【天津大学学报英文版】 | 能源专辑（2019—2020）

01 RESEARCH ARTICLE

介孔石墨烯骨架/金属锂复合负极

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He Liu, Xinbing Cheng, Rui Zhang, Peng Shi, Xin Shen, Xiaoru Chen, Tao Li, Jiaqi Huang, Qiang Zhang
🔖Trans Tianjin Univ, 2020, 26(2):127-134

本文亮点

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本文采用具有高比表面积的导电介孔石墨烯骨架(MGH)材料作为沉积骨架，调控金属锂负极的沉积行为，具有以下优势：

(1) MGH的高比表面积(2090 ㎡/g)可以有效降低电极的局部电流密度，使成核均匀，抑制锂离子在沉积过程中枝晶的出现。

(2) MGH为锂沉积和剥离过程提供了一个互连的导电通路，从而缓解了死锂的形成。

(3) MGH能保持长期的结构稳定性，在长周期内保证均匀的沉积/剥离行为。

这促进了MGH电极的高库伦效率、低极化和长寿命，特别是在15.0 mA/c㎡的超高倍率下的优异性能。

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02 RESEARCH ARTICLE

Highly Selective LithiumIon Adsorbents: Polymeric Porous Microsphere with Crown Ether Groups

Caideng Yuan, Lei Zhang, Haichao Li, Ruiwei Guo, Meng Zhao, Lan Yang
🔖Trans Tianjin Univ, 2019, 25(2):101-109
Abstract 
In this study, we prepared and applied polymeric porous microsphere adsorbents with selectivity for  Li⁺ extraction from aqueous solution. We synthesized the adsorbents by suspension polymerization using methacryloyoxyme-12-crown-4 (M12C4) as a functional monomer, which had been synthesized from 2-hyroxymethyl-12-crown-4 and methacryloyl chloride. We verified the chemical composition by solid nuclear magnetic resonance (¹³C-NMR) spectroscopy and observed the porous structure by scanning electron microscopy (SEM). We conducted adsorption isothermal and kinetic tests to determine the adsorption properties. It was found that the adsorbents showed high adsorption efficiency and an adsorption equilibrium time of 200 min. In addition, since the crown ether used in this work could form a stable complex with  Li⁺, we observed good selectivity for  Li⁺ in the prepared solution compared with other ions such as  Na⁺,  K⁺,  Mg²⁺, and  Ca²⁺. We reused the adsorbents five times with no significant decrease in adsorptive capacity. 

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03 RESEARCH ARTICLE

Ni-Doped BiVO₄ with V⁴⁺ Species and Oxygen Vacancies for Efficient Photoelectrochemical Water Splitting

Dechao Kong, Jie Qi, Danyang Liu, Xiangwen Zhang, Lun Pan, Jijun Zou

🔖Trans Tianjin Univ, 2019, 25(4):340-347

Abstract

Bismuth vanadate is a promising photoanode material for photoelectrochemical (PEC) water splitting, but its activity and stability need to be further improved. In this work, we synthesized Ni-doped  BiVO₄ abundant with V⁴⁺ species and oxygen defects through an in situ electrodeposition method. The effective doping can decrease the particle size of  BiVO₄ and lead to the formation of  V⁴⁺ species/oxygen defects. Accordingly, the doped and defective  BiVO₄ showed high optical absorption and rapid charge transfer, and further showed much higher PEC activity than pure  BiVO₄. Specifically, 5-Ni-BiVO₄ exhibits the highest activity in PEC water splitting, with a photocurrent of 2.39 mA/cm² at 1.23 V versus RHE (the reversible hydrogen electrode), which is 2.5 times higher than pure  BiVO₄ (0.94 mA/cm²), and much higher incident photon-to-current efficiency (IPCE) value of 45% (while only 25% for  BiVO₄ at ca. 400 nm). This work provides an in situ method for the development of a high-performance photoanode. 

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04 RESEARCH ARTICLE

Hierarchical NiCo LDH–rGO/Ni Foam Composite as Electrode Material for High-Performance Supercapacitors

Shirun Yang, Zilan Zhang, Jinghong Zhou, Zhijun Sui, Xinggui Zhou

🔖Trans Tianjin Univ, 2019, 25(3):266-275

Abstract

In this study, a bulk composite material symbolized as NiCo LDH–rGO/Ni F was developed by a solvothermal process for the first time. This material was fabricated through simultaneous growth of nickel–cobalt layered double hydroxide (NiCo LDH) and reduced graphene oxide (rGO) on nickel foam. This bulk composite can be used directly as a binder-free electrode for supercapacitors (SCs). The physicochemical properties of this composite were characterized by scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy. The electrochemical properties of the composite were measured by the cyclic voltammetry and galvanostatic charge–discharge. The results show that this composite had a hierarchical structure and exhibited a significantly enhanced specific capacitance of up to 3383 F/g at 1 A/g. The asymmetric SC using this composite as a positive electrode had a high energy density of 40.54 Wh/kg at the power density of 206.5 W/kg and good cycling stability. Owing to the synergies between the metal oxides and the rGO, the preparation method of in situ growth and its hierarchical structure, this bulk composite displayed excellent electrochemical performance and had a promising application as an efficient electrode for high-performance SCs. 

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05 RESEARCH ARTICLE

From Jackfruit Rags to Hierarchical Porous N-Doped Carbon: A High-Performance Anode Material for Sodium-Ion Batteries

Baisheng Zhao, Yichun Ding, Zhenhai Wen

🔖Trans Tianjin Univ, 2019, 25(5):429-436

Abstract 

Renewable biomass-derived carbon materials have attracted increasing research attention as promising electrode materials for electrochemical energy storage devices, such as sodium-ion batteries (SIBs), due to their outstanding electrical conductivity, hierarchical porous structure, intrinsic heteroatom doping, and environmental friendliness. Here, we investigate the potential of hierarchical N-doped porous carbon (NPC) derived from jackfruit rags through a facile pyrolysis as an anode material for SIBs. The cycling performance of NPC at 1 A/g for 2000 cycles featured a stable reversible capacity of 122.3 mA·h/g with an outstanding capacity retention of 99.1%. These excellent electrochemical properties can be attributed to the unique structure of NPC; it features hierarchical porosity with abundant carbon edge defects and large specific surface areas. These results illuminate the potential application of jackfruit rags-derived porous carbon in SIBs. 

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06 RESEARCH ARTICLE

Hydrogen Bonding-Assisted Synthesis of Silica/Oxidized Mesocarbon Microbeads Encapsulated in Amorphous Carbon as Stable Anode for Optimized/Enhanced Lithium Storage

Zongjie Cao, Huitian Liu, Wenlong Huang, Peng Chen, Yuansheng Liu, Yu Yu, Zhongqiang Shan, Shuxian Meng

🔖Trans Tianjin Univ, 2020, 26(1):13-21

Abstract 

The practical application of silica-based composites as an alternative to commercial graphite anode materials is hampered by their large volumetric expansion, poor conductivity, and low Coulombic efficiency. In this work, a novel silica/oxidized mesocarbon microbead/amorphous carbon  (SiO₂/O’MCMB/C) hierarchical structure in which  SiO₂ is sandwiched between spherical graphite and amorphous carbon shell was successfully fabricated through hydrogen bonding-assisted self-assembly and post-carbon coating method. The obtained three-layer hierarchical structure effectively accommodates the volumetric expansion of  SiO₂ and significantly enhances the electronic conductivity of composite materials. Moreover, the outer layer of amorphous carbon effectively increases the diffusion rate of lithium ions and promotes the formation of stable SEI film. As a result, the  SiO₂/O’MCMB/C composite exhibits superior electrochemical performance with a reversible capacity of 459.5 mA h/g in the first cycle, and the corresponding Coulombic efficiency is 62.8%. After 300 cycles, the capacity climbs to around 600 mA h/g. This synthetic route provides an efficient method for preparing  SiO₂ supported on graphite with excellent electrochemical performance, which is likely to promote its commercial applications. 

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07 RESEARCH ARTICLE

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Chang Zhang, Cong Wu, Zhiwei Zhang, Yanran Shen, Wei Liu

🔖Trans Tianjin Univ, 2020, 26(2):142-147

本文亮点

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本文通过溶胶-凝胶法成功地合成了钙钛矿型LaNiO₃（LNO）氧化物作为新型负极材料。通过SEM和XRD测试了其表面形貌和晶相结构，并通过CV、EIS和GCD对其电化学性能进行表征，系统地研究了在不同温度下煅烧的LNO的微观结构和电化学性能。

LNO负极材料具有以下性能：

（1）LNO在6 C高温下比容量达到77 mAh/g。

（2）LNO在1 C高温下循环200次后比容量达到92 mAh/g。

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08 RESEARCH ARTICLE

Optical and Irradiation-Resistant Properties of ITO Films on F46 and PI Substrates

Chao Zhou, Hui Zhou, Yanchun He, Miao Yang, Yuqing Xiong, Lingmao Xu, Yi Wang

🔖Trans Tianjin Univ, 2019, 25(2):195-200

Abstract

This study investigated indium tin oxide (ITO) films that were deposited on fluororesin-46 (F46) and polyimide (PI) transparent flexible substrates by a DC magnetron sputtering system. The optical properties of ITO films on F46 and PI including transmittance and reflectance in visible, near-infrared, and infrared spectral regions were obtained, and the surface morphology, and optical and electrical properties of ITO/F46 and ITO/PI after vacuum ultraviolet irradiation were investigated. The results showed that the mean transmittances of ITO/F46 and ITO/PI decreased and the sheet resistance increased after the irradiation, and these effects were mainly attributed to the greater surface roughness and crystal defects caused by the irradiation. 

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09 RESEARCH ARTICLE

Facile One-Pot Synthesis of ZSM-5 Aggregates with Inter- and Intra-Crystalline Mesopores for Methanol to Gasoline Conversion

Yaquan Wang, Chunyang Fan, Hongyao Li, Xiao Wang, Fanjun Meng, Chao Sun, Liying Sun

🔖Trans Tianjin Univ, 2019, 25(1):9-22

Abstract 

ZSM-5 aggregates consisting of superfine and hierarchical nanocrystals (combined with micropores and intra-crystalline mesopores) with an average size of 30 nm were prepared through one-pot synthesis with the assistance of anionic polyacrylamide (APAM). The resultant zeolites (AHN-ZSM-5) were characterized by XRD, ICP-OES, SEM, TEM, BET,  NH₃-TPD, Py-IR, and TG analyses and evaluated in the methanol to gasoline (MTG) reaction. Characterization results show that the hierarchical ZSM-5 aggregates possessed two kinds of mesopores, namely inter- and intra-crystalline mesopores. The amount of APAM considerably influenced the mesoporosity and textural properties of AHN-ZSM-5 zeolites. With the addition of APAM in the synthesis, the AHN-ZSM-5 zeolites exhibited large mesopore volume, large external surface area, and appropriate acidity. When applied in the MTG reaction, AHN-ZSM-5 demonstrated a catalytic lifetime that was 1.6 times longer than that of conventional ZSM-5 synthesized in the absence of APAM. 

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10 RESEARCH ARTICLE

Facile Fabrication of Fe₃O₄@TiO₂@C Yolk–Shell Spheres as Anode Material for Lithium Ion Batteries

Wenming Liao, Zhongqiang Shan, Jianhua Tian

🔖Trans Tianjin Univ, 2020, 26(1):3-12

Abstract

Transition metal oxides have been actively exploited for application in lithium ion batteries due to their facile synthesis, high specific capacity, and environmental-friendly. In this paper,  Fe₃O₄@TiO₂@C yolk–shell (Y–S) spheres, used as anode material for lithium ion batteries, were successfully fabricated by Stӧber method. XRD patterns reveal that  Fe₃O₄@TiO₂@C Y–S spheres possess a good crystallinity. But the diffraction peaks’ intensity of  Fe₃O₄ crystals in the composites is much weaker than that of bare  Fe₃O₄ spheres, indicating that the outer anatase  TiO₂@C layer can cover up the diffraction peaks of inner  Fe₃O₄ spheres. The yolk–shell structure of  Fe₃O₄@TiO₂@C spheres is further characterized by TEM, HAADFSTEM, and EDS mapping. The yolk–shell structure is  good for improving the cycling stability of the inner  Fe₃O₄ spheres during lithium ions insertion–extraction processes. When tested at 200 mA/g, the  Fe₃O₄@TiO₂@C Y–S spheres can provide a stable discharge capacity of 450 mAh/g over 100 cycles, which is much better than that of bare  Fe₃O₄ spheres and  TiO₂@C spheres. Furthermore, cyclic voltammetry curves show that the composites have a good cycling stability compared to bare  Fe₃O₄ spheres. 

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11 RESEARCH ARTICLE

Evaluation and Analysis of Battery Technologies Applied to Grid-Level Energy Storage Systems Based on Rough Set Theory

Zhiyuan Xie, Liang Du, Xiaojun Lv, Qing Wang, Jianglei Huang, Tianyi Fu, Shengyue Li

🔖Trans Tianjin Univ, 2020, 26(3):228-235

Abstract

Interest in the development of grid-level energy storage systems has increased over the years. As one of the most popular energy storage technologies currently available, batteries offer a number of high-value opportunities due to their rapid responses, flexible installation, and excellent performances. However, because of the complexity, multifunctionality, and wide deployment of power grids, trade-offs in battery performance exist, especially when considering economics, environmental effects, and safety. Therefore, establishing a comprehensive assessment of battery technologies is an urgent undertaking. In this work, we present an analysis of rough sets to evaluate the integration of battery systems (e.g., lead–acid batteries, lithium-ion batteries, nickel/metal–hydrogen batteries, zinc–air batteries, and Na–S batteries) into a power grid. Specifically, technological properties, economic significance, environmental effects, and safety of these battery systems are evaluated on the basis of rough set theory. In addition, some perspectives are provided to promote the development of battery technologies for grid-level energy storage. 

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12 REVIEW

电网侧储能用电池技术

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Xiayue Fan, Bin Liu, Jie Liu, Jia Ding, Xiaopeng Han, Yida Deng, Xiaojun Lv, Ying Xie, Bing Chen, Wenbin Hu, Cheng Zhong

🔖Trans Tianjin Univ, 2020, 26(2):92-103

本文亮点

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◆电网侧储能有助于平衡发电、分配和使用的供需关系，避免电网侧的过量发电，缓解电网的供电缺口，提高发电设备的利用效率，减少电网建设投资，为电网系统安全稳定运行提供强有力的保证；

◆与传统的储能技术相比，电池具有易于模块化、响应快速、安装灵活和构建周期短的优点，被认为是电网侧的理想储能设备；

◆电网侧储能的特定应用需求包括削峰填谷、调压调频、应急响应；

◆电网侧储能用电池技术应具有快速响应、低成本、长寿命、高功率和能量效率等特点；

◆分析了几种具有发展前景的电网侧储能用电池技术（铅酸电池、镍镉电池、镍氢电池、钠硫电池、锂离子电池、液流电池）的电池构造设计、工作机理以及应用于电网侧储能方面的优缺点。

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13 REVIEW

Applications of Lithium-Ion Batteries in Grid-Scale Energy Storage Systems

Tianmei Chen, Yi Jin, Hanyu Lv, Antao Yang, Meiyi Liu, Bing Chen, Ying Xie, Qiang Chen

🔖Trans Tianjin Univ, 2020, 26(3):208-217

Abstract 

In the electrical energy transformation process, the grid-level energy storage system plays an essential role in balancing power generation and utilization. Batteries have considerable potential for application to grid-level energy storage systems because of their rapid response, modularization, and flexible installation. Among several battery technologies, lithium-ion batteries (LIBs) exhibit high energy efficiency, long cycle life, and relatively high energy density. In this perspective, the properties of LIBs, including their operation mechanism, battery design and construction, and advantages and disadvantages, have been analyzed in detail. Moreover, the performance of LIBs applied to grid-level energy storage systems is analyzed in terms of the following grid services: (1) frequency regulation; (2) peak shifting; (3) integration with renewable energy sources; and (4) power management. In addition, the challenges encountered in the application of LIBs are discussed and possible research directions aimed at overcoming these challenges are proposed to provide insight into the development of grid-level energy storage systems. 

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14 REVIEW

层状磷在储能中的应用综述

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Cheng Liu, Yinghao Wang, Jie Sun, Aibing Chen

🔖Trans Tianjin Univ, 2020, 26(2):104-126

本文亮点

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◆磷具有多种同素异形体及多种拓扑结构，其中具有层状结构的磷（黑磷、蓝磷）由于具有良好的导电性和热稳定性，且带隙可调等优点而备受关注。

◆本文从层状磷的结构、维度、及所处化学环境等角度综述了层状磷在储能领域中的应用，包括锂离子电池、钠离子电池、钾离子电池、镁离子电池、锂硫电池、锂空气电池及超级电容器。

◆在储能领域的应用中，层状磷表现出独特优势：碱/碱土金属离子在层状磷中扩散能垒低；还原态的碱/碱土金属磷化物的电子导电率高；对可溶性多硫化物具有吸附再活化作用；高离子/电子电导率及高亲锂性，诱导金属锂的均匀沉积；催化氧还原反应，降低形成过氧化锂所需的反应活化能。

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15 REVIEW

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Daokuan Jiao, Kui Jiao, Qing Du

🔖Trans Tianjin Univ, 2020, 26(3):197-207

本文亮点

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◆水管理对于提升质子交换膜燃料电池性能具有重要作用。在保证质子交换膜的润湿性的同时，又要避免过多的产物水堵塞气体传输通道，造成“水淹”。

◆文章对于多孔电极（催化层，微孔层，气体扩散层）的重构方法进行了回顾，并对相关重构方法的适用性，以及多孔电极重构过程中的局限性进行了评价。

◆从数值仿真角度，对于多孔电极内两相流的主要研究内容进行了总结；对于两相流研究过程中面临的难点进行了说明。

◆文章对现有多孔电极内两相流的研究方法、研究内容的优化方向提出了相关建议；并对未来可能提高燃料电池多孔电极内水管理性能的研究方向进行了展望。

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