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Preparation and electrochemical performance of ultra-thin reduced graphene oxide/lithium metal composite foils 超薄还原氧化石墨烯/锂金属复合箔的制备及其电化学性能
IF 5.7 3区 材料科学 Q2 Materials Science Pub Date : 2023-08-01 DOI: 10.1016/S1872-5805(23)60729-2
Er-yang Mao , Jun-mou Du , Xiang-rui Duan , Ling-yue Wang , Xian-cheng Wang , Guo-cheng Li , Lin Fu , Yong-ming Sun

Ultra-thin (≤50 μm) lithium metal anodes (LMAs) are highly desirable for high energy density lithium metal batteries (LMBs). However, their fabrication is complicated and costly due to the sticky and brittle nature of metallic Li, and they have a worse cycling stability than their thick counterparts. We report the fabrication of ultra-thin reduced graphene oxide/Li metal (rGO/Li) composite foils with thicknesses ranging from 10 to 50 μm. During the fabrication, disordered rGO sheets and molten metallic Li were stirred and combined at 200 ºC to produce micrometer-thick rGO/Li sheets, which were processed to form an ultra-thin uniform composite foil. The rGO sheets were randomly distributed in the rGO/Li composite to form a three-dimensional network, which is different from the laminated rGO structure previously reported, and supported stable Li plating/stripping behavior. As expected, a superior electrochemical performance was achieved using this composite sheet for the anode. A 50 μm-thick rGO/Li composite foil electrode displayed stable cycling for > 1 600 h at 1 mA cm−2 and 1 mAh cm−2 in symmetrical cells in an ether-based electrolyte. A full cell consisting of a 50 μm-thick rGO/Li composite foil anode and a sulfurized polyacrylonitrile cathode had a high capacity retention of 675 mAh g−1 after 220 cycles at 0.2 C.

超薄(≤50μm)锂金属阳极(LMA)是高能量密度锂金属电池(LMB)的理想选择。然而,由于金属Li的粘性和脆性,它们的制造是复杂和昂贵的,并且它们的循环稳定性比厚的对应物差。我们报道了厚度范围为10至50μm的超薄还原氧化石墨烯/锂金属(rGO/Li)复合箔的制备。在制造过程中,将无序的rGO片和熔融的金属Li在200ºC下搅拌并结合,以生产微米厚的rGO/Li片,对其进行处理以形成超薄均匀的复合箔。rGO片随机分布在rGO/Li复合材料中,形成三维网络,这与之前报道的层状rGO结构不同,并支持稳定的Li电镀/剥离行为。正如预期的那样,使用该复合片材作为阳极实现了优异的电化学性能。50μm厚的rGO/Li复合箔电极在>;在醚基电解质中的对称电池中,在1 mA cm−2和1 mAh cm−2下1 600 h。由50μm厚的rGO/Li复合箔阳极和硫化聚丙烯腈阴极组成的全电池在0.2℃下220次循环后具有675 mAh g−1的高容量保持率。
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引用次数: 0
Advances in the use of carbonaceous scaffolds for constructing stable composite Li metal anodes 碳质支架构建稳定复合锂金属阳极的研究进展
IF 5.7 3区 材料科学 Q2 Materials Science Pub Date : 2023-08-01 DOI: 10.1016/S1872-5805(23)60734-6
Yue Chen, Lu-kang Zhao, Jun-long Zhou, Yu-hua Bian, Xuan-wen Gao, Hong Chen, Zhao-meng Liu, Wen-bin Luo

Compositing lithium metal anodes (LMAs) with carbon-based materials has been given much attention because of the latter's low density, high mechanical strength, stable electrochemical properties, and large specific surface area. Such a composite LMA stands out because of its ability to reduce the volume expansion, lower the local current density, and provide active nucleation sites for uniform Li+ plating. Recent research advances in carbon-based materials as scaffolds to make composite anodes are reviewed, including composites with pure metals and their alloys, and compositing strategies to improve anode stability.

锂金属阳极(LMAs)与碳基材料的复合由于其低密度、高机械强度、稳定的电化学性能和大的比表面积而备受关注。这样的复合LMA脱颖而出,因为它能够减少体积膨胀,降低局部电流密度,并为均匀的Li+电镀提供活性成核位点。综述了碳基材料作为复合阳极支架的最新研究进展,包括与纯金属及其合金的复合材料,以及提高阳极稳定性的复合策略。
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引用次数: 0
Understanding the process of lithium deposition on a graphite anode for better lithium-ion batteries 了解锂在石墨阳极上沉积的过程,以获得更好的锂离子电池
IF 5.7 3区 材料科学 Q2 Materials Science Pub Date : 2023-08-01 DOI: 10.1016/S1872-5805(23)60747-4
Yu-jie Xu , Bing Wang , Yi Wan , Yi Sun , Wan-li Wang , Kang Sun , Li-jun Yang , Han Hu , Ming-bo Wu

A brief overview of recent developments in the formation, detection, and suppression of lithium dendrites in carbon-based lithium-ion batteries is presented. The electrochemical processes that result in the formation of lithium dendrites on the anode surface are reviewed, and various detection methods, including the essential operando technique for understanding the complex mechanism, are then introduced. Methods for suppressing lithium dendrite formation are discussed and prospects for future research and development are presented.

简要概述了碳基锂离子电池中锂枝晶的形成、检测和抑制的最新进展。综述了导致锂枝晶在阳极表面形成的电化学过程,并介绍了各种检测方法,包括理解复杂机制的基本操作技术。讨论了抑制锂枝晶形成的方法,并对未来的研究和发展前景进行了展望。
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引用次数: 0
Carbon-based materials for advanced lithium metal batteries based on carbon units of different dimensions 基于不同尺寸碳单元的先进锂金属电池用碳基材料
IF 5.7 3区 材料科学 Q2 Materials Science Pub Date : 2023-08-01 DOI: 10.1016/S1872-5805(23)60768-1
Xing-hao Zhang , Ting Xie , De-bin Kong , Lin-jie Zhi

We discuss recent advances in the control and design of carbon hosts/carriers based on their dimensionality (0D, 1D, 2D and 3D) for achieving high performance Li metal anodes. Representative modification strategies for these different carbons for studying their lithium affinity and their influence on the anode performance are highlighted and discussed. Prospects for the design of carbon hosts/carriers for practical rechargeable LMBs are discussed.

我们讨论了基于碳主体/载体的维度(0D、1D、2D和3D)来实现高性能锂金属阳极的控制和设计方面的最新进展。重点讨论了这些不同碳的代表性改性策略,以研究其对锂的亲和力及其对阳极性能的影响。对实用可充电LMB的碳载体/载体的设计进行了展望。
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引用次数: 0
Advances in carbon-based composite anodes with gradients of lithiophilicity and conductivity used for stable lithium metal batteries 具有亲锂性和电导率梯度的碳基复合阳极用于稳定锂金属电池的研究进展
IF 5.7 3区 材料科学 Q2 Materials Science Pub Date : 2023-08-01 DOI: 10.1016/S1872-5805(23)60744-9
Ya-nan Wang , Ying-xin Zhan , Xue-qiang Zhang , Jia-qi Huang

To address the issues of non-uniform Li plating/stripping and the large volume fluctuations during their repeated cycling, Li metal anodes, a composite Li anode with a three-dimensional (3D) host has been proposed as a promising strategy to improve the uniformity of Li plating/stripping and relieve volume fluctuations. One key strategy in this area is to develop 3D carbon hosts with gradients of lithiophilicity and conductivity to guide Li deposition from bottom to top, thus maximizing the positive effect of this composite Li anode. Such anodes have recently received significant attention due to the flexibility, adjustability, (electro)chemical stability and light weight of the carbon hosts. This review summarizes recent advances in these anodes, categorizing them into those that have hosts with a lithiophilicity gradient, hosts with a conductivity gradient, and those that have both. Latest research findings are discussed and these different anode categories are reviewed. Prospects for the design of such anodes to promote the use of Li metal anodes in high-energy-density rechargeable batteries are presented.

为了解决不均匀的Li电镀/剥离及其重复循环过程中的大体积波动问题,Li金属阳极,一种具有三维(3D)主体的复合Li阳极,已被提出作为一种有前途的策略,以提高Li电镀/剥除的均匀性并缓解体积波动。该领域的一个关键策略是开发具有亲锂性和导电性梯度的3D碳主体,以从下到上引导锂沉积,从而最大限度地发挥这种复合锂阳极的积极作用。由于碳主体的灵活性、可调节性、(电)化学稳定性和重量轻,这种阳极最近受到了极大的关注。这篇综述总结了这些阳极的最新进展,将其分为具有亲锂性梯度的基质、具有导电性梯度的宿主和两者兼有的宿主。讨论了最新的研究结果,并对这些不同的阳极类别进行了综述。展望了这种阳极的设计,以促进锂金属阳极在高能量密度可充电电池中的应用。
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引用次数: 0
The role, formation and characterization of LiC6 in composite lithium anodes LiC6在复合锂阳极中的作用、形成和表征
IF 5.7 3区 材料科学 Q2 Materials Science Pub Date : 2023-08-01 DOI: 10.1016/S1872-5805(23)60773-5
Zhou-qing Xue , Zi-you Wang , Jun-dong Zhang , Yang Lu , Wen-ze Huang , Ai-bing Chen , Chen-zi Zhao , Kuzmina Elena , Karaseva Elena , Kolosnitsyn Vladimir , Li-zhen Fan , Qiang Zhang

To solve the problems of large volume changes and the formation of lithium dendrites in lithium metal batteries, the incorporation of carbon into the lithium metal anodes has gained considerable attention due to its excellent chemical and electrochemical stability, as well as its exceptional mechanical strength that allows repeated cycling. This review provides a comprehensive overview of the formation of lithiated graphite (LiC6) and its role in both bulk and electrode-electrolyte interface regions during lithium plating and stripping. In bulk form, LiC6 has excellent lithiophilic properties, reducing the overpotential for lithium nucleation and promoting uniform lithium deposition. Additionally, when LiC6 is introduced at the electrode-electrolyte interfaces, it improves contact between the electrode and electrolyte by acting as a buffering layer, thereby reducing interfacial impedance. Finally, prospects and challenges for the development of Li/C composite anodes are discussed.

为了解决锂金属电池中体积变化大和锂枝晶形成的问题,将碳掺入锂金属阳极由于其优异的化学和电化学稳定性,以及允许重复循环的优异机械强度而受到了相当大的关注。这篇综述全面概述了锂化石墨(LiC6)的形成及其在锂电镀和剥离过程中在本体和电极电解质界面区域中的作用。在体相形式下,LiC6具有优异的亲锂性能,降低了锂成核的过电位,促进了锂的均匀沉积。此外,当在电极-电解质界面处引入LiC6时,它通过充当缓冲层来改善电极和电解质之间的接触,从而降低界面阻抗。最后,对锂/碳复合阳极的发展前景和面临的挑战进行了展望。
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引用次数: 0
The factors that influence the electrochemical behavior of lithium metal anodes: electron transfer and Li-ion transport 影响锂金属阳极电化学行为的因素:电子转移和锂离子输运
IF 5.7 3区 材料科学 Q2 Materials Science Pub Date : 2023-08-01 DOI: 10.1016/S1872-5805(23)60766-8
Meng-tian Zhang, Hao-tian Qu, Guang-min Zhou

Structured carbon-based hosts for the Li anode both improve the transport of Li-ions and reduce the electron transfer rate and have proven to be an effective way to suppress dendrite growth in lithium metal anodes. An in-depth understanding of these effects is needed to clarify the intrinsic electrochemical mechanism involved. We used the finite element method to simulate the two crucial processes controlling Li-ion behavior, electron transfer and Li-ion transport, and visualized the local deposition rate, the overpotential, and the Li-ion concentration in a three-dimensional (3D) Li//electrolyte//Li cell. Our analysis showed a competitive relationship between the rates of Li-ion transport and electron transfer. When the electron transfer rate is relatively slow, there are sufficient Li-ions available near the anode surface and the deposition behavior is controlled by electron transfer. However, when the number of Li-ions is low, Li-ion transport dominates the deposition process because it is unable to keep up with electron transfer, and this causes dendrite formation. Therefore, reducing the reactivity of the Li anode and accelerating Li-ion transport are the two key factors to produce uniform Li metal deposition on the anode, particularly under fast charging conditions and in practical use.

用于锂阳极的结构化碳基主体既改善了锂离子的传输,又降低了电子转移速率,并且已被证明是抑制锂金属阳极中枝晶生长的有效方法。需要深入了解这些效应,以阐明所涉及的内在电化学机制。我们使用有限元方法模拟了控制锂离子行为的两个关键过程,即电子转移和锂离子传输,并可视化了三维(3D)Li//电解质//Li电池中的局部沉积速率、过电位和锂离子浓度。我们的分析显示了锂离子传输速率和电子转移速率之间的竞争关系。当电子转移速率相对较慢时,在阳极表面附近有足够的Li离子可用,并且沉积行为由电子转移控制。然而,当锂离子的数量较低时,锂离子传输在沉积过程中占主导地位,因为它无法跟上电子转移的步伐,这会导致枝晶的形成。因此,降低锂阳极的反应性和加速锂离子传输是在阳极上产生均匀锂金属沉积的两个关键因素,特别是在快速充电条件下和实际使用中。
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引用次数: 0
Recent advances in Mxene-based nanomaterials as hosts for high-performance lithium metal anodes and as additives for improving the properties of solid electrolytes mxene基纳米材料作为高性能锂金属阳极的载体和改善固体电解质性能的添加剂的最新进展
IF 5.7 3区 材料科学 Q2 Materials Science Pub Date : 2023-08-01 DOI: 10.1016/S1872-5805(23)60767-X
Jia-lu Yang , Yue Qian , Ke Wang, Hua-dong Yuan, Jian-wei Nai, Yu-jing Liu, Yao Wang, Jian-min Luo, Xin-yong Tao

To tackle the issues of rapid electrode degradation and severe safety issues caused by the uncontrollable growth of lithium dendrites in Li metal anodes (LMAs), two-dimensional transition metal carbides/nitrides (MXenes) with a high electrical conductivity, excellent mechanical properties, and abundant surface functional groups have been used as hosts to induce uniform Li nucleation and alleviate the volume changes, eventually inhibiting the formation of Li dendrites. Recent advances in the use of MXene-based nanomaterials in LMAs are summarized. The problems with using LMAs are first considered, and the ways of using MXene-based nanomaterials for suppressing Li dendrite growth and constructing stable LMAs are then summarized. These include the use of MXenes, MXene-metal hybrids, MXene-carbon hybrids, and MXene derivatives as hosts for the anodes and as additives to modify the electrolyte compositions to increase ionic conductivity and inhibit polymer crystallization. Finally, the challenges and prospects for using MXene-based nanomaterials in next-generation LMAs are briefly discussed.

为了解决锂金属阳极(LMA)中锂枝晶的不可控生长引起的电极快速退化和严重的安全问题,丰富的表面官能团已被用作主体,以诱导均匀的Li成核并缓解体积变化,最终抑制Li枝晶的形成。综述了MXene基纳米材料在LMA中的最新应用进展。首先考虑了LMAs的使用问题,然后总结了使用MXene基纳米材料抑制Li枝晶生长和构建稳定LMAs的方法。其中包括使用MXene、MXene金属杂化物、MXene碳杂化物和MXene衍生物作为阳极的主体和添加剂来改性电解质组合物,以增加离子导电性并抑制聚合物结晶。最后,简要讨论了在下一代LMA中使用MXene基纳米材料的挑战和前景。
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引用次数: 0
The role of carbon materials in suppressing dendrite formation in lithium metal batteries 碳材料在抑制锂金属电池枝晶形成中的作用
IF 5.7 3区 材料科学 Q2 Materials Science Pub Date : 2023-08-01 DOI: 10.1016/S1872-5805(23)60762-0
Huang-lin Dou , Zhen-xin Zhao , Sun-bin Yang , Xiao-min Wang , Xiao-wei Yang

This review highlights several recent models of Li dendrite formation that have been proposed. Based on the comprehensive understanding and insight gained from these models, carbon materials have been developed to prevent the formation of Li dendrites by virtue of their exceptional electrical conductivity, electrochemical stability, mechanical properties and mouldability. A comprehensive review of the advantages of using carbon materials, such as graphene, carbon nanotubes, carbon fibers and hollow carbons, to deal with the formation of Li dendrites in recent years is provided. Finally, the limitations of carbon materials and future research directions for inhibiting Li dendrite formation are summarized as a reference for the development of new carbon materials for high-performance Li metal anodes.

这篇综述重点介绍了最近提出的几种Li枝晶形成模型。基于从这些模型中获得的全面理解和见解,碳材料已被开发出来,凭借其优异的导电性、电化学稳定性、机械性能和可成型性来防止Li枝晶的形成。综述了近年来使用石墨烯、碳纳米管、碳纤维和空心碳等碳材料处理锂枝晶形成的优点。最后,总结了碳材料在抑制锂枝晶形成方面的局限性和未来的研究方向,为开发用于高性能锂金属阳极的新型碳材料提供参考。
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引用次数: 0
Fabrication of vulcanized cross-linked polystyrene grafted on carbon nanotubes for use as an advanced lithium host 接枝碳纳米管的硫化交联聚苯乙烯的制备
IF 5.7 3区 材料科学 Q2 Materials Science Pub Date : 2023-08-01 DOI: 10.1016/S1872-5805(23)60745-0
Xian-lan Ke , Yu-heng Lu , Jin-lun Wu , Ding-cai Wu

We report the fabrication of vulcanized cross-linked polystyrene grafted on carbon nanotubes (CNTs) for use as an advanced three-dimensional Li host. First, polystyrene was grafted from Br-modified CNTs to form brush-like structure by surface-initiated atom-transfer radical polymerization. Polystyrene grafted on carbon nanotubes was then cross-linked using a Friedel-Crafts reaction and finally vulcanized with sulfur. Vulcanized cross-linked polystyrene grafted on carbon nanotubes was used as a support for the Li metal, and its macro-, meso- and microporous structure increased Li ion transport, buffered the volume changes of the Li anode, and provided a high specific surface area to reduce local current density, which assisted rapid and uniform Li plating/stripping. At the same time, the homogenously distributed sulfur in the support reacted with Li to produce a Li2S-containing SEI layer, while the CNTs provided conductive pathways for the rapid transmission of electrons. As a result, a Li|Li symmetric cell using this anode material and a Cu current collector had a stable cycling performance of more than 500 h at a current density of 1 mA cm−2. When LiFePO4 was used as the cathode, a full cell had a high discharge capacity of 101 mAh g−1 with a capacity retention of 77% after 600 cycles at 1 C.

我们报道了在碳纳米管(CNTs)上接枝硫化交联聚苯乙烯作为先进的三维Li主体的制备。首先,通过表面引发的原子转移自由基聚合,将溴化碳纳米管接枝到聚苯乙烯上,形成刷状结构。然后使用Friedel-Crafts反应将接枝在碳纳米管上的聚苯乙烯交联,并最终用硫硫化。将接枝在碳纳米管上的硫化交联聚苯乙烯用作锂金属的载体,其宏观、中微观和微孔结构增加了锂离子的传输,缓冲了锂阳极的体积变化,并提供了高比表面积以降低局部电流密度,这有助于快速、均匀地镀/剥离锂。同时,载体中均匀分布的硫与Li反应,产生含有Li2S的SEI层,而CNT为电子的快速传输提供了导电途径。因此,使用这种阳极材料和Cu集电器的Li|Li对称电池在1 mA cm−2的电流密度下具有超过500小时的稳定循环性能。当使用LiFePO4作为阴极时,全电池具有101 mAh g−1的高放电容量,在1℃下600次循环后容量保持率为77%。
{"title":"Fabrication of vulcanized cross-linked polystyrene grafted on carbon nanotubes for use as an advanced lithium host","authors":"Xian-lan Ke ,&nbsp;Yu-heng Lu ,&nbsp;Jin-lun Wu ,&nbsp;Ding-cai Wu","doi":"10.1016/S1872-5805(23)60745-0","DOIUrl":"https://doi.org/10.1016/S1872-5805(23)60745-0","url":null,"abstract":"<div><p>We report the fabrication of vulcanized cross-linked polystyrene grafted on carbon nanotubes (CNTs) for use as an advanced three-dimensional Li host. First, polystyrene was grafted from Br-modified CNTs to form brush-like structure by surface-initiated atom-transfer radical polymerization. Polystyrene grafted on carbon nanotubes was then cross-linked using a Friedel-Crafts reaction and finally vulcanized with sulfur. Vulcanized cross-linked polystyrene grafted on carbon nanotubes was used as a support for the Li metal, and its macro-, meso- and microporous structure increased Li ion transport, buffered the volume changes of the Li anode, and provided a high specific surface area to reduce local current density, which assisted rapid and uniform Li plating/stripping. At the same time, the homogenously distributed sulfur in the support reacted with Li to produce a Li<sub>2</sub>S-containing SEI layer, while the CNTs provided conductive pathways for the rapid transmission of electrons. As a result, a Li|Li symmetric cell using this anode material and a Cu current collector had a stable cycling performance of more than 500 h at a current density of 1 mA cm<sup>−2</sup>. When LiFePO<sub>4</sub> was used as the cathode, a full cell had a high discharge capacity of 101 mAh g<sup>−1</sup> with a capacity retention of 77% after 600 cycles at 1 C.</p></div>","PeriodicalId":19719,"journal":{"name":"New Carbon Materials","volume":"38 4","pages":"Pages 743-751"},"PeriodicalIF":5.7,"publicationDate":"2023-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"49756610","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
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New Carbon Materials
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