芘对聚苯胺锂硫电池低温性能的影响机制研究

提出在电解液中加入电荷转移中间体改善锂硫电池低温性能的思路,在电解液中添加芘作为电荷转移中间体,加速低温下聚苯胺锂硫电池电化学反应的平衡过程.循环伏安研究证明,芘在锂硫电池放电过程中的高压平台附近具有电化学活性,并通过X射线光电子能谱证实芘的引入能够使锂硫电池在低温下提高多硫化物平衡速率,延长第一平台,生成更多长链多硫化锂.对同样电极材料组成的聚苯胺/硫复合正极材料构成的锂硫电池,当在电解液中加入0.1 mol/L的芘时,相比于不含芘的锂硫电池,其第50次充放电循环下容量在0oC时能够提升22.8%,而在-15oC时能提升25.1%.     

LiF和LiCl对石墨电极电化学性能的影响

六氟磷酸锂是目前商品化锂离子电池中使用最广泛的电解质锂盐,LiF和LiCl是除水和酸之外六氟磷酸锂产品中最重要的杂质.运用扫描电子显微镜（SEM）、充放电、循环伏安法（CV）以及电化学阻抗谱测试（EIS）等研究了LiF和LiCl对石墨电极电化学性能的影响.充放电结果表明,在1 mol/L LiPF₆-EC：DEC：DMC电解液中添加饱和的LiF,可以显著提高石墨电极的充放电可逆容量并改善其循环性能,而在1 mol/L LiPF₆-EC：DEC：DMC电解液中添加饱和的LiCl,虽也可提高石墨电极的首次充电容量,但严重恶化石墨电极的充放电循环稳定性.CV结果表明,电解液中LiF、LiCl的存在对EC的还原分解过程影响较小.但SEM和EIS的结果指示,LiF、LiCl对石墨电极表面SEI膜的形成过程影响较大.在添加饱和LiF的电解液中石墨电极表面形成的SEI膜较薄且电阻较小,进而提高了石墨电极的可逆循环容量及改善了其循环稳定性;但在饱和的LiCl电解液中石墨电极表面形成的SEI膜较厚且电阻较大,严重恶化石墨电极的电化学循环稳定性.     

锂金属电池用高浓度电解液体系研究进展

锂金属二次电池具有极高的能量密度,是下一代储能电池的研究热点。然而,金属锂负极在传统碳酸酯电解液1 mol·L^?1 LiPF6-EC/DEC(ethylene carbonate/diethyl carbonate)中充放电时,存在严重的枝晶生长和循环效率低下等问题,阻碍了其商业化应用。因此,开发与锂负极兼容的新型电解液体系是目前重要的研究任务。与传统稀溶液相比,高浓度电解液体系具有独有的物化性质和优异的界面相容性,并且能有效抑制锂枝晶生长、显著提升锂负极的循环可逆性,因而格外受到关注。本文综述了高浓度电解液及局部高浓电解液体系的最新研究进展,分析了其溶液化学结构和物化性质,对其与锂负极的界面相容性、枝晶抑制效果、效率提升能力及界面稳定性机制进行了探讨;文章着重介绍了高浓与局部高浓电解液体系在锂金属二次电池中的应用,同时从基础科学研究和应用研究两个层面对高浓电解液和局部高浓电解液存在的主要问题进行了简要分析,并对其未来发展方向进行了展望。     

亲锂电解液在LiNi0.6Mn0.2Co0.2O2／Li二次锂金属电池中的电化学性能

金属锂电池被认为是具有良好前景的下一代高能量密度电池。然而,传统的碳酸酯类电解液与锂的亲和性差,在循环过程中由于锂枝晶的生长和固体电解质膜（SEI）的不稳定导致金属锂电池性能快速衰减。采用1.2 mol／L六氟磷酸锂（LiPF₆）／二氟草酸硼酸锂（LiDFOB）／氟代碳酸乙烯酯（FEC）／碳酸二乙酯（DEC）,并添加了双三氟甲磺酰亚胺锂（LiTFSI）作为电解液,对其在LiNi_0.6Mn_0.2Co_0.2O₂／40 μm-Li（单位面积上负／正极材料的实际容量的比N／P＝2.85）电池中的电化学性能进行了研究。LiNi_0.6Mn_0.2Co_0.2O₂／40 μm-Li电池表现出优异的循环稳定性（循环120圈后,容量保持率>93%）和倍率性能（3C倍率下放电比容量为110 mA·h／g）。良好的电化学性能主要归因于该电解液可以在金属锂表面形成致密且稳定的SEI,并抑制锂枝晶的产生。     

硝酸锂作添加剂对锂硫电池电化学性能的影响

采用充放电测试和交流阻抗测试研究了硝酸锂作电解液添加剂对锂硫电池电化学性能的影响. 采用电子扫描显微镜观察分析了添加剂对锂负极的影响, 探讨了硝酸锂的作用机理.  结果表明, 采用硝酸锂作为锂硫电池电解液的添加剂, 可以在锂负极表面形成具有钝化负极活性表面及保护锂负极的界面膜.  该膜可以抑制电解液中高价态聚硫离子与锂负极的副反应, 避免在锂负极表面形成不可逆的硫化锂, 从而提高锂硫电池的循环性能和放电容量. 采用硝酸锂作添加剂的锂硫电池首次放电比容量达1172 mA?h/g, 循环100次比容量保持为629 mA?h/g.     

锂硫电池电解质研究进展

锂硫电池由于其高能量密度(理论高达2600 Wh/kg)、低成本、环境友好等优点而广受关注. 但是锂硫电池仍存在正极活性物质利用率低、循环性能差等问题. 造成这些问题的主要原因是易溶于有机电解液的中间产物聚硫锂Li₂S_n (4≤n≤8)和不溶于有机电解液的硫化锂造成的. 简要介绍了锂硫电池体系的主要问题,并结合本研究小组的研究,对锂硫电池用电解质体系从有机电解液组成、电解液添加剂、聚合物电解质和无机固体电解质等方面进行了详细的综述,最后对电解质的发展前景进行了展望.     

高浓度LiI实现硫正极稳定的高效利用

具有高比容量和低成本的锂硫电池被认为是下一代电池的重要候选者.然而,低的硫利用率、严重的穿梭效应以及金属锂负极枝晶的生长制约其实际应用.在电解液中引入添加剂被证实是一种简单有效的性能改善策略.为此,本文将高浓度的LiI引入到Li-S电池的常规电解液中,研究高浓度的LiI电解液对硫正极的利用、金属锂负极的保护以及对应电池电化学性能的影响.结果表明,高浓度的碘化锂电解液能够在金属锂负极表层形成稳定的保护层,抑制了锂枝晶的产生.与此同时,碘化锂的引入大幅度提高电池的比容量、有效改善电池的倍率性能和循环稳定性.通过优化发现,浓度为0.5 mol·L^-1的LiI具有最佳的电化学性能.采用此电解液的锂硫电池,在1 C倍率下,放电容量高达1 200 mAh·g^-1. 200次循环之后,容量仍能保持在880 mAh·g^-1,容量保持率接近75%.此外,电池展示了良好的倍率性能,在5 C倍率下,放电容量依然高达700 mAh·g^-1.     

锂离子电池正极材料LiNi1/3Co1/3Mn1/3O2在不同电解液中的性能研究

应用低热固相合成法制备锂离子电池正极材料L iCo1/3N i1/3Mn1/3O2.研究该材料的结构与形貌,并比较它在商品L iPF6盐和在实验室合成的L iBOB(L iB(C2O4)2)盐电解液中的电化学性能.在L iPF6/EC+DMC+DEC电解液中,该材料表现出优良的电化学性能,其于0.5C、1C、1.5C、2C、3C放电倍率的初始比容量依次为167、163、163、157、147mAh/g,电池的循环性能也较好,说明低热固相合成的材料的有较好的高倍率性能.在L iBOB/EC+DEC+DE电解液中,0.5C倍率下比容量为160 mAh/g,较之L iPF6盐电解液的相差不大,但在高倍率下的比容量有所下降.     

柱状金属锂沉积物:电解液添加剂的影响

二次电池的能量密度已成为推动电动汽车和便携式电子产品技术向前发展的重要指标。使用石墨负极的锂离子电池正接近其理论能量密度的天花板,但仍难以满足高端储能设备的需求。金属锂负极因其极高的理论比容量和极低的电极电位,受到了广泛关注。然而,锂沉积过程中枝晶的生长会导致电池安全性差等问题。电解液对金属锂的沉积有着至关重要的影响。本文设计了一种独特的电解槽体系来进行柱状锂的沉积,研究了不同电解液体系(1mol·L^-1LiPF6-碳酸乙烯酯/碳酸二乙酯(EC/DEC,体积比为1:1)、1 mol·L^-1 LiPF6-氟代碳酸乙烯酯(FEC,体积分数5%)-EC/DEC (体积比为1:1))对金属锂沉积的影响。对两种电解液中金属锂沉积物长径比的研究表明,电解液的组分可以显著地影响金属锂的沉积形貌,在加入氟代碳酸乙烯酯(FEC)添加剂之后,柱状锂的直径从0.3–0.6μm增加到0.7–1.3μm,长径比从12.5下降到5.6。长径比的降低有助于减小金属锂和电解液的反应面积,提高金属锂负极的利用率和循环寿命。通过考察循环后锂片的表面化学性质,发现FEC的分解增加了锂表面固态电解质界面层中氟化锂(LiF)组分的比例,提高了界面层中锂离子的扩散速率,减少了锂的成核位点,从而给予锂核更大的生长空间,降低了沉积出的柱状锂的长径比。     

锂离子电池电解液中甲醇杂质对石墨电极性能影响机制的电化学阻抗谱研究

运用电化学阻抗谱和循环伏安法研究了在1mol/LLiPF6-EC/DEC/DMC电解液中,不同甲醇杂质含量对石墨电极性能的影响及其机制.结果表明,甲醇对石墨电极性能的影响与电解液中甲醇的含量有关;其对石墨电极性能的影响机制为甲醇在2.0V左右还原生成的甲氧基锂沉积在石墨电极表面上,形成一层初始SEI膜,影响了EC的还原分解成膜过程.     

4.5 V High‐Voltage Rechargeable Batteries Enabled by the Reduction of Polarization on the Lithium Metal Anode

Lithium metal is used to achieve high‐energy‐density batteries due to its large theoretical capacity and low negative electrochemical potential. The introduction of quasi‐solid electrolytes simultaneously overcomes the safety problems induced by the liquid electrolytes and the high interfacial resistance issues confronted by all solid‐state electrolytes. In‐depth investigations involving interfacial behaviors in quasi‐solid lithium metal batteries are inadequate. Herein an ultrathin Li₃OCl quasi‐solid‐state electrolyte layer (500 nm thickness) is used to cover a lithium anode. The polarization of the anode is remarkably reduced by introducing the Li₃OCl quasi‐solid‐state electrolyte. In contrast to the decomposition of solvents in a standard electrolyte (EC‐DEC,1.0 m LiPF₆), the established quasi‐solid‐state electrolyte interfaces can significantly inhibit the decomposition of solvents when the cut‐off voltage is 4.5 V.     

Anion receptor for enhanced thermal stability of the graphite anode interface in a Li-ion battery

The thermal stability of the solid electrolyte interphase (SEI) formed on a graphite anode has been enhanced by adding an anion receptor, tris(pentafluorophenyl)borane (TPFPB), to the electrolyte. The investigated electrolyte was LiBF₄ in a 2:1 mixture of ethylene carbonate (EC) and diethyl carbonate (DEC). Two concentrations of TPFPB have been investigated, 0.2 and 0.8 M. Galvanostatic cycling and differential scanning calorimetry (DSC) were used to study the effect of TPFPB on the electrochemical performance and thermal stability of graphite anodes. The best performance is obtained for a graphite anode cycled in an electrolyte with 0.2 M TPFPB: cyclability is improved, and the onset temperature for the first thermally activated reaction is increased by more than 60 °C up to 140–160 °C. X-ray photoelectron spectroscopy (XPS) has been used to examine the composition of the SEI formed in the different electrolytes; the improved performance for the graphite cycled with 0.2 M TPFPB is attributed to a reduced amount of LiF in the SEI.     

Stabilizing the Electrochemistry of Lithium-Selenium Battery via In situ Gelated Polymer Electrolyte: A Look from Anode

Li metal possesses a high theoretical specific capacity,high electronic conductivity,and a low electrochemical potential,making it a promising anode material for building next-generation rechargeable metal batteries.In case conventional liquid electrolytes were used,and the anode using Li metal has been hindered by unstable(electro)chemistry at Li/electrolyte interface and the accompanied dendrite issue.Specifically,for the Li-Se batteries,the dissolution and shuttle of polyselenide intermediates lead to the deposition of poorly-conductive species on the anode,which further aggravates the chemical environment at the anode.In this work,we proposed to stabilize the Li-Se electrochemistry by constructing a gel polymer electrolyte via in situ gelations of conventional ether-based electrolytes at room temperature.The results demonstrate that the in situ gelated electrolyte helps to build electrochemically stable electrode/electrolyte interfaces and promote the efficient transfer of charge carriers across the interface.Compared with the liquid electrolytes,the gelated electrolyte shows improved chemical compatibility with the Li metal anode,which effectively alleviates the unfavorable side reactions and dendrite formation at the anode/electrolyte interface,and the polyselenide shuttle from the cathode to the anode.As a result,the Li-Se battery shows a higher Coulombic efficiency and improved cycling performance.     

Low-temperature performance of Li-ion cells with a LiBF<Subscript>4</Subscript>-based electrolyte

The effect of LiBF₄ on the low-temperature performance of a Li-ion cell was studied by using a 1:1:1 (wt) EC/DMC/DEC mixed solvent. The results show that the LiBF₄-based electrolyte has a 2- to 3-fold lower ionic conductivity and shows rather higher freezing temperature compared with a LiPF₆-based electrolyte. Owing to electrolyte freezing, cycling performance of the Li-ion cell using LiBF₄ was significantly decreased when the temperature fell below –20 °C. However, impedance data show that at –20 °C the LiBF₄ cell has lower charge-transfer resistance than the LiPF₆ cell. In spite of the relatively lower conductivity of the LiBF₄-based electrolyte, the cell based on it shows slightly lower polarization and higher capacity in the liquid temperature range (above –20 °C) of the electrolyte. This fact reveals that ionic conductivity of the electrolytes is not a limitation to the low-temperature performance of the Li-ion cell. Therefore, LiBF₄ may be a good salt for the low-temperature electrolyte of a Li-ion cell if a solvent system that is of low freezing temperature, high solubility to LiBF₄, and good compatibility with a graphite anode can be formulated. Electronic Publication     

锂离子电池电解质的新型锂盐――双乙二酸硼酸锂

介绍了一种新型锂盐――双乙二酸硼酸锂(LiBOB)的基本性质及制备进展,并重点综述了其在锂电中应用的有关研究,包括基于LiBOB电解液的导电性研究,对负极材料、正极材料的稳定性研究,与其他锂盐在锂离子电池中混合使用的性能研究等。     

石墨负极在Et4NBF4+LiPF6/EC+PC+DMC电解液中的电化学行为

在PC+EC+DMC复合溶剂体系中, 研究了Et4NBF4(四氟硼酸四乙基铵)与LiPF6组成的复合盐电解质对石墨负极材料界面性质的影响. 用循环伏安和恒电流充放电测试方法研究了电解液与石墨负极的相容性, 通过傅里叶变换红外光谱(FTIR)对固体电解质中间相膜(SEI)的成分变化进行了研究. 结果表明, 电解液中的Et4NBF4参与了SEI膜的形成; 当Et4NBF4浓度为0.2 和0.5 mol·L-1时, 电池首次充放电不可逆容量损失明显减少, 循环效率分别上升到76.0%和81.6%. Et4NBF4/LiPF6复合盐电解质改善了PC基电解质与石墨负极的相容性.     

V_2O_5/C电化学电容器有机电解液的性能研究

以偏钒酸铵为反应原料,采用液相沉淀法制备出不定型V2O5电极材料.以V2O5为正极,石墨为负极,分别选用1.0 mol/L LiClO4/EC+DMC、1.0 mol/L LiPF6/EC+DEC+DMC、1.6 mol/L Et4NBF4/AN 3种有机电解液组成不对称电化学电容器,恒流充放电、循环伏安和交流阻抗等测试该模拟电容器,如以1.0 mol/LLiClO4/EC+DMC作电解液则具有良好的循环性能和较小的阻抗,且在500 mA/g电流密度下比能量达到8.4Wh/kg,充放电效率达98%.     

硫酸盐功能电解液增强水系钠离子电池NaTi2(PO4)3/C负极材料电化学性能的研究

水系钠离子电池具有钠资源丰富、成本低廉、安全可靠、维护简单等特点,在可再生能源规模储存领域具有重要应用前景。NASICON型NaTi₂(PO₄)₃具有可逆容量高、工作电位低、离子传输快等优点,是目前最受关注的水系钠离子电池负极材料。但是,该材料在传统的水系电解液中结构不稳定,循环性能不足。本论文通过调控Na₂SO₄浓度和引入MgSO₄添加剂,构建了一种新型硫酸盐功能电解液(2 mol·L^-1 Na₂SO₄ + 0.3 mol·L^-1 MgSO₄)。该电解液能够显著增强NaTi₂(PO₄)₃/C材料在充放电循环过程中的结构稳定性,从而提高其电化学可逆性和稳定性。电化学测试表明,NaTi₂(PO₄)₃/C基于该电解液在100 mA·g^-1条件下的可逆容量为93.4 mAh·g^-1,循环100次后容量保持率高达96.5%;基于该电解液构建的Na₂Ni[Fe(CN)₆]|NaTi₂(PO₄)₃/C电池可以稳定循环500次以上。本论文结合XRD、XPS等技术讨论分析了该电解液的功能作用机制,其研究结果为设计低成本高性能水系钠离子电池提供了新思路和实验基础。     

Designing solid-state interfaces on lithium-metal anodes: a review

Li-metal anodes are one of the most promising energy storage systems that can considerably exceed the current technology to meet the ever-increasing demand of power applications. The apparent cycling performances and dendrite challenges of Li-metal anodes are highly influenced by the interface layer on the Li-metal anode because the intrinsic high reactivity of metallic Li results in an inevitable solid-state interface layer between the Li-metal and electrolytes. In this review, we summarize the recent progress on the interfacial chemistry regarding the interactions between electrolytes and ion migration through dynamic interfaces. The critical factors that affect the interface formation for constructing a stable interface with a low resistance are reviewed. Moreover, we review emerging strategies for rationally designing multiple-structured solid-state electrolytes and their interfaces, including the interfacial properties within hybrid electrolytes and the solid electrolyte/electrode interface. Finally, we present scientific issues and perspectives associated with Li-metal anode interfaces toward a practical Li-metal battery.