architecture is formed. Systematic electrochemical studies manifest that this nanocomposite as anode material for lithium‐ion batteries delivers a high charge capacity of 1027 mAh g^?1 at 0.2 A g^?1 after 100 cycles. Meanwhile, the as‐developed nanocomposite still retains a charge capacity of 524 mAh g^?1 at 0.1 A g^?1 after 100 cycles for sodium‐ion batteries. In addition, the electrochemical kinetics analysis verifies the basic principles of enhanced rate capacity. The appealing electrochemical performance for both lithium‐ion batteries and sodium‐ion batteries can be mainly related to the porous 3D interconnected architecture, in which the nanoscale SnS nanosheets not only offer decreased ion diffusion pathways and fast Li⁺/Na⁺ transport kinetics, but also the 3D interconnected conductive networks constructed from the hollow mesoporous carbon spheres and reduced graphene oxide enhance the conductivity and ensure the structural integrity.     

CeO2纳米晶的添加对锂硫电池电化学性能的影响

以Ce(OH)₄为原料, 采用热分解法制备得到粒径小于10 nm的CeO₂纳米晶。制备得到的CeO₂纳米晶表面存在丰富的羟基和硝基, 作为硫正极添加剂, 一方面可以有效吸附硫和多硫化锂, 抑制多硫化锂在电解液中的溶解和穿梭效应的发生, 进而提高电池的循环性能。同时, 可以改善电极和电解液之间的接触性, 提高活性物质利用率。其中, 含有5wt%的CeO₂纳米晶的锂硫电池在0.1C和0.5C(1C=1675 mA/g)的充放电倍率下, 100周之后放电比容量分别达750 mAh/g和598 mAh/g, 远高于不含有CeO₂纳米晶的523 mAh/g和395 mAh/g, 同时, 循环前后的电池阻抗也明显降低。     

Pressure-Stabilized High-Entropy (FeCoNiCuRu)S2 Sulfide Anode toward Simultaneously Fast and Durable Lithium/Sodium Ion Storage

Pressure-stabilized high-entropy sulfide (FeCoNiCuRu)S₂ (HES) is proposed as an anode material for fast and long-term stable lithium/sodium storage performance (over 85% retention after 15 000 cycles @10 A g⁻¹). Its superior electrochemical performance is strongly related to the increased electrical conductivity and slow diffusion characteristics of entropy-stabilized HES. The reversible conversion reaction mechanism, investigated by ex-situ XRD, XPS, TEM, and NMR, further confirms the stability of the host matrix of HES after the completion of the whole conversion process. A practical demonstration of assembled lithium/sodium capacitors also confirms the high energy/power density and long-term stability (retention of 92% over 15 000 cycles @5 A g⁻¹) of this material. The findings point to a feasible high-pressure route to realize new high-entropy materials for optimized energy storage performance.     

锂离子电池正极材料LiNi-x-yCoxMnyO2的研究现状

正极材料对锂离子电池的性能和价格具有决定性的作用，对正极材料的研究一直是锂离子电池研究中的热点。主要对一类新型正极材料LiNi-x-yCoxMnyO2的国内外研究现状进行了综述，并比较了不同合成方法对其电化学性能的影响，最后对这类正极材料的研究给予了展望。     

石墨烯/CuO锂离子电池负极材料的研究进展

石墨烯作为一种锂离子电池负极材料表现出优异的电化学性能,但石墨烯在充放电过程中容易团聚,导致其容量衰减特别快。而金属氧化物在充放电过程中体积膨胀大,因此其容量衰减也非常快;另外,金属氧化物的电导率低,导致其倍率性能差。将金属氧化物与石墨烯复合,两者性能互补,石墨烯可提高复合材料的电导率,缓解金属氧化物在充放电过程中的体积效应;金属氧化物可提高复合材料的储锂容量,并能阻止石墨烯在充放电过程中团聚。本文介绍了石墨烯/CuO锂离子电池负极材料的制备方法,分析了石墨烯与氧化铜及其复合材料的储锂机制,展望了石墨烯/CuO锂离子电池负极材料的应用前景,并指出了当前研究中存在的问题。     

稳定性膜萃取锂离子的研究

盐湖蕴藏的锂资源中较高的镬锂比增加了锂提取的难度,本文报道膜萃取技术在锂离子提取的方面的工作进展.耐有机萃取剂的膜材料是膜萃取技术的关键.采用亲水/疏水复合材料,避免了有机萃取剂流失和解决材料在有机相中的稳定性问题.结果表明,采用TBP萃取剂可以实现锂镁有效分离,为下一步工作奠定了基础.     

PPy/SiO2纳米复合材料作锂二次电池正极的研究

首先以化学氧化聚合法制备出电导率较高的聚吡咯/二氧化硅(PPy/SiO2)纳米复合材料,将其制成正极片后,以锂片为负极组装成扣式电池,通过充放电测试初步探索其电化学性能。考察了复合正极材料电导率、充放电电流和正极片成型压力对电池性能的影响。结果表明,以导电率较高的PPy/1% APS SiO2 纳米复合材料作正极活性物质,以较小充电电流0.1mA,适当的成型压力20MPa时电池比容量最高,接近40mAh/g。并且用扫描电镜(SEM)分析了充放电对正极材料结构的影响。     

固态锂电池用MOF/聚氧化乙烯复合聚合物电解质(英文)

固态聚合物电解质具有柔韧性好和易于加工的优势,可制备各种形状的固态锂电池,杜绝漏液问题。但固态聚合物电解质存在离子电导率低以及对锂金属负极不稳定等问题。本研究以纳米金属–有机框架材料UiO-66为聚合物电解质的填料,用于改善电解质的性能。UiO-66与聚氧化乙烯(poly(ethylene oxide), PEO)链上醚基的氧原子的配位作用以及与锂盐中阴离子的相互作用,可显著提高聚合物电解质的离子电导率(25℃,3.0×10^–5 S/cm;60℃,5.8×10^–4 S/cm),并将锂离子迁移数提高至0.36,电化学窗口拓宽至4.9V。此外,制备的PEO基固态电解质对金属锂具有良好的稳定性,对称电池在60℃、0.15mA·cm^–2电流密度下可稳定循环1000h,锂电池的电化学性能得到显著改善。     

Lithium iron oxide as alternative anode for li-ion batteries

Lithium–iron oxide Li–Fe–O was synthesized by solid state reaction between Li₂CO₃ and Fe₂O₃. The sample was characterized by X-ray powder diffraction. The XRD patterns showed well defined reflections corresponding to α-LiFeO₂ and the spinel LiFe₅O₈ in a molar ratio of 9:1. The material was tested as alternative anode for lithium-ion batteries. It exhibited good cyclability delivering about 120 mAh/g after 500 deep charge/discharge cycles. Unlikely, the use of the material as intercalation anode in practical cells is hindered by the irreversible uptake of lithium that takes place during the first lithium insertion. X-ray diffraction pattern showed that during this step a reduction of the lithium iron oxide occurs leading to the formation of lithium oxide and iron metal.     

锂磷氧氮电解质在无机薄膜锂电池中的应用

锂磷氧氮(LiPON,lithium phosphorous oxynitride)薄膜具有较高的离子电导率,极低的电子电导率,很宽的电化学稳定窗口等优点而成为全固态无机薄膜锂电池首选的电解质材料.简要介绍了LiPON薄膜的特性与制备方法,综述了国内外LiPON薄膜为电解质的薄膜锂电池的研究情况,并简要评述了目前薄膜锂电池制备中遇到的困难和今后的研究方向.     

锂电池正极材料LiNi_(0.8)Co_(0.2)O_2的制备

用固相烧结合成方法合成了Li离子电池用正极材料LiNi0.8Co0.2O2,试验分析了合成温度、时间、预处理方式和Li/(Ni+Co)摩尔比等因素对产物的结构和性能的影响。通过严格控制各影响因素,制得LiNi0.8Co0.2O2正极材料,其松装密度大于2.0g/cm3,首次放电容量大于160mAh/g。     

Lithium Cobalt Titanate with the Spinel Structure as an Anode Material for Lithium Ion Batteries

Inorganic Materials - Mesoporous lithium cobalt titanate powder with the spinel structure, potentially attractive as an anode material for lithium ion batteries, has been prepared by...     

Construction of 3D Electronic/Ionic Conduction Networks for All‐Solid‐State Lithium Batteries

High and balanced electronic and ionic transportation networks with nanoscale distribution in solid‐state cathodes are crucial to realize high‐performance all‐solid‐state lithium batteries. Using Cu₂SnS₃ as a model active material, such a kind of solid‐state Cu₂SnS₃@graphene‐Li₇P₃S₁₁ nanocomposite cathodes are synthesized, where 5–10 nm Cu₂SnS₃ nanoparticles homogenously anchor on the graphene nanosheets, while the Li₇P₃S₁₁ electrolytes uniformly coat on the surface of Cu₂SnS₃@graphene composite forming nanoscaled electron/ion transportation networks. The large amount of nanoscaled triple‐phase boundary in cathode ensures high power density due to high ionic/electronic conductions and long cycle life due to uniform and reduced volume change of nano‐Cu₂SnS_3. The Cu₂SnS₃@graphene‐Li₇P₃S₁₁ cathode layer with 2.0 mg cm^?2 loading in all‐solid‐state lithium batteries demonstrates a high reversible discharge specific capacity of 813.2 mAh g^?1 at 100 mA g^?1 and retains 732.0 mAh g^?1 after 60 cycles, corresponding to a high energy density of 410.4 Wh kg^?1 based on the total mass of Cu₂SnS₃@graphene‐Li₇P₃S₁₁ composite based cathode. Moreover, it exhibits excellent rate capability and high‐rate cycling stability, showing reversible capacity of 363.5 mAh g^?1 at 500 mA g^?1 after 200 cycles. The study provides a new insight into constructing both electronic and ionic conduction networks for all‐solid‐state lithium batteries.     

TiO2/石墨烯复合物的制备及其嵌脱锂行为研究

以钛酸丁酯为TiO₂前驱体, 通过水热法制得TiO₂/石墨烯复合物。使用X射线衍射(XRD)、热重分析(TG)、透射电镜(TEM)、扫描电镜(SEM)和电化学充放电等手段对材料进行了表征和分析。结果表明: TiO₂颗粒均匀地分散在石墨烯的表面, 复合物中石墨烯的含量为24.67%。当该材料用作锂离子电池负极材料时, 在2C的放电倍率下, 首次放电容量为384.35 mAh/g, 循环100次后的放电容量为130.26 mAh/g, 是纯TiO₂电极放电容量的2.93倍。与纯TiO₂电极相比, TiO₂/石墨烯复合物的电荷转移电阻较低。TiO₂/石墨烯复合物具有较好的倍率性能和较高的电化学反应活性。     

锂离子电池多孔硅/碳复合负极材料的研究

以商业化多晶硅粉为原料, 采用金属银催化剂诱导化学腐蚀的方法制得三维多孔硅材料。通过优化腐蚀条件, 得到孔径约为130 nm, 比表面为4.85 m²/g的多孔硅材料。将多孔硅和PAN溶液混合球磨并经高温烧结后在多孔硅表面包覆上一层致密的无定形碳膜, 从而制得多孔硅/碳复合材料作为锂离子电池的负极材料。3D多孔硅结构可以缓解电化学嵌/脱锂过程中材料的体积效应, 无定形碳膜层可有效改善复合材料的导电性能。电化学性能测试表明, 该多孔硅/碳复合负极材料电池在0.4 A/g的恒电流下, 首次放电容量3345 mAh/g, 首次循环库伦效率85.8%, 循环55次后容量仍保持有1645 mAh/g。并且在4 A/g的倍率下, 容量仍维持有1174 mAh/g。该方法原料成本低廉, 可规模化生产。     

Preparation and Characterization of Porous PVdF-HFP/clay Nanocomposite Membranes

Polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP) / clay nanocomposite membranes were prepared by phase inversion method through controlling retention time to apply for a lithium ion secondary batteries. Increased membrane porosity with macrovoids was observed at increasing retention time. Partially intercalated structures of PVdF-HFP/clay nanocomposite membranes were confirmed by X-ray diffraction (XRD) analysis. PVdF-HFP membranes containing various kind of clay showed the increase of membrane modulu...