Hard-carbon hybrid Li-ion/metal anode enabled by preferred mesoporous uniform lithium growth mechanism

To achieve high energy density in lithium batteries,the construction of lithium-ion/metal hybrid anodes is a promising strategy.In particular,because of the anisotropy of graphite,hybrid anode formed by graphite/Li metal has low transport kinetics and is easy to causes the growth of lithium dendrites and accumulation of dead Li,which seriously affects the cycle life of batteries and even causes safety problems.Here,by comparing graphite with two types of hard carbon,it was found that hybrid anode formed by hard carbon and lithium metal,possessing more disordered mesoporous structure and lithophilic groups,presents better performance.Results indicate that the mesoporous structure provides abundant active site and storage space for dead lithium.With the synergistic effect of this structure and lithophilic functional groups(–COOH),the reversibility of hard carbon/lithium metal hybrid anode is maintained,promoting uniform deposition of lithium metal and alleviating formation of lithium dendrites.The hybrid anode maintains a 99.5%Coulombic efficiency(CE)after 260 cycles at a specific capacity of 500 m Ah/g.This work provides new insights into the hybrid anodes formed by carbon-based materials and lithium metal with high specific energy and fast charging ability.

A novel design of 3D carbon host for stable lithium metal anode

Rational design of porous conductive hosts with high electrical conductivity,large surface area,and adequate interior space is desirable to suppressing dendritic lithium growth and accommodating large volume change of lithium metal anode during the Li plating/stripping process.However,due to the conductive nature of the conductive hosts,Li is easily deposited directly on the top of the hosts,which hinders it from fully functioning.To circumvent the issue,in this study,we designed a novel porous carbon host with a gradient-pore-size structure based on one-dimensional(1D)carbon with different diameters.With this kind of host,stable cycling with high and stable Coulombic efficiency of~98%is achieved at 0.5 mA cm^(−2) with an areal capacity of 1 mAh cm^(−2) over 320 cycles.In contrast,the normal three-dimensional(3D)carbon nanotube host presents a moss-like Li morphology with wildly fluctuating Coulombic efficiency after 100 cycles.The results reveal that the unique gradient-pore-size structure of the 3D conductive host greatly improves the performance of lithium metal batteries.

Acetylene/argon mixture plasma to build ultrathin carbon bridge of CF_(x)/C/MnO_(2) for high-rate lithium primary battery

Forming an ultrathin conducting layer on a fluorinated carbon(CFx)surface for reducing severe electrochemical polarization in lithium/fluorinated carbon primary batteries(Li/CF_(x))remains a considerable challenge for achieving batteries with excellent rate capability.Herein,CFxwas modified by using acetylene/argon mixture plasma combined with MnO_(2)particles.The CF_(x)/C/MnO_(2)composite effectively reduced the voltage hysteresis and improved the electrochemical performance of Li/CF_(x).The excellent rate performance of CF_(x)/C/MnO_(2)was due to the high electrochemical activity provided by the atomicscale conductive carbon layer and ultrafine MnO_(2)particles.Compared with pristine CF_(x),the charge transfer resistance of the optimized CF_(x)/C/MnO_(2)decreased from 218.5 to 48.2Ω,the discharge rate increased from 2C to 10C,and the power density increased from 3.11 to 13.44 kW·g^(-1),The intrinsic reason for the enhanced rate performance was attributed to the fact that the ultrathin carbon layer acted as a conductive bridge to reduce the voltage hysteresis at the initial stage of the Li/CF_(x)discharge,and the high electrochemical activity of the ultrafine MnO_(2)particles provided a faster lithium-ion diffusion rate.

Naphthalene-modulated microporous carbon layers of LiFePO_4 improve the high-rate electrochemical performance

Carbon layers with microporous structures fine-modulated by naphthalene(NAP) were prepared to coat on LiFePO_4, aiming to enhance the Li+diffusion coefficient for Li-ion batteries. Characterized by BET, XRD, TEM, EIS, etc., it is indicated that in the presence of NAP, the carbon-coated LiFePO_4/C-NAP composites have the enlarged micropore size of 1.66 nm and the enhanced Li^+ diffusion coefficient of2.83 × 10^(-12)cm^2s^(-1), which is about five times higher than that of LiFePO4/C prepared in the absence of NAP. At a high rate of 20 C, the discharge capacity of the LiFePO_4/C-NAP is up to 120.1 mA h g^(-1) and maintains a good retention rate of 93.2% after 400 cycles. It is suggested that the NAP-modulated carbon coating is a promising route to accelerate the Li-ion diffusion rate and enhance the electrochemical performance for lithium ion batteries.

Li/CF_(x)一次电池研究进展

锂/氟化碳(Li/CF_(x))一次电池是目前能量密度最高的化学电源,具有输出电压稳定、安全性好、使用温度范围宽和自放电率低等特点,在军事(单兵作战系统)、医疗(心脏起搏器)、太空探索(空间站)等关键领域具有无可替代的重要性。然而,氟化碳材料的电子导电性较差,很大程度地影响了电化学反应的电极过程动力学,导致Li/CF_(x)一次电池存在高倍率放电性能差、初始放电电压延迟严重、放电过程中发热量大等问题。本文通过对近期相关文献的探讨,首先综述了Li/CF_(x)一次电池在放电机理方面的研究进展,包括两相放电反应机理模型、生成石墨层间化合物中间相的放电反应机理模型、“核-壳”模型反应机理和边缘传播放电反应机理以及最近刚被提出的三步放电反应机理等。其次,重点分析了Li/CF_(x)一次电池面临问题的解决方法,包括氟化碳材料前驱体的选择、氟化方法的改进、复合材料的构建以及电解液的改性和优化方法。其中,氟化碳纳米管、氟化富勒烯、氟化石墨烯等新型氟化碳基材料的应用为氟化碳的发展提供了新的前景。在复合材料的构建策略上,导电聚合物、金属纳米颗粒、氧化物的加入可显著降低电压延迟时间和提升倍率性能。在电解液的调控策略上,氟离子结合剂的引入和氟化锂晶体生长动力学的计算,对于溶解氟化锂和控制氟化锂的生长具有重要作用,有望实现兼具高能量密度和高功率密度的宽温域Li/CF_(x)一次电池。

Synthesis and characterization of LiFePO_4/C composite used as lithium storage electrodes

LiFePO4/C composites with good rate capability and high energy density were prepared by adding sugar to the synthetic precursor. A significant improvement in electrode performance was achieved. The resulting carbon contents in the sample 1 and sample 2 are 3.06% and 4.95%（mass fraction）, respectively. It is believed that the synthesis of LiFePO4 with sugar added before heating is a good method because the synthesized particles having uniform small size are covered by carbon. The performance of the cathodes was evaluated using coin cells. The samples were characterized by X-ray diffraction and scanning electron microscope observation. The addition of carbon limits the particles size growth and enables high electron conductivity. The LiFePO4/C composites show very good electrochemical performance delivering about 142 mAh/g specific capacity when being cycled at the C/10 rate. The capacity fade upon cycling is very small.

Tailoring fluorine-rich solid electrolyte interphase to boost high efficiency and long cycling stability of lithium metal batteries

Lithium metal batteries(LMBs)are regarded as the most promising next-generation battery system due to their high energy density.However,Li dendrite growth and low Coulombic efficiency(CE)of Li metal anodes limit their commercialization.Regulating solid electrolyte interphase(SEI)is an extremely effective method to solve these problems and using electrolyte additives to regulate the SEI is one of the most effective strategies.Herein,we study the feasibility of trans-difluoroethylene carbonate(DFEC)used as the solvent additive in conventional ether electrolyte,which has excellent anti-reduction stability against Li metal.The result shows that a Li/Cu half-cell with the modified electrolyte can be steadily cycled for 300 cycles with an average CE of 97.41%at the current density of 0.5 m A cm^(-2)and with 97.1%for 140 cycles at 1 m A cm^(-2).Besides,the Li/LFP full cell with the modified electrolyte displays an improved capacity retention of 94.55%after 520 cycles with an average CE of 99.74%at 1 C.By contrast,the capacity retention of 56.2%and CE of 99.15%is obtained for the cell with pure ether electrolyte.The SEM images show that the DFEC enables dense Li deposition,and the FTIR and XPS spectra confirm the formation of Li Frich SEI with the DFEC.This work demonstrates the feasibility of using DFEC as the solvent additive in ether electrolyte to construct Li F-rich SEI,and it will provide important insight in developing high-performance electrolytes for LMBs.

LiFePO_(4)锂离子电池关键材料的湿法回收

废旧磷酸铁锂(LiFePO_(4))锂离子电池经破碎分选后制得黑粉,对黑粉采取湿法回收及再生,其中,锂、铁、磷的浸出率(回收率)可达97%以上。对浸出液采取化学沉淀法除铜、铝,铁粉置换法除铜,可将铜质量分数降至0.0001%以下,采用硫酸铵化学沉淀,可将铝质量分数降至0.0006%,达成深度除杂效果。除杂后的精制溶液可合成电池级无水磷酸铁及碳酸锂,并通过高温固相法制备LiFePO_(4)正极材料。制备的扣式电池以0.1 C在2.00~3.75 V循环,充放电比容量分别为162.96 mAh/g、159.31 mAh/g,首次循环的库仑效率为97.76%。

LiFePO_4锂离子电池正极材料的电化学性能

以碳凝胶作为碳添加剂, 采用固相法制备了复合型LiFePO4 /C锂离子电池正极材料。研究了不同掺碳量对样品性能的影响。利用X射线衍射仪、扫描电镜和碳硫(质量分数)分析方法对所得样品的晶体结构、表面形貌、含碳量进行分析研究。结果表明: 样品中的碳含量(质量分数)分别为 0%、5%、10%、22%, 所得样品均为单一的橄榄石型晶体结构, 碳的加入使LiFePO4 颗粒粒径减小。另外, 碳分散于晶体颗粒之间, 增强了颗粒之间的导电性。合成样品的电化学性能测试结果表明, 掺碳后的LiFePO4 放电比容量和循环性能都得到显著改善。其中,含碳量为 22%的LiFePO4 /C在 0 1C倍率下放电, 首次放电容量达 143 4mA·h/g, 充放电循环 6次后电容量为142 7mA·h/g, 容量仅衰减 0 7%。

高倍率性能锂离子电池Li[Ni1/3Co1/3Mn1/3]O2正极材料的制备及其电化学性能

采用改进的碳酸盐共沉淀与高温固相法相结合的方法制备出了高倍率性能的锂离子电池正极材料Li[Ni1/3Co1/3Mn1/3]O2,通过X射线衍射(XRD)、扫描电镜(SEM)、循环伏安扫描(CV)、电化学阻抗谱(EIS)和电化学性能测试等手段对材料进行表征.结果表明,该方法制备的材料具有良好的α-Na Fe O2型层状结构(R3m(166)),一次粒径平均大小为157 nm,二次颗粒成球形.同传统碳酸盐制备得到的材料相比,该材料具备良好的倍率性能和循环性能,在2.7-4.3 V电压范围内,0.1C(1.0C=180 m A?g-1)倍率下,首次放电比容量为156.4m Ah?g-1,库仑效率为81.9%.在较高倍率下,即0.5C、5.0C和20C时,其放电比容量分别为136.9、111.3、81.3m Ah?g-1.在1C倍率下100次循环容量保持率为92.9%,高于传统共沉淀法得到的材料(87.0%).

水热法制备锂电池正极材料o-LiMnO_2及其碳纳米管改性

Mn Cl2、Li OH、EDTA和Na Cl O混合溶液一步水热反应合成锂离子电池正极材料正交LiMnO2(o-LiMnO2),进一步在反应体系中添加碳纳米管(CNTs)制备碳纳米管改性的o-LiMnO2(o-LiMnO2/CNTs复合材料)。采用X-射线衍射和扫描/透射电镜表征产物的晶体结构、微观形貌,循环伏安法和恒流充放电测试得活性材料电化学性能。结果表明,体系中nLi∶nMn控制为8∶1,在180℃反应24 h得到目标产物;反应体系中添加CNTs形成复合材料可降低o-LiMnO2颗粒粒径、提高导电率。o-LiMnO2首次放电容量为76.0 m Ah·g-1,100周后容量保持为124.1 m Ah·g-1;o-LiMnO2/CNTs复合材料首次及100周放电容量(基于o-LiMnO2/CNTs的质量)分别高达94.1和159.8 m Ah·g-1。

磷酸钒锂/碳复合材料在锂离子电池中的电化学性能及电极反应动力学研究

相比于溶胶-凝胶法制备的Li_(3)V_(2)(PO_(4))_(3)/C(LVP/C-S),采用水热超声辅助流变相法结合溶液沉积法制备的Li_(3)V_(2)(PO_(4))_(3)/C(LVP/C-R)复合正极材料具有更优异的电化学性能。通过XRD、SEM和Raman光谱仪等对合成材料进行表征。将合成材料作为锂离子电池正极组装半电池进行倍率和循环性能测试,同时通过循环伏安法、电化学阻抗以及恒流间歇滴定技术分析电极反应动力学。结果表明,水热超声辅助流变相法合成的Li_(3)V_(2)(PO_(4))_(3)(LVP-R)通过溶液沉积法包覆碳层后,晶面间距增大,粒径更小,导电性、振实密度增大,分散性明显提升。这有利于Li^(+)在正极材料中嵌入/脱出,以及缩短Li^(+)的扩散路径,从而促使锂离子电池的倍率性能、库仑效率和循环稳定性提高。LVP/C-R作为锂离子电池正极材料,在0.1 C电流密度下表现出较高的初始放电比容量(160.12 mA·h/g),且在1 C倍率下循环200圈后放电容量保持率为89.16%,远高于LVP/C-S。此外,相比于LVP/C-S和LVP-R,LVP/C-R在锂离子电池中具有更大的Li^(+)表观扩散系数且动力学性能更优。

多孔微纳结构富锂正极材料0.6Li_2MnO_3·0.4LiNi_(0.5)Mn_(0.5)O_2的制备及其电化学性能

采用碳酸盐共沉淀与燃烧法相结合的方法制备得到了多孔微纳球形结构的富锂正极材料0.6Li_2MnO_3·0.4LiNi_(0.5)Mn_(0.5)O_2。借助X射线衍射(XRD)分析、X射线光电子能谱(XPS)、扫描电镜(SEM)、透射电镜(TEM)、N2吸附-脱附和恒电流充放电测试研究了其晶体结构、微观形貌和电化学性能。结果表明该方法制备出的材料是由一次颗粒径约300 nm的小颗粒组成的多孔微纳球形结构,比表面积为13 m2·g^(-1),具有完善的α-NaFeO_2层状结构(空间群为R3m)。电化学性能测试结果证实该材料具有优异的高容量、高循环稳定性和高倍率性能。在2.0~4.8 V,电流密度为0.1C、0.2C、0.5C、1C、3C、5C和10C时的放电比容量分别为:266、254、235、205、186、149和107 m Ah·g^(-1);在0.5C下循环100次后,放电比容量仍为217 m Ah·g^(-1)(容量保持率为94%)。

Influence of pretreatment process on structure, morphology and electrochemical properties of Li[Ni_(1/3)Co_(1/3)Mn_(1/3)]O_2 cathode material

The layered Li[Ni1/3Mn1/3Co1/3]O2 was separately synthesized by pretreatment process of ball mill method and solution phase route, using [Ni1/3Co1/3Mn1/3]3O4 and lithium hydroxide as raw materials. The physical and electrochemical behaviors of Li[Ni1/3Mn1/3Co1/3]O2 were characterized by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, field emission scanning electron microscopy （FESEM） and electrochemical charge/discharge cycling tests. The results show that the difference in pretreatment process results in the difference in compound Li[Ni1/3Co1/3Mn1/3]O2 structure, morphology and the electrochemical characteristics. The Li[Ni1/3Mn1/3Co1/3]O2 prepared by solution phase route maintains the uniform spherical morphology of the [Ni1/3Co1/3Mn1/3]3O4, and it exhibits a higher capacity retention and better rate capability than that prepared by ball mill method. The initial discharge capacity of this sample reaches 178 mA-h/g and the capacity retention after 50 cycles is 98.7% at a current density of 20 mA/g. Moreover, it delivers high discharge capacity of 135 mA-h/g at a current density of 1 000 mA/g.

不同碳源对制备LiFePO_4/C复合材料性能影响

分别以蔗糖、葡萄糖、酚醛树脂、酚醛树脂和葡萄糖混合物为碳源用固相碳热还原法制备了四种不同碳含量的LiFePO4/C正极材料。利用X-射线粉末衍射(XRD)、扫描电镜(SEM)等测试手段对合成材料进行了表征,通过恒流充放电和循环伏安测试研究了材料的电化学性能。结果表明:所合成的LiFePO4均为纯相,但是用蔗糖合成的样品颗粒更细小,电化学性能明显优于用其他碳源制备的样品,其中含碳3.01%的样品在0.1 C、1 C下的放电比容量分别为158.9、146.5 mAh/g。

焙烧温度对Li[Mn_(1/3)Ni_(1/3)Co_(1/3)]O_2结构及电化学性能影响

采用碳酸盐共沉淀法制备了Li[Mn1/3Ni1/3Co1/3]O2,研究了前驱体的焙烧温度对材料结构和电化学性能的影响。XRD测试结果表明,800℃下焙烧得到的样品具有较好的层状结构和较低的阳离子混排程度。SEM测试表明合成材料具有球状形貌,平均粒径可达5μm,组成它的一次颗粒粒径平均为200 nm。在2.8~4.3 V（vs.Li/Li＋）0.2 C条件下进行充放电测试,800℃下合成的样品的首次放电比容量最高（159.06 mAh.g-1）,容量损失最小,循环50次后能保持初始放电比容量的95.7%。EIS分析结果表明,800℃焙烧的样品的电化学活性最好。

锂离子电池用LiPF_6/PC+FEC电解液的低温性能

研究氟代碳酸乙烯酯(fluoroethylene carbonate,FEC)添加剂对锂离子电池用碳酸丙烯酯(PC)基电解液低温放电性能和常温循环性能的影响,并通过电化学阻抗谱(EIS)、X线光电子能谱(XPS)以及气质联用谱(GC-MS)等对FEC在PC基电解液中的作用机理进行探讨。研究结果表明:往PC电解液中添加质量分数为5%的FEC可以在石墨电极表面形成完整且致密的SEI膜,从而有效阻止PC在负极石墨的共嵌入;电池在低温-20℃及-40℃下0.5C放电容量分别可达到室温容量的98%及87%;FEC形成的SEI膜有效降低了锂离子电池的低温电荷转移阻抗,是提高电池低温性能的主要因素之一;FEC在正极钴酸锂材料表面形成了导电性能优异的SEI膜层,改善了锂离子电池的低温性能和常温循环性能。

多孔氮氟共掺杂碳气凝胶的制备及其在锂硫电池中的应用

锂硫电池以其超高的理论能量密度,已成为最具发展潜力的新一代电化学储能技术,但硫正极存在电导率低、体积膨胀、多硫化物穿梭效应等技术瓶颈问题,制约了其实际应用。通过甲醛和3-氨丙基三乙氧基硅烷的醛胺缩合和溶胶-凝胶化反应合成了席夫碱二氧化硅凝胶,经与聚四氟乙烯乳液冷冻干燥、热处理同步刻蚀二氧化硅以及碳化制备了多孔氮氟共掺杂碳气凝胶(NF-CA)。以NF-CA为载体制备的NF-CA/S正极材料表现出优异的循环性能和倍率性能,0.2 C循环初始放电比容量高达1322 mA∙h/g,1 C循环200圈可逆比容量可保持564 mA∙h/g,2C倍率下可逆比容量高达598mA∙h/g。

中空Li_4Ti_5O_(12)纳米材料的合成及电化学性能

运用碳模板法制备单分散性的钛酸锂（Li4Ti5O12），采用XRD、透射电镜（TEM）和恒流充放电测试对样品的物相、形貌和电化学性能进行分析。样品是平均粒径为480nm的尖晶石型Li4Ti5O12纯相，为中空微球。在1．0．2．5V充放电，0．2C的首次和第100次循环的放电比容量分别为174mAh／g、129mAh／g；依次以0．2C、1．0C和2．0C在各倍率均循环20次，第60次循环的放电比容量仍有127mAh／g。

废旧锂离子电池回收过程中钙镁渣制备电池级碳酸锂研究

以废旧锂离子电池回收过程中产生的钙镁渣为原料,通过复分解浸出-净化-沉锂-碳化分解工艺制备电池级碳酸锂。结果表明,在MgSO_(4)·7H_(2)O用量为理论量的1.1倍、初始pH值1.5、反应时间2.0 h、固液比1∶6、反应温度90℃、终点pH值3.5条件下,Li浸出率为98.39%,浸出液中Li质量浓度为18.03 g/L。浸出液通过树脂除氟、碱液除杂、碳酸钠沉锂,制备出纯度为95.11%的粗制碳酸锂。粗制碳酸锂通过碳化-树脂除钙镁-热解工艺制备出质量分数为99.64%的电池级碳酸锂。该工艺锂回收率为95.08%,经济价值高,具有良好的工业应用前景。