锂硫电池硫正极材料研究进展

由化石燃料的大量使用导致的全球能源和环境问题日益严重,已对人们的生产和生活产生了明显的影响.开发利用储量丰富的清洁能源(如太阳能、水能和风能等)有望较好地解决全球能源和环境问题.由于这些清洁能源存在地域性、间歇性等特点,高效的能量转化和存储技术是实现清洁能源规模化利用的关键和基础.锂离子电池作为绿色环保的储能器件,已在手机、笔记本电脑、相机等便携电子产品中广泛使用.近年来,锂离子电池开始在电动汽车等动力电池领域得到应用.但是,由于其能量密度不够高,导致锂离子电池电动汽车续航短、充电频繁及购车成本高.由金属锂为负极和硫为正极组成的锂硫电池的能量密度(2600 Wh·kg-1)远高于目前广泛使用的锂离子电池.此外,硫正极材料具有储量丰富、毒性低、价格便宜、环境友好等突出优点.因此,锂硫电池被认为是当前最具研究前景的高能量密度二次电池之一.硫正极材料的本征导电性差、在充放电过程中存在较大的体积膨胀和收缩,储放锂过程中形成的多硫化锂易溶于电解液,使得锂硫电池的倍率性能、循环寿命和库伦效率等电化学性能离实际应用仍有较大距离.迄今为止,关于硫正极材料的研究工作,主要集中于如何提升其导电性、抑制或消除由多硫化锂的溶解引起的穿梭效应以及在反复的循环过程中保持电极材料微结构的稳定性等方面.相关研究表明,将硫与不同形貌的碳材料复合构筑成具有特殊微观结构的硫/碳复合正极材料可显著提高其导电性、抑制多硫化锂的穿梭效应和减缓储放锂前后的体积变化,进而改善倍率性能、循环稳定性和充放电效率等.此外,在硫正极材料中引入异质元素掺杂碳材料、金属氧化物和导电集合物均可通过化学吸附实现对易溶解多硫化锂的有效吸附.将上述多种改性方法结合也可使硫正极材料具有优异的电化学储锂性能.本文从锂硫电池的工作原理出发,总结了硫正极材料存在的主要问题,综述了近几年锂硫电池复合正极材料的研究进展,最后对锂硫电池正极材料的研究思路与发展趋势进行了分析和展望.     

锂硫电池正极材料的研究进展

能源领域未来发展趋势着重于绿色清洁能源,锂硫电池以其高比能量以及成本低廉等优点,成为电池研究中的新热点。然而,目前锂硫电池仍存在较多问题阻碍其商业化,如正极材料硫导电性能差、正极产物多硫化物的穿梭效应、在充放电过程中,电池内部电极表现出体积膨胀等。本研究综述了近年来锂硫电池正极材料的研究进展,主要讨论了金属有机骨架化合物、碳材料以及导电聚合物在锂硫电池正极材料中的应用,并对锂硫电池正极材料的发展进行了展望。     

Dealloying-derived nanoporous deficient titanium oxide as high-performance bifunctional sulfur host-catalysis material in lithium-sulfur battery

In this work,we report a facile dealloying strategy to tailor the surface state of nanoporous TiO2 towards high-efficiency sulfur host material for lithium-sulfur(Li-S)batteries.When used as a sulfur cathode material,the oxygen-deficient TiO2-x exhibits enhanced lithium polysulfides(LiPS)adsorption and con-version kinetics that effectively tackle the shuttle effect in lithium-sulfur batteries.The excellent ability of the oxygen vacancy sites on TiO2-x surface to trap LiPS is proved by experimental observations and density functional theory(DFT)calculations.Meanwhile,it also promotes conversion kinetics of lithium polysul-fides,as verified by the asymmetric cell experiment.Accordingly,compared with the S/TiO2 cathode,the oxygen-deficient S/TiO2-x electrode exhibits preeminent rate and cycling performance in lithium-sulfur batteries:it delivers an ultra-low capacity decay of0.039％per cycle after 1000 cycles at 1 C.Tunning the surface state of metal oxides by dealloying method offers a new facile strategy to design efficient sulfur cathode materials for lithium-sulfur batteries.     

自组装二氧化锰纳米片包覆嵌硫多通道碳纳米纤维复合物在锂硫电池阴极中的应用

由于可充电锂硫电池在能量密度方面具有显著的优势,因此被认为是很有前途的下一代储能体系.然而,多硫化物的穿梭和硫的绝缘特性,导致了锂硫电池严重的容量衰减和低硫利用率,阻碍了它们的实际应用.因此,本研究合理设计制备了一种二氧化锰纳米片包覆嵌硫多通道碳纳米纤维复合物用于锂硫电池阴极.多孔多通道碳纳米纤维的高导电性促进了电极中电子和离子的传输动力学,多孔结构将硫包裹并隔离在其内部空隙中,在物理上延缓了高阶多硫化物的溶解.此外,二氧化锰壳层对高阶多硫化物的物理限制和化学吸附相结合,可以隔离长时间充放电循环后从碳基体中泄漏的多硫化物,从而进一步提高电极的电化学性能.     

Coordinated Immobilization and Rapid Conversion of Polysulfide Enabled by a Hollow Metal Oxide/Sulfide/Nitrogen-Doped Carbon Heterostructure for Long-Cycle-Life Lithium-Sulfur Batteries

Lithium-sulfur batteries (LSBs) are recognized as the prospective candidate in next-generation energy storage devices due to their gratifying theoretical energy density. Nonetheless, they still face the challenges of the practical application including low utilization of sulfur and poor cycling life derived from shuttle effect of lithium polysulfides (LiPSs). Herein, a hollow polyhedron with heterogeneous CoO/Co₉S₈/nitrogen-doped carbon (CoO/Co₉S₈/NC) is obtained through employing zeolitic imidazolate framework as precursor. The heterogeneous CoO/Co₉S₈/NC balances the redox kinetics of Co₉S₈ with chemical adsorption of CoO toward LiPSs, effectively inhibiting the shuttle of LiPSs. The mechanisms are verified by both experiment and density functional theory calculation. Meanwhile, the hollow structure acts as a sulfur storage chamber, which mitigates the volumetric expansion of sulfur and maximizes the utilization of sulfur. Benefiting from the above advantages, lithium-sulfur battery with S-CoO/Co₉S₈/NC achieves a high initial discharge capacity (1470 mAh g⁻¹ ) at 0.1 C and long cycle life (ultralow capacity attenuation of 0.033% per cycle after 1000 cycles at 1 C). Even under high sulfur loading of 3.0 mg cm⁻² , lithium-sulfur battery still shows the satisfactory electrochemical performance. This work may provide an idea to elevate the electrochemical performance of LSBs by constructing a hollow metal oxide/sulfide/nitrogen-doped carbon heterogeneous structure.     

Ordered SnO nanoparticles in MWCNT as a functional host material for high-rate lithium-sulfur battery cathode

Lithium-sulfur battery has become one of the most promising candidates for next generation batteries,and it is still restricted due to the low sulfur conductivity,large volume expansion and severe polysulfide shuttling.Herein,we present a novel hybrid electrode with a ternary nanomaterial based on sulfur-impregnated multiwalled carbon nanotubes filled with ordered tin-monoxide nanoparticles (MWCNT-SnO/S).Using a dry plasma reduction method,a mechanically robust material is prepared as a cathode host material for lithium-sulfur batteries.The MWCNT-SnO/S electrode exhibits high conductivity,good ability to capture polysulfides,and small volume change during a repeated charge-discharge process.In situ transmission electron microscopy and ultraviolet-visible absorption results indicate that the MWCNT-SnO host efficiently suppresses volume expansion during lithiation and reduces polysulfide dissolution into the electrolyte.Furthermore,the ordered SnO nanoparticles in the MWCNTs facilitate fast ion/electron transfer during the redox reactions by acting as connective links between the walls of the MWCNTs.The MWCNT-SnO/S cathode with a high sulfur content of 70 wt.％ exhibits an initial discharge capacity of 1,682.4 mAh·g-1 at 167.5 mA·g-1 (0.1 C rate) and retains a capacity of 530.1 mAh·g-1 at 0.5 C after 1,000 cycles with nearly 100％ Coulombic efficiency.Furthermore,the electrode exhibits the high capacity even at a high current rate of 20 C.     

高能球磨法制备PTFE/科琴黑-C柔性复合材料及其电化学应用

对荷叶进行多阶温度炭化得到前驱炭材料,将材料与科琴黑（KB）、聚四氟乙烯（PTFE）按照2:2:3的质量比球磨混合后真空抽滤制备一种锂硫电池中间层柔性材料,PTFE/KB-C复合材料的多孔结构能为高阶硫化物Li₂S_n（4≤n≤8）的进一步还原提供较多的三相反应位点,并利用PTFE/KB-C复合材料良好的多层多孔化学吸附作用来抑制可溶性多硫化物的穿梭。该中间层在以纯硫材料为正极的锂硫电池电性能测试表征中,1.0 C（电流密度1 675 mA·g-1）倍率下首次放电比容量达1 350 mAh·g-1,没有硝酸锂添加剂条件下经过100次充放电循环后比容量依旧保持在960 mAh·g-1,库伦效率基本在95%以上,保持了良好的循环稳定性。      

多壁碳纳米管纸作正极集流体的锂硫电池性能

为了改善锂硫电池的循环性能,以纸纤维为基体,多壁碳纳米管(MWCNTs)为导电剂,采用真空抽滤法制得MWCNTs导电纸,并将MWCNTs导电纸作为正极集流体代替铝箔应用于锂硫电池。对MWCNTs导电纸进行了形貌结构表征和电化学性能测试,并对循环后的MWCNTs导电纸电极进行EDS检测。结果显示,MWCNTs均匀地附着在纸纤维基体上,多空隙的MWCNTs导电纸三维结构明显。采用MWCNTs导电纸作集流体的锂硫电池在0.05C和1C倍率充放电下循环30次,比容量分别保持615mAh/g、496mAh/g,库伦效率达97.5%以上,且电荷转移电阻在循环后降低。EDS元素分析结果证实MWCNTs导电纸对多硫化锂有吸附作用,从而一定程度抑制了锂硫电池的穿梭效应。因此,以MWCNTs导电纸作为集流体能有效增加活性物质硫的负载量和接触面积,使锂硫电池具有良好的循环稳定性和库伦效率性能。     

锂硫电池隔膜改性研究进展

锂硫电池因高比容量和高能量密度引起了研究者们的广泛关注,成为新型锂电池研究热点之一。隔膜作为锂硫电池的重要组成部分,是提高电池各方面性能的关键。现阶段锂硫电池隔膜改性工作主要集中于高性能涂层材料的设计与合成以及新型隔膜材料的开发。本文综述了锂硫电池隔膜改性的研究现状,分别从碳涂层隔膜、元素掺杂碳涂层隔膜、金属氧化物/碳复合涂层隔膜、新型薄膜材料和多层隔膜等五个方面进行介绍,指出了从隔膜入手提高导电性、抑制穿梭效应、减轻锂电极腐蚀,从而提高电池电化学性能的重要性。     

Multilevel structured carbon film as cathode host for Li-S batteries with superhigh-areal-capacity

The commercialization of lithium-sulfur (Li-S) battery could be accelerated by designing advanced sulfur cathode with high sulfur utilization and stable cycle life at a high sulfur loading. To allow the energy density of Li-S batteries comparable to that of commercial Li-ion batteries, the areal capacity of sulfur cathode should be above 4 mA·h·cm?2. In general, a high sulfur loading often causes rapid capacity fading by slowing electron/ion transport kinetics, catastrophic shuttle effect and even cracking the electrodes. To address this issue, herein, a multilevel structured carbon film is built by covering highly conductive CNTs and hollow carbon nanofiber together with carbon layer via chemical vapor deposition. The self-standing carbon film exhibits well-interweaved conductive network, hollow fibrous structure and abundant N, O co-doped active sites, which combine the merits of high electronic conductivity (1200·S·m?1), high porosity and polar characteristic in one host. Benefiting from this attractive multilevel structure, the obtained sulfur cathode based on the carbon film host shows an ultra-high areal capacity of 8.9 mA·h·cm?2 at 0.2 C with outstanding cyclability over 60 cycles. This work shed light on designing advanced sulfur host for Li-S batteries with high areal capacity and high cycle stability, and might make a contribution to the commercialization of Li-S batteries.     

Nickel embedded porous macrocellular carbon derived from popcorn as sulfur host for high-performance lithium-sulfur batteries

Due to the demands for high performance and ecological and economical alternatives to conventional lithium-ion batteries (LiBs),the development of lithium-sulfur (Li-S) batteries with remarkably higher theoretical capacity (1675 mA h g-1) has become one of the extensive research focus directions world-wide.However,poor conductivity of sulfur,critical cyclability problems due to shuttle of polysulfides as intermediate products of the cathodic reaction,and large volume variation of the sulfur composite cathode upon operation are the major bottlenecks impeding the implementation of the next-generation Li-S batteries.In this work,a unique three-dimensional (3D) interconnected macrocellular porous carbon (PC) architecture decorated with metal Ni nanopatticles was synthesized by a simple and facile strategy.The as-fabricated Ni/PC composite combines the merits of conducting carbon skeleton and highly adsorptive abilities of Ni,which resulted in efficient trapping of lithium polysulfides (LiPSs) and their fast conversion in the electrochemical process.Owing to these synergistic advantageous features,the composite exhibited good cycling stability (512.3 mA h g-1 after 1000 cycles at 1 C with an extremely low capacity fading rate 0.03 ％ per cycle),and superior rate capability (747.5 mAh g-1 at 2 C).Accordingly,such Ni nanoparticles embedded in a renewable puffed corn-derived carbon prepared via a simple and effective route represent a promising active type of sulfur host matrix to fabricate high-performance Li-S batteries.     

锂/硫电池的研究现状、问题及挑战

锂/硫电池是以金属锂为负极、单质硫为正极而构筑的二次电池体系。锂/硫电池具有高的理论能量密度 (2600 Wh/kg), 成为最具发展潜力的高能化学电源体系。但这种基于溶解?沉积反应的锂/硫电池体系仍面临一些无法避免的问题, 包括金属锂负极的显著结构变化、硫正极材料存在的活性物质利用率低和循环性能差等缺点, 制约了锂/硫电池的发展。本文结合近年来关于锂/硫电池的突破进展, 简要阐述了锂/硫电池的研究现状、问题及面临的挑战。     

负载ZnS的介孔炭复合硫正极材料的制备及性能研究

为了获得高性能的锂硫电池正极材料, 采用先超声分散再进行热处理的方法制备了负载ZnS的介孔炭复合材料(ZnS/MC), 进而用热复合法获得负载有ZnS的介孔炭复合硫正极材料(ZnS/MC/S)。XRD、SEM、EDS和N2吸附脱附等温线表明, 当ZnS含量低于17wt%时, 通过超声波分散, ZnS可以均匀负载到介孔炭中; 但热处理或提高ZnS含量时ZnS会发生聚集, 形成闪锌矿型ZnS晶相。循环伏安测试表明, ZnS对多硫离子的氧化起促进作用; 充放电测试表明, ZnS/MC/S电极的初始放电比容量为1354.6 mAh/g, 首次充放电库仑效率为98.7%; 50次循环后容量仍有650 mAh/g。     

Modulating d-Band Electronic Structures of Molybdenum Disulfide via p/n Doping to Boost Polysulfide Conversion in Lithium-Sulfur Batteries

Polysulfide shuttle effect and sluggish sulfur reaction kinetics severely impede the cycling stability and sulfur utilization of lithium-sulfur (Li-S) batteries. Modulating d-band electronic structures of molybdenum disulfide electrocatalysts via p/n doping is promising to boost polysulfide conversion and suppress polysulfide migration in lithium-sulfur batteries. Herein, p-type V-doped MoS₂ (V-MoS₂) and n-type Mn-doped MoS₂ (Mn-MoS₂) catalysts are well-designed. Experimental results and theoretical analyses reveal that both of them significantly increase the binding energy of polysulfides on the catalysts’ surface and accelerate the sluggish conversion kinetics of sulfur species. Particularly, the p-type V-MoS₂ catalyst exhibits a more obvious bidirectional catalytic effect. Electronic structure analysis further demonstrates that the superior anchoring and electrocatalytic activities are originated from the upward shift of the d-band center and the optimized electronic structure induced by duplex metal coupling. As a result, the Li-S batteries with V-MoS₂ modified separator exhibit a high initial capacity of 1607.2 mAh g⁻¹ at 0.2 C and excellent rate and cycling performance. Moreover, even at a high sulfur loading of 6.84 mg cm⁻², a favorable initial areal capacity of 8.98 mAh cm⁻² is achieved at 0.1 C. This work may bring widespread attention to atomic engineering in catalyst design for high-performance Li-S batteries.     

Watermelon Flesh-Like Ni3S2@C Composite Separator with Polysulfide Shuttle Inhibition for High-Performance Lithium-Sulfur Batteries

The shuttle effect limits the practical application of lithium-sulfur (Li-S) batteries with high specific capacity and cheap price. Herein, a three-dimensional carbon substrate containing Ni₃S₂ nanoparticles is created to modify the separator. The in situ optical visualization battery proves that the material can realize the rapid conversion of Li₂S₆. Moreover, the impact of lithium-ion diffusion on the reactions in the cell is investigated, and the mechanism of Ni₃S₂@C in the cell is proposed based on the “adsorption-diffusion-conversion” mechanism. The “adsorption-diffusion-conversion” process of polysulfide is carried out on the surface of the composite separator, showing positive effects on the inhibition of polysulfide shuttle and the promotion of conversion. The separator is modified to improve sulfur utilization and reduce dead sulfur accumulation through a strategy of chemical immobilization and physical blocking. This helps to bridge the existing gaps of Li-S batteries.     

Ultra-high conductive 3D aluminum photonic crystal as sulfur immobilizer for high-performance lithium-sulfur batteries

Nano Research - The practical application of lithium-sulfur (Li-S) batteries is hampered by the insulative nature of sulfur, sluggish electrochemical kinetics, and large volume variation, which...     

椰壳活性炭孔结构对Li-S电池性能的影响

以椰壳为原料,采用化学活化法制备不同比表面积和孔结构的活性炭,通过改变制备工艺参数来调节活性炭的比表面积和孔结构。将活性炭负载60%(质量分数)硫后,作为锂硫电池的正极材料,研究活性炭孔结构对锂硫电池性能的影响。结果表明:随着活性炭比表面积的增加,中孔比例增加,锂硫电池比容量逐步提高。其中,当活化剂与炭化料的质量比为4时,活性炭的比表面积达到2900m2/g,中孔率达到15.36%。在电流密度为200mA/g时,首次放电比容量高达1294.5mAh/g,循环100次后的可逆比容量仍然高达809.3mAh/g。     

MOFs及衍生复合材料在锂硫电池中的设计应用

在能源危机与环境问题日益凸显的背景下,电化学储能技术得到了迅速发展。在“超越锂”储能领域的竞争者中,锂硫电池(Li-S)因其具有高理论比容量、高质量能量密度并且环境友好、价格低廉等优点,成为最有前途的新储能技术。但是,锂硫电池的发展仍存在一些瓶颈问题需要解决,例如正极材料导电性能差、多硫化物穿梭效应及在充放电过程中电极体积膨胀等。作为锂硫电池的关键组成部分,电极和隔膜材料的设计和制备对解决这些问题及电池整体性能提升起到了重要的作用。金属有机骨架(MOFs)及衍生的复合材料作为锂硫电池电极或隔膜修饰材料,具有质量轻、电子和离子传导性好、孔道丰富和活性位点均匀分布等优势。此外,这类复合材料还具备形貌和组分可控、来源丰富和孔径可调等特性,从而便于机制研究。本文全面介绍了锂硫电池组成、工作原理并综述了近几年MOFs及衍生复合材料在锂硫电池中的研究进展,重点讨论了其在正极材料和隔膜材料中的应用,并对未来该材料在锂硫电池研究方向上的前景和突破进行了展望。      

活化剂对焦煤基多孔碳制备的影响及其在锂硫电池中的应用

煤炭作为一种来源广泛的非金属矿物,是制备大量多孔碳的理想原料。本文以1/3焦煤为原料,NaOH和KOH为活化剂,制备了多孔碳,并研究了硫/多孔碳复合正极材料的电化学性能。结果表明:采用NaOH和KOH单独活化时制备的多孔碳比表面积很大,分别为1 649 m2/g和1 867 m2/g,而采用NaOH和KOH混合活化制备的多孔碳比表面积大幅度下降,当NaOH与KOH质量比为1:1活化时多孔碳的比表面积最小,为290 m2/g。电化学测试表明,NaOH与KOH质量比为1:1混合活化的硫/多孔碳正极材料的电性能优于NaOH和KOH单独活化的硫/多孔碳正极材料,0.2 C下首次放电比容量为790 mA·h/g,库仑效率为93.16%,100次循环后放电比容量为740 mA·h/g。还分析讨论了煤基多孔碳孔径分布对电化学性能的影响。      

Rational Design of a High-Loading Polysulfide Cathode and a Thin-Lithium Anode for Developing Lean-Electrolyte Lithium–Sulfur Full Cells

Lithium-sulfur cells are attractive energy-storage systems because of their high energy density and the electrochemical utilization rates of the high-capacity lithium-metal anode and the low-cost sulfur cathode. The commercialization of high-performance lithium–sulfur cells with high discharge capacity and cyclic stability requires the optimization of practical cell-design parameters. Herein, a carbon structural material composed of a carbon nanotube skeleton entrapping conductive graphene is synthesized as an electrode substrate. The carbon structural material is optimized to develop a high-loading polysulfide cathode with a high sulfur loading capacity (6–12 mg cm⁻²), rate performance (C/10–C/2), and cyclic stability for 200 cycles. A thin lithium anode based on the carbon structural material is developed and exhibits long lithium stripping/plating stability for ≈2500 h with a lithium-ion transference number of 0.68. A lean-electrolyte lithium–sulfur full cell with a low electrolyte-to-sulfur ratio of 6 µL mg⁻¹ is constructed with the designed high-loading polysulfide cathode and the thin lithium anode. The integration of all the critical cell-design parameters endows the lithium–sulfur full cell with a low negative-to-positive capacity ratio of 2.4, while exhibiting stable cyclability with an initial discharge capacity of 550 mAh g⁻¹ and 60% capacity retention after 200 cycles.