2018年清洁能源开发热点回眸

 2018年清洁能源领域取得了一系列激动人心的进展，提出了液态阳光的概念，不依赖p-n结的光伏转化新原理被发现以及锂硫电池步入商业化应用等。本文评述了太阳能电池、燃料电池、锂电池及生物质能源等技术在2018年的重要突破，并展望了未来清洁能源领域的发展方向。     

基于有监督核自组织映射的锂电池健康状态预测

高效准确地预测锂电池的健康状态(State of health,SOH)可以保证锂电池的正常运行,提高维护效率及电池本身的稳定性。提出一种基于有监督核自组织映射(Supervised kernel self-organizing map,SKSOM)的建模方法用于锂电池SOH预测。首先,对锂电池的原始放电数据进行预处理及归一化;然后,设计并优化了针对SKSOM的输入特征,在此基础上训练出SOH预测模型;最后,在美国国家航空航天局(National Aeronautics and Space Administration,NASA)的标准锂电池数据集上进行验证。实验结果表明,该文所用的预测模型能有效挖掘出锂电池的SOH规律,预测性能优于其他已有的SOH预测模型。     

石墨烯负载的氧配位钴单原子稳定金属锂负极

Lithium (Li)-based batteries are the dominant energy source for consumer electronics, grid storage, and electrified transportation. However, the development of batteries based on graphite anodes is hindered by their limited energy density. With its ultrahigh theoretical capacity (3860 mAh∙g⁻¹), low redox potential (−3.04 V), and satisfactorily low density (0.54 g∙cm⁻³), Li metal is the most promising anode for next-generation high-energy-density batteries. Unfortunately, the limited cycling life and safety issues raised by dendrite growth, unstable solid electrolyte interphase, and "dead Li" have inhibited their practical use. An effective strategy is to develop a suitable lithiophilic matrix for regulating initial Li nucleation behavior and controlling subsequent Li growth. Herein, single-atom cobalt coordinated to oxygen sites on graphene (Co-O-G SA) is demonstrated as a Li plating substrate to efficiently regulate Li metal nucleation and growth. Owing to its dense and more uniform lithiophilic sites than single-atom cobalt coordinated to nitrogen sites on graphene (Co-N-G SA), high electronic conductivity, and high specific surface area (519 m²∙g⁻¹), Co-O-G SA could significantly reduce the local current density and promote the reversibility of Li plating and stripping. As a result, the Co-O-G SA based Li anodes exhibited a high Coulombic efficiency of 99.9% at a current density of 1 mA∙cm⁻² with a capacity of 1 mAh∙cm⁻², and excellent rate capability (high current density of 8 mA∙cm⁻²). Even at a high plating capacity of 6 mAh∙cm⁻², the Co-O-G SA electrode could stably cycle for an ultralong lifespan of 1300 h. In the symmetric battery, the Co-O-G SA based Li anode (Co-O-G SA/Li) possessed a stable voltage profile of 18 mV for 780 h at 1 mA∙cm⁻², and even at a high current density of 3 mA∙cm⁻², its overpotential maintained a small hysteresis of approximately 24 mV for > 550 h. Density functional theory calculations showed that the surface of Co-O-G SA had a stronger interaction with Li atoms with a larger binding energy, −3.1 eV, than that of Co-N-G SA (−2.5 eV), leading to a uniform distribution of metallic Li on the Co-O-G SA surface. More importantly, when matched with a sulfur cathode, the resulting Co-O-G SA/lithium sulfur full batteries exhibited a high capacity of 1002 mAh∙g⁻¹, improved kinetics with a small polarization of 191 mV, and an ultralow capacity decay rate of 0.036% per cycle for 1000 cycles at 0.5C (1C = 1675 mA∙g⁻¹) with a steady Coulombic efficiency of nearly 100%. Therefore, this work provides novel insights into the coordination environment of single atoms for the chemistry of Li metal anodes for high-energy-density batteries.     

新型固体电解质Li_3PO_4-LiAlO_2的合成及其电化学性能研究

采用固相合成法制备了Li3PO4-LiAlO2固态锂离子电解质材料.研究了摩尔配比、煅烧温度对产物相组成、颗粒形貌、电性能的影响.结果表明:当P/Al化学计量比为1∶1时,煅烧后试样中存在片状的γ-LiAlO2和球状的γ-Li3PO4两相,粒径约为0.5~1μm.当P/Al化学计量比为3∶1时,煅烧后试样主要是Al掺杂的球状γ-Li3PO4固溶体.此样品1 000℃煅烧后,离子电导率为6.4×10-5S/cm,说明Al掺杂能有效提高γ-Li3PO4无机固体电解质离子电导率.1 100℃煅烧后,样品锂离子电导率降低.循环伏安曲线研究表明,Al掺杂γ-Li3PO4无机固体电解质样品在饱和LiNO3水溶液中具有较好的可逆性,其电化学窗口达到1.5V.     

立体碳包覆钛掺杂LiFePO_4的制备及高低温性能研究

以高价的Ti 4+为掺杂离子、聚乙烯醇(PVA)为碳源,通过高温固相法制备了原位立体碳包覆的LiFe0.96Ti0.02PO4/C正极材料.采用XRD,SEM,TEM及EDS对材料的微观结构进行了表征,通过循环伏安、交流阻抗以及恒流充放电实验测试材料的电化学性能.结果表明,PVA的热解碳导电优良且最易于实现原位立体包覆LiFePO4,经过原位立体碳包覆和钛掺杂综合改性后,活性材料在不降低原有高温结构稳定性的前提下,具备了更优良的低温电化学性能和倍率性能:于0℃时0.1C和30℃时5C的放电比容量分别为128.7mAh/g和97.4mAh/g.     

醚链改性聚环氧乙烷的合成及性能研究

考察烷基磷酸铝催化剂i-Bu₃Al/H₃PO₄/DBU催化环氧乙烷(EO)、甘醇甲基缩水甘油醚(nGE)与烯丙基缩水甘油醚(AGE)二元及三元共聚合的催化性能,通过核磁共振波谱(NMR)、凝胶渗透色谱(GPC)和示差扫描量热仪(DSC)对共聚物微观结构和热性能进行表征分析。结果表明25℃甲苯溶剂中,i-Bu₃Al/H₃PO₄/DBU催化剂可以高效催化不同比例的EO、nGE和AGE共聚合,以100%收率获得组成精确可控的高分子量EO-nGE二元及EO-AGE-nGE三元无规共聚物;nGE的醚链长度对聚合性能无影响,二甘醇甲基缩水甘油醚(2GE)和四甘醇甲基缩水甘油醚(4GE)均可实现可控引入聚环氧乙烷制备醚链改性聚环氧乙烷。EO-AGE-nGE三元共聚物以1,2-乙二硫醇为交联剂制备了交联聚合物。测试醚链改性聚环氧乙烷的性能,发现醚链长度、含量及交联对聚合物电导率和力学性能有很大影响。4GE为共聚单体的聚环氧乙烷电导率高于2GE。随着醚链含量增大,聚合物电导...     

锂电池中的“锂键”效应

由于广泛存在,氢键在化学领域备受重视。“锂键”具有类似于氢键的一些性质,但锂的金属性和相对较大的原子半径,又使得“锂键”具有自己独特的一些特征。在氢键的基础上,介绍了“锂键”的概念、结构特点及其在锂电池中的应用,有助于人们深刻理解和应用“锂键”。考虑到“锂键”的新概念目前在化学教学中还较少涉及,期望今后可以适当增加“锂键”化学的相关知识,紧跟科技发展的潮流,进一步培养学生的科研创新意识。     

LiNi0.5Mn1.5O4-xFx高电压电极高温保存下的电化学行为

采用溶胶-凝胶法结合高温热处理制备了锂离子电池用5 V正极材料LiNi0.5Mn1.5O4-xFx(x=0, 0.1). 通过X射线衍射(XRD)、扫描电子显微镜(SEM)和低温氮吸附法(BET)表征了粉体材料的结构、表面形貌和比表面特性, 并以其为正极材料装配电池后, 在85 ℃下高温保存24 h, 测量了保存前后电池的一系列电化学性质变化. 结果表明, 高温保存时电池开路电压会因自放电而较快地下降. 材料的比表面积和氟掺杂显著地影响电池的电压保持能力. 比表面积愈大, 电压保持时间愈短. 氟掺杂有利于提高电池在高温条件下的电压稳定性, 并可以改善电极与电解液之间的界面性质,使充放电性能更好.     

电动汽车锂电池组的新型双向均衡法

由于电池制造工艺的制约导致生产出的电池间存在一定的离散性,多次充放电后不一致性更加严重,因此有必要对电动汽车电池组进行均衡.在分析了锂电池间不一致性的基础上建立了双向均衡结构,采用粒子滤波PF(Particle Filter)法估算电池初始剩余电量SOC(State Of Charge),提出了先让高SOC电池放电和先给低SOC电池充电的均衡法.该方法相比传统基于充电电压的均衡法能更精确的反映电池能量状态.实验结果表明,对于要求低能耗的系统采用先让高SOC电池放电均衡至±2%平均SOC界限范围;对于要求均衡结果一致性较高的系统采用先给低SOC电池充电均衡至±1%平均SOC界限范围.该均衡方法有效改善了电池组间的不一致性,对于提高电动汽车锂离子电池的使用寿命和续航里程具有实际意义.