包覆结构Si/C复合负极材料研究进展

以包覆结构Si/C复合材料作为负极的锂离子电池(LIBs)具有能量密度高、自放电效率低、循环寿命长等特点。然而,锂在硅中插入/脱出过程的体积膨胀和固体电解质界面膜(SEI)的不稳定性,阻碍了硅的商业化应用。本文通过对近年来新型包覆结构Si/C复合负极材料的构筑方法、电化学性能、比容量和循环性能进行分析和研究,发现包覆结构Si/C复合负极材料不仅可以缓解硅在锂化过程中的体积膨胀和炭层破裂,而且可以有效提高LIBs循环稳定性。因此,Si/C复合材料有望取代石墨成为高容量LIBs的主要负极材料。     

薄膜厚度对α-SiOx薄膜负极电化学性能的影响

近年来, SiO_x作为锂离子电池负极, 由于其良好的循环稳定性、较大的容量以及对成分调控的可行性, 引起了广泛的关注。以往的许多研究都集中在阐明氧含量对SiO_x负极的影响, 尺寸效应对性能的影响规律很少被研究。此工作研究了不同厚度的薄膜型SiO_x负极材料的电化学性能。溅射制备SiO_x电极的Si/O比值为0.7、膜厚为450 nm时, 电极初始库仑效率(ICE)为71.68%、容量保持率92.01%。以上的最优性能主要归功于电荷转移电阻低、SEI层形成减少和循环过程中电极的结构稳定性。研究表明, 作为LIBs负极, 控制SiO_x负极的厚度可以有效改善电极材料的电化学性能。     

锂离子电池Si/C/石墨复合负极材料的电化学性能

采用热裂解方法, 热解分散于聚偏二氟乙烯溶液中的硅和石墨, 得到了具有稳定电化学循环性能的Si/C/石墨复合负极材料。透射电子显微镜观察发现, 复合材料形貌为无定型碳包裹硅颗粒的核壳结构。通过系统研究不同Si粒径和石墨含量对电极电化学性能的影响, 发现Si颗粒粒径越小复合材料电化学循环稳定性能越优越, 适当的降低石墨含量有利于电极材料剩余比容量的提高。当Si粒径为50 nm, Si与石墨质量比1:1时, 电极材料具有1741.6 mAh/g的首次放电比容量和72.5%的首次库仑效率, 60次循环后, 可逆比容量保持在820 mAh/g。热解有机物形成碳包覆的结构能有效地改善硅基类负极材料的电化学循环性能。     

薄膜厚度对α-SiO_x薄膜负极电化学性能的影响（英文）

近年来, SiO_x作为锂离子电池负极,由于其良好的循环稳定性、较大的容量以及对成分调控的可行性,引起了广泛的关注。以往的许多研究都集中在阐明氧含量对SiO_x负极的影响,尺寸效应对性能的影响规律很少被研究。此工作研究了不同厚度的薄膜型SiO_x负极材料的电化学性能。溅射制备SiO_x电极的Si/O比值为0.7、膜厚为450 nm时,电极初始库仑效率(ICE)为71.68%、容量保持率92.01%。以上的最优性能主要归功于电荷转移电阻低、SEI层形成减少和循环过程中电极的结构稳定性。研究表明,作为LIBs负极,控制SiO_x负极的厚度可以有效改善电极材料的电化学性能。     

中空硅纳米球锂离子电池负极材料的制备及电化学性能

采用直流电弧等离子体蒸发法原位合成了Si-Al纳米颗粒(Si-AlNPs),获得了由晶体Si包覆单晶金属Al核的纳米胶囊结构。通过化学酸洗处理去除Al核制备出中空结构的Si纳米球(Si HNSs),并将其作为锂离子电池的负极材料,研究了电极的循环和倍率电化学性能。与Si-AlNPs电极相比,Si HNSs电极的循环稳定性及倍率性能都显著提高,这源于中空结构的Si纳米球为嵌/脱锂过程中的体积变化提供了有效缓冲空间,同时也为锂离子迁移提供了更多通道。     

基于工业废料的Si/TiN/TiSi2多相复合锂离子电池负极材料的制备及其电化学性能

Si负极材料理论容量高,但其电子电导率低和脱嵌锂过程体积变化大易粉化,使其循环稳定性和倍率性能差以及高性能硅基锂离子电池负极材料成本高,这均妨碍了其大规模产业化应用.本研究提出以太阳能电池硅片切割废料Si粉和TiN粉为原材料,采用低成本的活性气体机械球磨法制备了一种高性能的Si/TiN/TiSi2多相复合负极储锂材料.研究发现,Si在H2气氛球磨过程中与部分TiN发生反应,原位生成了纳米尺度的TiSi2,TiN和新形成的TiSi2弥散于亚微米尺度的Si基体中.Si/TiN/TiSi2复合材料的电化学性能与TiN的添加量紧密相关.其中,物质的量比Si/0.2TiN的体系具有最佳的电化学性能,在300 mA·g-1电流密度下,其首次可逆容量为2394 mA·h·g-1,首次库伦效率达75.8％,经过200次循环后,容量仍保持1295 mA·h·g-1,保持率高达54％.在2.0 A·g-1电流密度下的可逆容量达到609 mA·h·g-1.机理分析表明:高导电的惰性相TiSi2和TiN弥散在Si基体中不仅有利于电极材料在充放电循环过程中的电子传输,且有效缓冲了Si在嵌脱锂过程的巨大体积变化.这是TiN添加改善硅基复合负极材料电化学性能的主要原因.     

C/SnO2/TiO2纳米复合物的制备及其电化学性能研究

通过碳化吸附在SnO2/TiO2电极上的葡萄糖制备出C/SnO2/TiO2纳米复合电极材料。采用晶体粉末衍射仪(XRD)、场发射扫描电镜(SEM)、X射线能谱分析(EDS)等手段对复合电极进行了表征。将复合电极作为锂离子电池负极材料,通过循环伏安和计时电位法研究了其电化学性能。结果表明,在大的电流密度200μA·cm-2下循环30次后,放电容量仍保持在120.1μAh·cm-2。相比SnO2/TiO2电极,C/SnO2/TiO2复合电极电化学性能显著提高,交流阻抗谱图也显示C/SnO2/TiO2纳米复合材料拥有更低的电荷转移电阻。     

两步煅烧法合成钛酸锂及其性能

以Li_2CO_3和TiO_2为原料,采用两步煅烧法合成锂离子电池负极材料钛酸锂。采用X射线衍射仪(XRD)、扫描电子显微镜(SEM)、恒电流充放电和电化学阻抗等技术研究合成材料的结构、形貌及电化学性能。结果表明:两步煅烧法合成出的Li_4Ti_5O_(12)晶粒大小均匀,表面光滑,分散性好。在0.5C下,首次放电比容量为153.5mAh/g,循环45次后,容量保持率高达95.1%;在2C时,首次放电比容量为100.1mAh/g。两步煅烧法合成出的Li_4Ti_5O_(12)在嵌脱锂过程中的极化较小,电荷转移阻抗值最小,材料表现出优良的电化学性能。     

锂离子电池Si/C复合负极材料的合成与性能

采用球磨-热解工艺制备了Si/C复合负极材料。研究了球磨时间对Si/C复合负极材料结构和电化学性能的影响,并分析了电极的失效机理。研究结果表明,通过球磨可以将纳米硅颗粒均匀分散于石墨基体材料表面,同时,葡萄糖热解后形成的无定形碳使两者紧密结合。球磨3h合成的材料具有最优的电化学性能。以100mA/g的电流密度放电,首次放电容量达到1340mAh/g,首次充放电效率为75.6%,循环50次后,容量保持率为34.2%。     

壳聚糖衍生碳包覆纳米硅复合材料锂离子电池性能研究

硅负极材料因具有较高的理论容量(Li₂₂Si₅合金相对应4 200 mAh/g)、较低的工作电压(0.2～0.3 V vs Li/Li⁺)和地球上丰富的原材料储备,成为代替石墨负极的理想材料之一。但是,低电导率及在循环过程中发生剧烈体积膨胀导致电极失效问题限制了硅负极材料的进一步发展。因此,本工作通过物理法利用壳聚糖和石墨对纳米硅实现碳包覆和复合,制备壳聚糖/石墨@纳米硅复合材料(C/G@Si复合材料),对C/G@Si复合材料的结构、形貌和电化学性能进行研究。结果表明：随着石墨添加量的提高,C/G@Si复合材料的可逆比容量略微下降,循环性能和导电性能显著提高。当添加50%(质量分数)石墨时,在100 mA/g的电流密度下,C/G@Si复合材料的首次放电比容量为1 136.1 mAh/g,循环充放电100次后剩余容量保持在658.5 mAh/g,展示出优异的电化学性能,对进一步推广硅碳负极材料具有一定的参考价值。     

Effects of mechanical milling and arc-melting processes on the electrochemical performance of Si-based composite materials

The Si–Ni composite and Si/Ni alloy composite were prepared by high-energy mechanical milling and arc-melting, respectively, in order to investigate the effects of these processes on the electrochemical performance. The microstructures of Si–Ni composite and Si/Ni alloy composite were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The electrochemical properties have been investigated during 50 cycles for Si–Ni–C composite and Si/Ni alloy–C composite. As a result, both composites demonstrate a higher reversible capacity accompanied with a good cycling stability than the existing Si–C composite. Homogeneously dispersed Ni improved electric conductivity and induced fast charge transport significantly in Si–Ni–C composite whereas the secondary phases (NiSi and NiSi₂) played a role of media to accommodate a large volume change of Si during cycling in Si/Ni alloy–C composite. Consequently, it was identified that electrochemical performances of electrode material are affected by structural factors caused by the different processes.     

Si–Ni–Carbon composite synthesized using high energy mechanical milling for use as an anode in lithium ion batteries

Si–Ni–Carbon composite was prepared by two-step high energy mechanical milling process. The microstructure was characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectrometry (EDS). The electrochemical properties have been investigated until the 50th cycle. As a result, Carbon was coated on the surface of the Si–Ni composite, where Ni was distributed in Si matrix and the Si–Ni–Carbon composite demonstrated a large reversible capacity of ca. 960 with an excellent cycling stability. The reasons for good electrochemical characteristics were analyzed by high resolution transmission electron microscope (HR-TEM), powder resistance analysis and Barret–Joiner–Halendar (BJH) analysis. Uniformly dispersed Ni improved electronic conductivity and induced fast charge transport significantly in the Si–Ni–Carbon composite. In addition, pores and disordered Carbon layer played a role of media to accommodate a large volume change of Si during cycling. Our experiments suggest that the Si–Ni–Carbon composite should be a promising new anode material for lithium ion secondary batteries with a high capacity.     

Understanding of the capacity contribution of carbon in phosphorus-carbon composites for high-performance anodes in lithium ion batteries

Phosphorus has recently received extensive attention as a promising anode for lithium ion batteries (LIBs) due to its high theoretical capacity of 2,596 mAh·g-1.To develop high-performance phosphorus anodes for LIBs,carbon materials have been hybridized with phosphorus (P-C) to improve dispersion and conductivity.However,the specific capacity,rate capability,and cycling stability of P-C anodes are still less than satisfactory for practical applications.Furthermore,the exact effects of the carbon support on the electrochemical performance of the P-C anodes are not fully understood.Herein,a series of xP-yC anode materials for LIBs were prepared by a simple and efficient ball-milling method.6P-4C and 3P-7C were found to be optimum mass ratios of x/y,and delivered initial discharge capacities of 1,803.5 and 1,585.3.mAh.g-1,respectively,at 0.1 C in the voltage range 0.02-2 V,with an initial capacity retention of 68.3％ over 200 cycles (more than 4 months cycling life) and 40.8％ over 450 cycles.The excellent electrochemical performance of the 6P-4C and 3P-7C samples was attributed to a synergistic effect from both the adsorbed P and carbon.     

碳酸氢铵电化学氧化阳极对含油海底沉积物微生物燃料电池性能影响及其加速降解研究

制备了3种阳极(未改性阳极、氨水改性阳极、NH_4HCO_3电化学氧化改性阳极)组建海底沉积物微生物燃料电池(MSMFCs),探究阳极的不同氨改性方法对含油MSMFCs电化学性能和石油降解率的影响。结果表明,电化学氧化改性阳极的电容特性是未改性阳极组的1.78倍,并且其抗极化能力最强,交换电流密度为2.57×10~(-2)A·m~(-2),是未改性的5.00倍;由电化学氧化改性阳极组建的电池的最大输出功率密度是1.53×102m W·m~(-2),较空白组的增加3.56倍,且该电池阳极沉积物中石油的降解率是空白组的10.40倍,这是因为改性阳极表面连入了有利于微生物附着的酰胺基团和氨基基团,提高了电池电化学性能并加速了石油的降解。     

氨气处理碳毡阳极对海底沉积物微生物燃料电池性能的影响

选取500℃、650℃、800℃对石墨碳毡阳极进行氨气处理,分别构建海底沉积物微生物燃料电池(MSMFCs)。结果表明:改性后其微生物活性和电化学活性均明显提高。500℃改性阳极表面微生物数量(10.420×10^11 cfu/m^2)是Blank组的2.9倍,说明500℃氨气改性增加了微生物的附着量。500℃改性阳极循环伏安电容性能(62.1 F/m^2)是Blank组的2.0倍,表明其氧化还原电化学活性显著提高;电荷转移电阻(14.46Ω)为Blank组(62.39Ω)的1/4,交换电流密度是Blank组的1.1倍,说明500℃氨气处理提高了阳极的电子转移动力学活性和抗极化能力。500℃改性阳极的输出功率(60.67 mW/m^2)为Blank组(29.17 mW/m^2)的2.1倍,其长期输出电压达到692 mV且产电更加稳定,电池性能显著提升。     

Closely packed Si@C and Sn@C nano-particles anchored by reduced graphene oxide sheet boosting anode performance of lithium ion batteries

Both silicon and tin are promising anodes for new generation lithium ion batteries due to high lithium storage capacities (theoretically 4200 mA h g-1 and 992 mA h g-1,respectively).However,their large volumetric expansions (both are above 300 ％) usually lead to poor cycling stability.In this case,we synthesized closely packed Si@C and Sn@C nano-particles anchored by reduced graphene oxide (denoted as Si@C/Sn@C/rGO) by the way of solution impregnation and subsequent hydrogenation reduction.Sn particles with a diameter of 100 nm are coated by carbon and surrounded by Si@C particles around 40 nm in average diameter through the high-resolution transmission electron microscopy.Expansions of Si and Sn are alleviated by carbon shells,and reduced graphene oxide sheets accommodate their volume changes.The prepared Si@C/Sn@C/rGO electrode delivers an enhanced initial coulombic efficiency (78％),rate capability and greatly improved cycle stability (a high reversible capacity of nearly 1000 mA h g-1 is achieved after 300 cycles at a current density of 1000 mA g-1).It can be believed that packing Sn@C nano-particles with Si@C relieves the volume expansion of both and releases the expansion stresses.Sn@C particles enhance anode process kinetics by reducing charge transfer resistance and increasing lithium ion diffusion coefficient.The present work provides a viable strategy for facilely synthesizing silicon-tin-carbon composite anode with long life.     

Si/C particles on graphene sheet as stable anode for lithium-ion batteries

Silicon is considered as one of the most promising anodes for Li-ion batteries (LIBs),but it is limited for commercial applications by the critical issue of large volume expansion during the lithiation.In this work,the structure of silicon/carbon (Si/C) particles on graphene sheets (Si/C-G) was obtained to solve the issue by using the void space of Si/C particles and graphene.Si/C-G material was from Si/PDA-GO that silicon particles was coated by polydopamine (PDA) and reacted with oxide graphene (GO).The Si/C-G material have good cycling performance as the stability of the structure during the lithiation/dislithiation.The Si/C-G anode materials exhibited high reversible capacity of 1910.5 mA h g-1 and 1196.1 mA h g-1 after 700 cycles at 357.9 mA g-1,and have good rate property of 507.2 mA h g-1 at high current density,showing significantly improved commercial viability of silicon electrodes in high-energy-density LIBs.     

An Advanced MoS2/Carbon Anode for High‐Performance Sodium‐Ion Batteries

Molybdenum disulfide (MoS₂) is a promising anode for high performance sodium‐ion batteries due to high specific capacity, abundance, and low cost. However, poor cycling stability, low rate capability and unclear electrochemical reaction mechanism are the main challenges for MoS₂ anode in Na‐ion batteries. In this study, molybdenum disulfide/carbon (MoS₂/C) nanospheres are fabricated and used for Na‐ion battery anodes. MoS₂/C nanospheres deliver a reversible capacity of 520 mAh g^?1 at 0.1 C and maintain at 400 mAh g^?1 for 300 cycles at a high current density of 1 C, demonstrating the best cycling performance of MoS₂ for Na‐ion batteries to date. The high capacity is attributed to the short ion and electron diffusion pathway, which enables fast charge transfer and low concentration polarization. The stable cycling performance and high coulombic efficiency (～100%) of MoS₂/C nanospheres are ascribed to (1) highly reversible conversion reaction of MoS₂ during sodiation/desodiation as evidenced by ex‐situ X‐ray diffraction (XRD) and (2) the formation of a stable solid electrolyte interface (SEI) layer in fluoroethylene carbonate (FEC) based electrolyte as demonstrated by fourier transform infrared spectroscopy (FTIR) measurements.     

Dendrimer Based Binders Enable Stable Operation of Silicon Microparticle Anodes in Lithium-Ion Batteries

High-capacity anode materials (e.g., Si) are highly needed for high energy density battery systems, but they usually suffer from low initial coulombic efficiency (CE), short cycle life, and low-rate capability caused by large volume changes during the charge and discharge process. Here, a novel dendrimer-based binder for boosting the electrochemical performance of Si anodes is developed. The polyamidoamine (PMM) dendrimer not only can be used as binder, but also can be utilized as a crosslinker to construct 3D polyacrylic acid (PAA)-PMM composite binder for high-performance Si microparticles anodes. Benefiting from maximum interface interaction, strong average peeling force, and high elastic recovery rate of PAA-PMM composite, the Si electrode based on PAA-PMM achieves a high specific capacity of 3590 mAh g⁻¹ with an initial CE of 91.12%, long-term cycle stability with 69.80% retention over 200 cycles, and outstanding rate capability (1534.8 mAh g⁻¹ at 3000 mA g⁻¹). This work opens a new avenue to use dendrimer chemistry for the development of high-performance binders for high-capacity anode materials.