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Review on cellulose paper-based electrodes for sustainable batteries with high energy densities

《化学科学与工程前沿（英文）》 2023年 第17卷 第8期   页码 1010-1027 doi: 10.1007/s11705-023-2307-y

摘要： Powering the future, while maintaining strong socioeconomic growth and a cleaner environment, is going to be one of the biggest challenges faced by mankind nowadays. Thus, there is a transition from the use of fossil fuels to renewable energy sources. Cellulose, the main component of paper, represents a unique type of bio-based building blocks featuring exciting properties: low-cost, hierarchical fibrous structures, hydrophilicity, biocompatible, mechanical flexibility, and renewability, which make it perfect for use in paper-based sustainable energy storage devices. This review focuses on lithium-ion battery application of celluloses with cellulose at different scales, i.e., cellulose microfibers, and nanocellulose, and highlights the new trends in the field. Recent advances and approaches to construct high mass loading paper electrodes toward high energy density batteries are evaluated and the limitations of paper-based cathodes are discussed. This will stimulate the use of natural resources and thereby the development of renewable electric energy systems based on sustainable technologies with low environmental impacts and carbon footprints.

关键词： cellulose     paper electrodes     Li-ion batteries     high energy density    

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电动车锂离子电池的材料问题

陈立泉

《中国工程科学》 2002年 第4卷 第11期   页码 32-36

摘要：

简要介绍了我国电动车的开发现状，指出了发展电动车的瓶颈是电池；阐明了锂离子电池对发展电动车的作用，特别强调目前的关键是研发适于电动车的锂离子电池材料；简述了作者的实验室在电动车锂离子电池关键材料研究方面的最新进展。

关键词： 电动车     混合电动车     锂离子电池     电池材料    

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Recent advances toward high voltage, EC-free electrolytes for graphite-based Li-ion battery

Tong Zhang, Elie Paillard

《化学科学与工程前沿（英文）》 2018年 第12卷 第3期   页码 577-591 doi: 10.1007/s11705-018-1758-z

摘要：

Lithium-ion batteries are a key technology in today’s world and improving their performances requires, in many cases, the use of cathodes operating above the anodic stability of state-of-the-art electrolytes based on ethylene carbonate (EC) mixtures. EC, however, is a crucial component of electrolytes, due to its excellent ability to allow graphite anode operation–also required for high energy density batteries–by stabilizing the electrode/electrolyte interface. In the last years, many alternative electrolytes, aiming at allowing high voltage battery operation, have been proposed. However, often, graphite electrode operation is not well demonstrated in these electrolytes. Thus, we review here the high voltage, EC-free alternative electrolytes, focusing on those allowing the steady operation of graphite anodes. This review covers electrolyte compositions, with the widespread use of additives, the change in main lithium salt, the effect of anion (or Li salt) concentration, but also reports on graphite protection strategies, by coatings or artificial solid electrolyte interphase (SEI) or by use of water-soluble binder for electrode processing as these can also enable the use of graphite in electrolytes with suboptimal intrinsic SEI formation ability.

关键词： lithium-ion     electrolyte     solid electrolyte interphase     additives     high voltage     graphite    

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原子界面催化合成SnP/CoP异质纳米晶嵌入碳杂化物用于高功率型锂离子电池 Article

胡晨, 胡彦杰, 陈爱平, 段学志, 江浩, 李春忠

《工程（英文）》 2022年 第18卷 第11期   页码 154-160 doi: 10.1016/j.eng.2021.11.026

摘要：

磷化锡（SnP）具有极佳的锂离子扩散能力和高理论比容量，是高功率锂离子电池的理想负极材料。然而，SnP的合成难度高，大尺寸晶粒导致的电化学不可逆也阻碍了其应用。根据密度泛函理论（DFT）计算，使用原位催化磷化方法可以显著降低SnP的相对生成能。因此，在还原氧化石墨烯（rGO）包裹的碳骨架内合成了SnP/CoP异质纳米晶。所得复合材料具有超快充放电能力（50 A·g−1时容量为260 mA·h·g−1），且循环1500次不会出现容量衰减（2 A·g−1时容量为645 mA·h·g−1）。充放电机理分析表明尺寸为4.0 nm的SnP/CoP纳米晶具有高反应可逆性，且CoP在较高电位生成的金属Co加速了低电位SnP反应的动力学，从而赋予材料超快充放电能力。相对电流密度的有限元模拟进一步验证了这一现象。

关键词： 催化磷化     磷化锡     异质纳米晶     快速充电     锂离子电池    

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Highly selective metal recovery from spent lithium-ion batteries through stoichiometric hydrogen ion

Weiguang Lv, Xiaohong Zheng, Li Li, Hongbin Cao, Yi Zhang, Renjie Chen, Hancheng Ou, Fei Kang, Zhi Sun

《化学科学与工程前沿（英文）》 2021年 第15卷 第5期   页码 1243-1256 doi: 10.1007/s11705-020-2029-3

摘要： Spent lithium-ion battery recycling has attracted significant attention because of its importance in regard to the environment and resource importance. Traditional hydrometallurgical methods usually leach all valuable metals and subsequently extract target meals to prepare corresponding materials. However, Li recovery in these processes requires lengthy operational procedures, and the recovery efficiency is low. In this research, we demonstrate a method to selectively recover lithium before the leaching of other elements by introducing a hydrothermal treatment. Approximately 90% of Li is leached from high-Ni layered oxide cathode powders, while consuming a nearly stoichiometric amount of hydrogen ions. With this selective recovery of Li, the transition metals remain as solid residue hydroxides or oxides. Furthermore, the extraction of Li is found to be highly dependent on the content of transition metals in the cathode materials. A high leaching selectivity of Li (>98%) and nearly 95% leaching efficiency of Li can be reached with LiNi Co Mn O . In this case, both the energy and material consumption during the proposed Li recovery is significantly decreased compared to traditional methods; furthermore, the proposed method makes full use of H to leach Li . This research is expected to provide new understanding for selectively recovering metal from secondary resources.

关键词： recycling     spent LIBs     selective recovery     hydrothermal treatment    

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Two-phase early prediction method for remaining useful life of lithium-ion batteries based on a neural

《能源前沿（英文）》 doi: 10.1007/s11708-023-0906-4

摘要： Lithium-ion batteries (LIBs) are widely used in transportation, energy storage, and other fields. The prediction of the remaining useful life (RUL) of lithium batteries not only provides a reference for health management but also serves as a basis for assessing the residual value of the battery. In order to improve the prediction accuracy of the RUL of LIBs, a two-phase RUL early prediction method combining neural network and Gaussian process regression (GPR) is proposed. In the initial phase, the features related to the capacity degradation of LIBs are utilized to train the neural network model, which is used to predict the initial cycle lifetime of 124 LIBs. The Pearson coefficient’s two most significant characteristic factors and the predicted normalized lifetime form a 3D space. The Euclidean distance between the test dataset and each cell in the training dataset and validation dataset is calculated, and the shortest distance is considered to have a similar degradation pattern, which is used to determine the initial Dual Exponential Model (DEM). In the second phase, GPR uses the DEM as the initial parameter to predict each test set’s early RUL (ERUL). By testing four batteries under different working conditions, the RMSE of all capacity estimation is less than 1.2%, and the accuracy percentage (AP) of remaining life prediction is more than 98%. Experiments show that the method does not need human intervention and has high prediction accuracy.

关键词： lithium-ion batteries     RUL prediction     double exponential model     neural network     Gaussian process regression (GPR)    

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Lithium-ion modified cellulose as a water-soluble binder for Li-O battery

《能源前沿（英文）》 2022年 第16卷 第3期   页码 502-508 doi: 10.1007/s11708-021-0750-3

摘要： An environment-friendly, water-soluble, and cellulose based binder (lithium carboxymethyl cellulose, CMC-Li) was successfully synthesized by using Li+ to replace Na+ in the commercial sodium carboxymethyl cellulose (CMC-Na). Li-O2 batteries based on the CMC-Li binder present enhanced discharge specific capacities (11151 mA·h/g at 100 mA/g) and a superior cycling stability (100 cycles at 200 mA/g) compared with those based on the CMC-Na binder. The enhanced performance may originate from the electrochemical stability of the CMC-Li binder and the ion-conductive nature of CMC-Li, which promotes the diffusion of Li+ in the cathode and consequently retards the increase of charge transfer resistance of the cathode during cycling. The results show that the water-soluble CMC-Li binder can be a green substitute for poly(vinylidene fluoride) (PVDF) binder based on organic solvent in the lithium oxygen batteries (LOBs).

关键词： cellulose     binder     specific capacity     cyclabi- lity     lithium-oxygen batteries    

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g-CN-coated MnO hollow nanorod cathode for stable aqueous Zn-ion batteries

《化学科学与工程前沿（英文）》 2023年 第17卷 第2期   页码 217-225 doi: 10.1007/s11705-022-2214-7

摘要： Aqueous zinc-ion batteries are attracting considerable attention because of their high safety compared with conventional lithium-ion batteries. Manganese-based materials have been widely developed for zinc-ion batteries cathode owning to their low cost, high security and simple preparation. However, the severe volume expansion and poor stability during charging and discharging limit the further development of manganese-based cathodes. Herein, superior α-MnO2@g-C3N4 was successfully prepared for stable zinc-ion batteries (ZIBs) cathode by introducing g-C3N4 nanosheets. Compared with pure α-MnO2, α-MnO2@g-C3N4 has a specific capacity of 298 mAh·g–1 at 0.1 A·g–1. Even at 1 A·g–1, the α-MnO2@g-C3N4 still retains 100 mAh·g–1 (83.4% retention after 5000 cycles), implying its excellent cycling stability. The α-MnO2@g-C3N4-based cathode has the highest energy density (563 Wh·kg–1) and power energy density (2170 W·kg–1). This work provides new avenues for the development of a wider range of cathode materials for ZIBs.

关键词： α-MnO2 hollow nanorods     g-C3N4     heterojunction     aqueous Zn-ion batteries    

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Alumina modified sodium vanadate cathode for aqueous zinc-ion batteries

《能源前沿（英文）》   页码 775-781 doi: 10.1007/s11708-023-0902-8

摘要： Aqueous zinc-ion batteries (ZIBs) have great prospects for widespread application in massive scale energy storage. By virtue of the multivalent state, open frame structure and high theoretical specific capacity, vanadium (V)-based compounds are a kind of the most developmental potential cathode materials for ZIBs. However, the slow kinetics caused by low conductivity and the capacity degradation caused by material dissolution still need to be addressed for large-scale applications. Therefore, sodium vanadate Na2V6O16·3H2O (NVO) was chosen as a model material, and was modified with alumina coating through simple mixing and stirring methods. After Al2O3 coating modification, the rate capability and long-cycle stability of Zn//NVO@Al2O3 battery have been significantly improved. The discharge specific capacity of NVO@Al2O3 reach up to 228 mAh/g (at 4 A/g), with a capacity reservation rate of approximately 68% after 1000 cycles, and the Coulombic efficiency (CE) is close to 100%. As a comparison, the capacity reservation rate of Zn//NVO battery is only 27.7%. Its superior electrochemical performance is mainly attributed to the Al2O3 coating layer, which can increase zinc-ion conductivity of the material surface, and to some extent inhibit the dissolution of NVO, making the structure stable and improving the cyclic stability of the material. This paper offers new prospects for the development of cathode coating materials for ZIBs.

关键词： cathodes     aqueous zinc-ion batteries     sodium vanadate     alumina     coating    

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钠离子电池工程化——机遇与挑战 Review

赵丽娜, 张腾, 李巍, 李涛, 张隆, 张晓光, 汪志义

《工程（英文）》 2023年 第24卷 第5期   页码 172-183 doi: 10.1016/j.eng.2021.08.032

摘要：

当前，在应对全球能源枯竭与环境恶化之际，可持续且环境友好的可再生能源正迎来重要的发展机遇。以二次电池为代表的电能存储（EES）技术，可实现绿色新能源安全且经济有效的存储和转化，被视为可平抑可再生能源间歇性并实现稳定并网输入的最佳解决方案。钠离子电池（SIB），受益于钠资源的丰富
性及低成本，是下一代大规模电化学存储系统最具应用前景的选择之一。本文详细讨论了锂离子电池（LIB）和钠离子电池在不同应用场景下的主要区别，并描述了当前对钠离子电池的理解。通过比较锂离子电池、铅酸电池（LAB）和钠离子电池之间的技术发展情况，进一步揭示钠离子电池的优势。本文以基于钠离子电池技术所取得的商业化成就为文章亮点，重点介绍了五家钠离子电池企业和相应的钠离子电池产品，以及各自的钠离子电池化学与技术。最后，讨论了下一代钠离子电池商业化的前景与挑战。

关键词： 电化学储能     钠离子电池     商业化     下一代    

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One-step synthesis of recoverable CuCo

Tongzhou Lu, Yongzheng Zhang, Chun Cheng, Yanbin Wang, Yongming Zhu

《化学科学与工程前沿（英文）》 2020年 第14卷 第4期   页码 595-604 doi: 10.1007/s11705-019-1818-z

摘要： A facile one-step hydrothermal method has been adopted to directly synthesize the CuCo S material on the surface of Ni foam. Due to the relatively large specific surface area and wide pore size distribution, the CuCo S material not only effectively increases the reactive area, but also accommodates more side reaction products to avoid the difficulty of mass transfer. When evaluated as anode for Li-ion batteries, the CuCo S material exhibits excellent electrochemical performance including high discharge capacity, outstanding cyclic stability and good rate performance. At the current density of 200 mA·g , the CuCo S material shows an extremely high initial discharge capacity of 2510 mAh·g , and the cycle numbers of the material even reach 83 times when the discharge capacity is reduced to 500 mAh·g . Furthermore, the discharge capacity can reach 269 mAh·g at a current of 2000 mA·g . More importantly, when the current density comes back to 200 mA·g , the discharge capacity could be recovered to 1436 mAh·g , suggesting an excellent capacity recovery characteristics.

关键词： copper cobalt sulfide     recoverability     one-step hydrothermal method     anode material     Li-ion battery    

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A review on the development of electrolytes for lithium-based batteries for low temperature applications

《能源前沿（英文）》 2023年 第17卷 第1期   页码 43-71 doi: 10.1007/s11708-022-0853-5

摘要： The aerospace industry relies heavily on lithium-ion batteries in instrumentation such as satellites and land rovers. This equipment is exposed to extremely low temperatures in space or on the Martian surface. The extremely low temperatures affect the discharge characteristics of the battery and decrease its available working capacity. Various solvents, cosolvents, additives, and salts have been researched to fine tune the conductivity, solvation, and solid-electrolyte interface forming properties of the electrolytes. Several different resistive phenomena have been investigated to precisely determine the most limiting steps during charge and discharge at low temperatures. Longer mission lifespans as well as self-reliance on the chemistry are now highly desirable to allow low temperature performance rather than rely on external heating components. As Martian rovers are equipped with greater instrumentation and demands for greater energy storage rise, new materials also need to be adopted involving next generation lithium-ion chemistry to increase available capacity. With these objectives in mind, tailoring of the electrolyte with higher-capacity materials such as lithium metal and silicon anodes at low temperatures is of high priority. This review paper highlights the progression of electrolyte research for low temperature performance of lithium-ion batteries over the previous several decades.

关键词： electrolyte     lithium-ion     low temperature     aerospace     solid-electrolyte interface    

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Enabling nickel ferrocyanide nanoparticles for high-performance ammonium ion storage

《化学科学与工程前沿（英文）》 2023年 第17卷 第2期   页码 226-235 doi: 10.1007/s11705-022-2198-3

摘要： Prussian blue and its analogs are extensively investigated as a cathode for ammonium-ion batteries. However, they often suffer from poor electronic conductivity. Here, we report a Ni2Fe(CN)6/multiwalled carbon nanotube composite electrode material, which is prepared using a simple coprecipitation approach. The obtained material consists of nanoparticles with sizes 30–50 nm and the multiwalled carbon nanotube embedded in it. The existence of multiwalled carbon nanotube ensures that the Ni2Fe(CN)6/multiwalled carbon nanotube composite shows excellent electrochemical performance, achieving a discharge capacity of 55.1 mAh·g–1 at 1 C and 43.2 mAh·g–1 even at 15 C. An increase in the ammonium-ion diffusion coefficient and ionic/electron conductivity based on kinetic investigations accounts for their high performance. Furthermore, detailed ex situ characterizations demonstrate that Ni2Fe(CN)6/multiwalled carbon nanotube composite offers three advantages: negligible lattice expansion during cycling, stable structure, and the reversible redox couple. Therefore, the Ni2Fe(CN)6/multiwalled carbon nanotube composite presents a long cycling life and high rate capacity. Finally, our study reports a desirable material for ammonium-ion batteries and provides a practical approach for improving the electrochemical performance of Prussian blue and its analogs.

关键词： nickel ferrocyanides     NH4+     electrochemistry     Prussian blue     aqueous ammonium ion batteries    

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Promoting Si-graphite composite anodes with SWCNT additives for half and NCM811 full lithium ion batteries

Jingning SHAN, Xiaofang YANG, Chao YAN, Yiguang JU, Lin CHEN, Fang ZHAO

《能源前沿（英文）》 2019年 第13卷 第4期   页码 626-635 doi: 10.1007/s11708-019-0650-y

摘要： Single wall carbon nanotube (SWCNT) additives were formulated into µm-Si-graphite composite electrodes and tested in both half cells and full cells with high nickel cathodes. The critical role of small amount of SWCNT addition (0.2 wt%) was found for significantly improving delithiation capacity, first cycle coulombic efficiency (FCE), and capacity retention. Particularly, Si (10 wt%)-graphite electrode exhibits 560 mAh/g delithiation capacity and 92% FCE at 0.2 C during the first charge-discharge cycle, and 91% capacity retention after 50 cycles (0.5 C) in a half cell. Scanning electron microscope (SEM) was used to illustrate the electrode morphology, compositions and promoting function of the SWCNT additives. In addition, full cells assembled with high nickel-NCM811 cathodes and µm-Si-graphite composite anodes were evaluated for the consistence between half and full cell performance, and the consideration for potential commercial application. Finally, criteria to assess Si-containing anodes are proposed and discussed from an industrial perspective.

关键词： lithium-ion battery     Si anode     Si-graphite composite     single wall carbon nanotube (SWCNT)     NCM811    

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Ion conduction path in composite solid electrolytes for lithium metal batteries: from polymer rich to

Zhouyu ZHANG, Hao CHEN, Zhenglin HU, Shoubin ZHOU, Lan ZHANG, Jiayan LUO

《能源前沿（英文）》 2022年 第16卷 第5期   页码 706-733 doi: 10.1007/s11708-022-0833-9

摘要： Solid-state electrolytes (SSEs) can address the safety issue of organic electrolyte in rechargeable lithium batteries. Unfortunately, neither polymer nor ceramic SSEs used alone can meet the demand although great progress has been made in the past few years. Composite solid electrolytes (CSEs) composed of flexible polymers and brittle but more conducting ceramics can take advantage of the individual system for solid-state lithium metal batteries (SSLMBs). CSEs can be largely divided into two categories by the mass fraction of the components: “polymer rich” (PR) and “ceramic rich” (CR) systems with different internal structures and electrochemical properties. This review provides a comprehensive and in-depth understanding of recent advances and limitations of both PR and CR electrolytes, with a special focus on the ion conduction path based on polymer-ceramic interaction mechanisms and structural designs of ceramic fillers/frameworks. In addition, it highlights the PR and CR which bring the leverage between the electrochemical property and the mechanical property. Moreover, it further prospects the possible route for future development of CSEs according to their rational design, which is expected to accelerate the practical application of SSLMBs.

关键词： composite solid electrolytes     active filler/framework     ion conduction path     interphase compatibility     multilayer design    

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标题 作者 时间 类型 操作

Review on cellulose paper-based electrodes for sustainable batteries with high energy densities

期刊论文

电动车锂离子电池的材料问题

陈立泉

期刊论文

Recent advances toward high voltage, EC-free electrolytes for graphite-based Li-ion battery

Tong Zhang, Elie Paillard

期刊论文

原子界面催化合成SnP/CoP异质纳米晶嵌入碳杂化物用于高功率型锂离子电池

胡晨, 胡彦杰, 陈爱平, 段学志, 江浩, 李春忠

期刊论文

Highly selective metal recovery from spent lithium-ion batteries through stoichiometric hydrogen ion

Weiguang Lv, Xiaohong Zheng, Li Li, Hongbin Cao, Yi Zhang, Renjie Chen, Hancheng Ou, Fei Kang, Zhi Sun

期刊论文

Two-phase early prediction method for remaining useful life of lithium-ion batteries based on a neural

期刊论文

Lithium-ion modified cellulose as a water-soluble binder for Li-O battery

期刊论文

g-CN-coated MnO hollow nanorod cathode for stable aqueous Zn-ion batteries

期刊论文

Alumina modified sodium vanadate cathode for aqueous zinc-ion batteries

期刊论文

钠离子电池工程化——机遇与挑战

赵丽娜, 张腾, 李巍, 李涛, 张隆, 张晓光, 汪志义

期刊论文

One-step synthesis of recoverable CuCo

Tongzhou Lu, Yongzheng Zhang, Chun Cheng, Yanbin Wang, Yongming Zhu

期刊论文

A review on the development of electrolytes for lithium-based batteries for low temperature applications

期刊论文

Enabling nickel ferrocyanide nanoparticles for high-performance ammonium ion storage

期刊论文

Promoting Si-graphite composite anodes with SWCNT additives for half and NCM811 full lithium ion batteries

Jingning SHAN, Xiaofang YANG, Chao YAN, Yiguang JU, Lin CHEN, Fang ZHAO

期刊论文

Ion conduction path in composite solid electrolytes for lithium metal batteries: from polymer rich to

Zhouyu ZHANG, Hao CHEN, Zhenglin HU, Shoubin ZHOU, Lan ZHANG, Jiayan LUO

期刊论文