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Artículos de revistas sobre el tema "Lithium-free"

Autor: Grafiati
Publicado: 12 de abril de 2025

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1

Shen, Kai, Zhenjiang Cao, Yongzheng Shi, Yongzheng Zhang, Bin Li y Shubin Yang. "3D Printing Lithium Salt towards Dendrite-free Lithium Anodes". Energy Storage Materials 35 (marzo de 2021): 108–13. http://dx.doi.org/10.1016/j.ensm.2020.11.022.

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2

Balaish, Moran, Emanuel Peled, Diana Golodnitsky y Yair Ein-Eli. "Liquid-Free Lithium-Oxygen Batteries". Angewandte Chemie 127, n.º 2 (3 de octubre de 2014): 446–50. http://dx.doi.org/10.1002/ange.201408008.

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3

Winterkorn, Martin M. y Tim Holme. "(Invited) Li-Free Anode Development at Quantumscape". ECS Meeting Abstracts MA2022-02, n.º 47 (9 de octubre de 2022): 1733. http://dx.doi.org/10.1149/ma2022-02471733mtgabs.

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QuantumScape is developing a solid-state battery with a lithium-metal anode to enable long-range, faster charging, low-cost EVs. The technology features an anode that is lithium-free as manufactured, with the lithium being delivered entirely from the cathode material. The lithium-free approach offers a significant cost savings relative to approaches that utilize an excess lithium foil or vapor deposition process. This talk will highlight the scientific and engineering challenges in developing an anode-free solid-state battery, with a historical overview and a snapshot of the progress at QuantumScape. QuantumScape was founded in 2010 with a mission to revolutionize energy storage to enable a sustainable future.
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4

Gervillie, Charlotte, Louis Ah, Alex Ruili Liu, Chen-Jui Huang y Shirley Meng. "Deciphering the Impact of the Active Lithium Reservoir in Anode-Free Pouch Cells". ECS Meeting Abstracts MA2024-02, n.º 7 (22 de noviembre de 2024): 889. https://doi.org/10.1149/ma2024-027889mtgabs.

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Anode-free batteries, which revolutionize energy storage by discarding traditional anodes in favor of copper foil to plate lithium directly from the cathode, offer increased energy densities and better safety than conventional lithium-metal cells. However, their advantage is tempered by a significantly reduced cycle life, attributed to lithium loss through parasitic reactions. As a result, inactive (‘dead’) lithium accumulates over cycling, including (electro)chemically formed Li+ compounds in the solid electrolyte interphase (SEI) and isolated unreacted metallic Li0, resulting in capacity loss and safety hazards. Consequently, to continue enhancing the performance of anode-free cells, it appears crucial to differentiate and quantify the various forms of lithium in these cells and monitor their distribution and evolution throughout the cycling process, depending on various conditions such as pressure or electrolytes. Compared to lithium metal cells, the problem might appear simplified for anode-free cells as there is no active lithium compensation from the anode, and all the active lithium is initially stored within the cathode. However, the intricate interplay of the cathode's first-cycle irreversibility and lithium plating/stripping efficiency significantly influences the shape of the capacity retention curves and the measurements of coulombic efficiency (CE). Herein we aim to clarify the contribution of the lithium reservoir to the anode-free cell performances. We report a systematic study of the active lithium reservoir and unreacted metallic Li0 evolution in anode-free LiNi0.6Mn0.2Co0.2O2 (NMC622)||Copper (Cu) commercial pouch cells. By taking advantage of a discharge characteristic of the NMC622 cathode at low voltage (<1.5 V), we could quantify the presence of remaining active lithium at the anode. Afterwards, titration gas chromatography was utilized to measure the remaining inactive Li0 on the discharged samples. By coupling the quantification techniques to observations of the anode local microstructure by cryogenic scanning electron microscopy, we elucidate the formation and evolution mechanism of the lithium reservoir and inactive metallic lithium in different types of electrolytes. As a result, we demonstrated that the once-considered drawback of Ni-rich layered oxide cathodes, namely the first cycled intrinsic irreversible capacity, can be manipulated to build a lithium reservoir at the anode and extend the cycle life of anode-free cells (see Figure 1, bottom left). Additionally, the formerly unclear reason for the capacity degradation discrepancy of anode-free cells under different C-rates was investigated and attributed to the correlation between lithium utilization and reservoirs (see Figure 1, bottom right). In contrast to the first-cycle irreversibility unique to certain types of cathode materials, this approach can be applied to all types of cells having polarization phenomena at high currents to enhance their longevity in anode-free configurations. Consequently, by employing protocols with slow charge and fast discharge, the lithium reservoir at the anode is maximized, and the performances of the anode-free cells appear stable for a longer number of cycles. With this knowledge, one can regulate the ratio between lithium utilization and lithium reservoirs for extended capacity retention or high initial reversible capacity designated for different applications. We believe the concept of this Li reservoir can be further extended to other approaches and opens new opportunities, taking advantage of cathode intrinsic irreversibility and kinetic limitations to extend anode-free cells’ lifespan. Figure 1
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5

Kalinina, A. A., I. A. Konopkina, O. V. Vakhnina, I. V. Koroleva, K. B. Zhogova y S. A. Annikova. "The choice of methods for lithium and boron determination in lithium-boron alloys". Industrial laboratory. Diagnostics of materials 89, n.º 1 (21 de enero de 2023): 20–27. http://dx.doi.org/10.26896/1028-6861-2023-89-1-20-27.

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A lithium-boron alloy (LBA) with a high lithium content (up to 70%) is used as an anode material for molten salt batteries in chemical sources of current. We present a complex of developed techniques for determining mass fractions of free lithium, total lithium, and total boron in lithium-boron alloys containing lithium mass fractions no more than 70%, boron mass fractions — no less than 26%. Optimal conditions for preparation of LBA samples and subsequent free lithium extraction from them are determined. The developed techniques are intended for i) extraction-titrimetric determination of free lithium in a content range of 20 - 50% (the relative total error no more than 1.1%); ii) determination of the total lithium content using flame atomic emission spectrometry in a content range of 59.0 - 96.0% (the relative overall error no more than 2.7%; iii) determination of the total boron content by two methods, i.e., potentiometric titration within a content range of 5 - 40% (the relative total error no more than 1.3%) and flame atomic absorption spectrometry within a content range of 4.9-50.7% (the relative total error no more than 4.9%). The results of analysis of full-scale LBA samples for the content of free lithium, total lithium and total boron are presented. It is shown that the application of two techniques for the determination of total boron content in lithium-boron alloys makes it possible to get the convergent results within the limits of measurement errors. The developed techniques are certified by the metrological service of the enterprise and can be used for the incoming and process control of the LBA production.
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6

Chen, Xiang, Zhuqing Zhao, Jiakang Qu, Beilei Zhang, Xueyong Ding, Yunfeng Geng, Hongwei Xie, Dihua Wang y Huayi Yin. "Electrolysis of Lithium-Free Molten Carbonates". ACS Sustainable Chemistry & Engineering 9, n.º 11 (11 de marzo de 2021): 4167–74. http://dx.doi.org/10.1021/acssuschemeng.1c00028.

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7

Kutbee, Arwa T., Mohamed T. Ghoneim, Sally M. Ahmad y Muhammad M. Hussain. "Free-Form Flexible Lithium-Ion Microbattery". IEEE Transactions on Nanotechnology 15, n.º 3 (mayo de 2016): 402–8. http://dx.doi.org/10.1109/tnano.2016.2537338.

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8

Schollhammer, Jean, Mohammad Amin Baghban y Katia Gallo. "Modal birefringence-free lithium niobate waveguides". Optics Letters 42, n.º 18 (11 de septiembre de 2017): 3578. http://dx.doi.org/10.1364/ol.42.003578.

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9

Scheers, Johan, Du-Hyun Lim, Jae-Kwang Kim, Elie Paillard, Wesley A. Henderson, Patrik Johansson, Jou-Hyeon Ahn y Per Jacobsson. "All fluorine-free lithium battery electrolytes". Journal of Power Sources 251 (abril de 2014): 451–58. http://dx.doi.org/10.1016/j.jpowsour.2013.11.042.

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10

Prachi Patel, special to C&EN. "Lithium-ion batteries go cobalt-free". C&EN Global Enterprise 98, n.º 29 (27 de julio de 2020): 9. http://dx.doi.org/10.1021/cen-09829-scicon5.

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11

Zheng, Zhaozhu, Shaozhe Guo, Yawen Liu, Jianbing Wu, Gang Li, Meng Liu, Xiaoqin Wang y David Kaplan. "Lithium-free processing of silk fibroin". Journal of Biomaterials Applications 31, n.º 3 (9 de julio de 2016): 450–63. http://dx.doi.org/10.1177/0885328216653259.

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12

Qian, Jiangfeng, Brian D. Adams, Jianming Zheng, Wu Xu, Wesley A. Henderson, Jun Wang, Mark E. Bowden, Suochang Xu, Jianzhi Hu y Ji-Guang Zhang. "Anode-Free Rechargeable Lithium Metal Batteries". Advanced Functional Materials 26, n.º 39 (18 de agosto de 2016): 7094–102. http://dx.doi.org/10.1002/adfm.201602353.

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13

Assegie, Addisu Alemayehu, Cheng-Chu Chung, Meng-Che Tsai, Wei-Nien Su, Chun-Wei Chen y Bing-Joe Hwang. "Multilayer-graphene-stabilized lithium deposition for anode-Free lithium-metal batteries". Nanoscale 11, n.º 6 (2019): 2710–20. http://dx.doi.org/10.1039/c8nr06980h.

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14

Zhang, Jian, Abrar Khan, Xiaoyuan Liu, Yuban Lei, Shurong Du, Le Lv, Hailei Zhao y Dawei Luo. "Research Progress of Anode-Free Lithium Metal Batteries". Crystals 12, n.º 9 (2 de septiembre de 2022): 1241. http://dx.doi.org/10.3390/cryst12091241.

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Lithium-metal batteries (LMBs) are regarded as the most promising candidate for practical applications in portable electronic devices and electric vehicles because of their high capacity and energy density. However, the uncontrollable growth of lithium dendrite reduces its cycling ability and even causes a severe safety concern, which impedes the development of the technology. Although great efforts have been devoted to solving the lithium dendrite issue in recent years, the contradiction between the high cost of thin Li foil and the severe safety hazard of excess Li still exists. This is precisely the factor that inspired the development of anode-free lithium-metal batteries (AFLMBs). Compared to lithium-metal batteries, AFLMBs with a zero-excess Li anode possess an incredible, conceivable, and specific energy. Additionally, because the use of metal lithium is limited, the battery manufacturing will be safer and simpler, leading to a significant decrease in cost. However, comprehensive reviews on anode-free batteries are rare. Therefore, in this review, we aim to explain the essential development factors influencing the cycle life, energy density, cost, and working mechanism of anode-free batteries. We summarize different strategies to improve the cycling stability of AFLMBs, and we discuss the application of anode-free electrodes in other electrochemical energy storage systems. Moreover, it is believed that the combination of modification techniques, including electrolytes and current collectors, and the application protocols will be the most important solution for future anode-free batteries.
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15

Kubota, K. y H. Matsumoto. "Solvent Free Lithium Molten Salt as Electrolyte of Lithium Secondary Battery". ECS Transactions 62, n.º 1 (17 de noviembre de 2014): 231–34. http://dx.doi.org/10.1149/06201.0231ecst.

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16

Xu, Ying, Tao Li, Liping Wang y Yijin Kang. "Interlayered Dendrite‐Free Lithium Plating for High‐Performance Lithium‐Metal Batteries". Advanced Materials 31, n.º 29 (3 de junio de 2019): 1901662. http://dx.doi.org/10.1002/adma.201901662.

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17

Louli, A. J., A. Eldesoky, Jack deGooyer, Matt Coon, C. P. Aiken, Z. Simunovic, M. Metzger y J. R. Dahn. "Different Positive Electrodes for Anode-Free Lithium Metal Cells". Journal of The Electrochemical Society 169, n.º 4 (1 de abril de 2022): 040517. http://dx.doi.org/10.1149/1945-7111/ac62c4.

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With a potential to deliver 60% greater energy density than conventional lithium-ion batteries, the simple design of anode-free lithium metal cells with liquid electrolytes has generated significant research interest. However, without excess lithium, the short lifetime and safety concerns for cells cycling lithium metal with liquid electrolytes make the development of anode-free cells particularly challenging. Herein, we investigate the effect of four different positive electrode materials on the performance of anode-free cells—LiNi0.5Mn0.3Co0.2O2 (NMC532), LiNi0.8Mn0.1Co0.1O2 (NMC811), LiCoO2 (LCO), and LiFePO4 (LFP). In-situ electrochemical impedance spectroscopy and electrolyte degradation measurements were performed on cells with dual-salt LiDFOB/LiBF4 electrolyte to elucidate cell failure. Additional state-of-the-art electrolyte systems as well as other testing conditions (temperature, pressure, depth of discharge) were also explored, along with nail safety tests and calendar aging cycle-hold experiments. We show that the rate of lithium inventory loss and impedance growth differs amongst these cell chemistries, ultimately resulting in the shortest lifetime for NMC811 and the longest lifetime for LCO anode-free cells of 200 cycles.
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18

Cheng, Xin-Bing, Ting-Zheng Hou, Rui Zhang, Hong-Jie Peng, Chen-Zi Zhao, Jia-Qi Huang y Qiang Zhang. "Dendrite-Free Lithium Deposition Induced by Uniformly Distributed Lithium Ions for Efficient Lithium Metal Batteries". Advanced Materials 28, n.º 15 (22 de febrero de 2016): 2888–95. http://dx.doi.org/10.1002/adma.201506124.

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19

Zhao, Pei, Jun Pan, Dongqi Zhang, Yufeng Tang, Zhixin Tai, Yajie Liu, Hong Gao y Fuqiang Huang. "Designs of Anode-Free Lithium-Ion Batteries". Batteries 9, n.º 7 (17 de julio de 2023): 381. http://dx.doi.org/10.3390/batteries9070381.

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Anodes equipped with limited lithium offer a way to deal with the increasing market requirement for high-energy-density rechargeable batteries and inadequate global lithium reserves. Anode-free lithium-ion batteries (AFLBs) with zero excess metal could provide high gravimetric energy density and high volumetric energy density. Moreover, the elimination of lithium with a bare current collector on the anode side can reduce metal consumption, simplify the cell technological procedure, and improve manufacturing safety. However, some great challenges, such as insufficient cycling stability, significant lithium dendrite growth, as well as unstable solid electrolyte interface, impede the commercial application of AFLBs. Fortunately, significant progress has been made for AFLBs with enhanced electrode stability and improved cycling performance. This review highlights research on the design of anode-free lithium-ion batteries over the past two decades, presents an overview of the main advantages and limitations of these designs, and provides improvement strategies including the modification of the current collectors, improvement of the liquid electrolytes, and optimization of the cycling protocols. Prospects are also given to broaden the understanding of the electrochemical process, and it is expected that the further development of these designs can be accelerated in both scientific research and practical applications.
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20

Zhu, Mengqi, Chuyi Cai, Xuran Li, Chunwen Shi y Jindan Zhang. "Interfacial MXene engineering enabled lamellar lithium nucleation for dendrite-free lithium anodes". Journal of Power Sources 633 (marzo de 2025): 236451. https://doi.org/10.1016/j.jpowsour.2025.236451.

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21

Xiang, Jingwei, Ying Zhao, Lixia Yuan, Chaoji Chen, Yue Shen, Fei Hu, Zhangxiang Hao, Jing Liu, Baixiang Xu y Yunhui Huang. "A strategy of selective and dendrite-free lithium deposition for lithium batteries". Nano Energy 42 (diciembre de 2017): 262–68. http://dx.doi.org/10.1016/j.nanoen.2017.10.065.

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22

Lee, Yong-Gun, Saebom Ryu, Toshinori Sugimoto, Taehwan Yu, Won-seok Chang, Yooseong Yang, Changhoon Jung et al. "Dendrite-Free Lithium Deposition for Lithium Metal Anodes with Interconnected Microsphere Protection". Chemistry of Materials 29, n.º 14 (17 de julio de 2017): 5906–14. http://dx.doi.org/10.1021/acs.chemmater.7b01304.

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23

Zhang, Fei, Ping Liu, Yue Tian, Jinfeng Wu, Xuewei Wang, Huili Li y Xiaoyan Liu. "Uniform lithium nucleation/deposition regulated by N/S co-doped carbon nanospheres towards ultra-stable lithium metal anodes". Journal of Materials Chemistry A 10, n.º 3 (2022): 1463–72. http://dx.doi.org/10.1039/d1ta09575g.

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N and S co-doped mesoporous carbon nanospheres show strong affinity towards lithium ions, which dramatically reduce the lithium nucleation barrier and improve the stability of SEI layer, boosting a dendrite-free lithium metal anode.
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24

Huang, Yu-Kai y Leif Nyholm. "Influence of Lithium Diffusion into Copper Current Collectors on Lithium Electrodeposition in Anode-Free Lithium-Metal Batteries". ECS Meeting Abstracts MA2023-02, n.º 20 (22 de diciembre de 2023): 1275. http://dx.doi.org/10.1149/ma2023-02201275mtgabs.

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With increasing demands for lithium-based batteries that have higher energy densities, access to better negative electrode materials becomes crucial. Lithium metal which has a very high theoretical specific capacity, a very low standard potential and a very low density can be considered one of the best negative electrode materials for next-generation lithium-based batteries. In order to fully exploit the merits of lithium metal, a cell configuration in which lithium is directly electrodeposited (and then stripped) on (from) the negative electrode current collector (i.e., copper foil) is essential. Such “anode-material-free” (or ”anode-free”) lithium-metal batteries can have significantly higher gravimetric and volumetric energy densities than conventional graphite-based lithium-ion batteries. However, poor control of the lithium electrodeposition directly on the copper current collector, especially in conventional carbonate electrolytes, limits the development of such batteries. It is therefore essential to improve the understandings of the lithium electrodeposition, especially its nucleation process, and the interactions between lithium and the copper substrate. According to the classical electrodeposition theory, a larger overpotential will lead to a decrease in both the critical free energy for the nucleation and the critical radius of the nuclei, which should facilitate the nucleation process since more clusters can reach the critical radius required to form stable nuclei with a lower energy barrier. The concept was utilized via the application of a potentiostatic nucleation pulse to attain two-dimensional instantaneous lithium nucleation on lithium-metal electrodes in a previous study by Rehnlund et al.[1] Using such a strategy should also provide some insights into the lithium nucleation on copper substrates. In addition, it is also important to consider interactions between lithium and the copper substrate. A study, in which Lv et al.[2] used operando neutron diffraction to track the spatial distribution of lithium during lithium electrodeposition and stripping on copper, revealed that some lithium was actually taken up by the copper substrates most likely via the grain boundaries during the electrodeposition. In other studies by Rehnlund et al., the results also showed that lithium can diffuse into copper and that the effect of this diffusion can be readily seen after electrodepositing a small amount of lithium (as would be the case during the lithium nucleation stage).[3,4] However, the relation between such a lithium diffusion behavior and the lithium nucleation on copper substrates is not clearly studied. With a series of electrodeposition experiments, we demonstrate that it is highly possible that the lithium diffusion into the copper substrate can influence the nucleation process. Due to the presence of such diffusion, small lithium clusters and nuclei may be lost during the nucleation process, which makes it difficult to obtain a larger number of lithium nuclei with a homogeneous distribution on the copper surface. This then leads to inhomogeneous lithium electrodeposits with poor morphologies. It is, however, demonstrated that the nucleation of lithium on copper can be significantly improved if an initial chemical prelithiation of the copper surface is performed. This prelithiation saturates the copper surface with lithium and hence decreases the influence of lithium diffusion via the grain boundaries. In this way, the lithium nucleation can be made to take place more homogenously on the copper surface, especially when a short potentiostatic nucleation pulse that can generate a large number of nuclei is used. [1] D. Rehnlund, C. Ihrfors, J. Maibach, L. Nyholm, Mater. Today 21 (2018) 1010–1018. [2] S. Lv, T. Verhallen, A. Vasileiadis, F. Ooms, Y. Xu, Z. Li, Z. Li, M. Wagemaker, Nat. Commun. 9 (2018) 1–12. [3] D. Rehnlund, F. Lindgren, S. Böhme, T. Nordh, Y. Zou, J. Pettersson, U. Bexell, M. Boman, K. Edström, L. Nyholm, Energy Environ. Sci. 10 (2017) 1350–1357. [4] D. Rehnlund, J. Pettersson, K. Edström, L. Nyholm, ChemistrySelect 3 (2018) 2311–2314.
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25

Horiike, Hiroshi, Mizuho Ida, Toshiyuki Iida, Shoji Inoue, Seiji Miyamoto, Takeo Muroga, Hideo Nakamura, Hiroo Nakamura, Izuru Matsushita y Nobuo Yamaoka. "Lithium free surface flow experiment for IFMIF". Fusion Engineering and Design 66-68 (septiembre de 2003): 199–204. http://dx.doi.org/10.1016/s0920-3796(03)00205-9.

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26

Xie, Hui, Jose A. Alonso, Yutao Li, Maria T. Fernández-Díaz y John B. Goodenough. "Lithium Distribution in Aluminum-Free Cubic Li7La3Zr2O12". Chemistry of Materials 23, n.º 16 (23 de agosto de 2011): 3587–89. http://dx.doi.org/10.1021/cm201671k.

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27

Parekh, Mihit H., P. Manikandan y Vilas G. Pol. "In Operando Lithiation of Lithium Free Cathodes". ECS Meeting Abstracts MA2020-02, n.º 1 (23 de noviembre de 2020): 83. http://dx.doi.org/10.1149/ma2020-02183mtgabs.

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28

张, 宇昊. "Advances on Anode Free Lithium Metal Batteries". Journal of Organic Chemistry Research 11, n.º 04 (2023): 245–62. http://dx.doi.org/10.12677/jocr.2023.114024.

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29

Hwang, Bing-Joe. "Development of Anode-Free Lithium Metal Batteries". ECS Meeting Abstracts MA2023-02, n.º 4 (22 de diciembre de 2023): 641. http://dx.doi.org/10.1149/ma2023-024641mtgabs.

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The continuous demand for high energy density storage devices, researchers has focused on a new energy storage system for their practical life. Absolutely, Lithium metal is a best anode candidate for high energy density Lithium Metal Battery (LMB) because it has high theoretical capacity, light weight and much lower negative reduction potential.However, the growth of Li dendrite and low Coulombic efficiency upon Li plating/stripping causes the safety issues and poor cycle life of LMBs because of challenges embedded from the interaction of the Li metal with electrolyte and unstable SEI layer formation. For that reason, people have focused on developing new chemistry/system to improve the energy density, cycle life and safe energy storage system for practical applications. Anode free lithium metal battery (AFLMB) is one of the alternate choices and new system for high energy density storage system because it has no active anode material initially. In addition, the fabrication of AFLMB is simple, low-cost, safe since Li metal is not directly used as an anode. However, since the Li amount is limited and electrolyte decomposition, consuming Li during the SEI formation, the capacity can fade quickly relative to LMB. The dead Li can affect the Coulombic efficiency, polarization, and cycle life of the cell during continues cycles of AFLMB. However, AFLMB is the best system to understand the detail chemistry like quantification of dead Li, polarization effect, electrolyte consumption easily compared to the LMB. In this presentation, various approaches including functional electrolytes and functional coating on Cu surface will be reported to improve the coulombic efficiency, energy density and cycle life for the AFLMB.
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30

Liu, Sheng, Xudong Yu, Yu Yan, Ting Zeng, Xinxiang Wang, Guilei Tian, Chuan Wang, Shuhan Wang, Ying Zeng y Chaozhu Shu. "Dendrite-free lithium deposition enabled by interfacial regulation via dipole-dipole interaction in anode-free lithium metal batteries". Energy Storage Materials 62 (septiembre de 2023): 102959. http://dx.doi.org/10.1016/j.ensm.2023.102959.

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31

Alexander, George y Eric D. Wachsman. "Enabling Lithium-Free Batteries through Newly Developed Lithium-Garnet with Mixed Ion and Electron Conduction". ECS Meeting Abstracts MA2024-02, n.º 8 (22 de noviembre de 2024): 1222. https://doi.org/10.1149/ma2024-0281222mtgabs.

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Garnet structured solid electrolyte with a lithium-metal anode and high voltage cathode is a promising battery system owing to its inherent safety with high energy density. However, integrating thick metallic lithium with garnet solid electrolyte is not viable for a scalable process due to its complexity and the excess volume of lithium-metal compared to the lithiated cathode. To overcome these challenges, “lithium-free” batteries fabricated in a discharged state of the battery with only the current collector at the anode side is garnering increasing attention.1 The major drawback of a “lithium-free” battery with a garnet solid electrolyte is the limited lithium plating capacity and poor coulombic efficiency. To address this, we developed a mixed ion electron conducting (MIEC) garnet with comparable lithium-ion and electron conductivity at room temperature.2 We demonstrate that with a porous MIEC framework supporting a thin dense garnet solid electrolyte the cells can be cycled with no dendrite-induced shorting, at room temperature and sub-zero temperature without any stack pressure. Through various electrochemical characterization and electron microscopy the role of porous MIEC was elucidated. Huang, Wen‐Ze, Chen‐Zi Zhao, Peng Wu, Hong Yuan, Wei‐Er Feng, Ze‐Yu Liu, Yang Lu et al. "Anode‐free solid‐state lithium batteries: a review." Adv. Energy Mat. 12, 2201044 (2022). Alexander, George V., Changmin Shi, Jon O’Neill, and Eric D. Wachsman. "Extreme lithium-metal cycling enabled by a mixed ion-and electron-conducting garnet three-dimensional architecture." Nat. Mat. 22, 1136-1143 (2023).
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32

Ramsbottom, C. A. y K. L. Bell. "The continuous free–free absorption coefficient of the negative lithium ion". Physica Scripta 54, n.º 3 (1 de septiembre de 1996): 250–53. http://dx.doi.org/10.1088/0031-8949/54/3/004.

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33

Galashev, Alexander y Alexey Vorob'ev. "An Ab Initio Study of Lithization of Two-Dimensional Silicon–Carbon Anode Material for Lithium-Ion Batteries". Materials 14, n.º 21 (4 de noviembre de 2021): 6649. http://dx.doi.org/10.3390/ma14216649.

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This work is devoted to a first-principles study of changes in the structural, energetic, and electronic properties of silicene anodes during their lithium filling. Anodes were presented by silicene on carbon substrate and free-standing silicene. The ratio of the amount of lithium to silicon varied in the range from 0.06 to 1.125 for silicene on bilayer graphene and from 0.06 to 2.375 for free-standing silicene. It is shown that the carbon substrate reduces the stability of the silicene sheet. Silicene begins to degrade when the ratio of lithium to silicon (NLi/NSi) exceeds ~0.87, and at NLi/NSi = 0.938, lithium penetrates into the space between the silicene sheet and the carbon substrate. At certain values of the Li/Si ratio in the silicene sheet, five- and seven-membered rings of Si atoms can be formed on the carbon substrate. The presence of two-layer graphene imparts conductive properties to the anode. These properties can periodically disappear during the adsorption of lithium in the absence of a carbon substrate. Free-standing silicene adsorbed by lithium loses its stability at NLi/NSi = 1.375.
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34

Kamenetskikh, Alexander, Nikolay Gavrilov, Alexey Ershov y Petr Tretnikov. "Effect of the Degree of Li3PO4 Vapor Dissociation on the Ionic Conductivity of LiPON Thin Films". Membranes 13, n.º 10 (23 de octubre de 2023): 847. http://dx.doi.org/10.3390/membranes13100847.

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Thin films of solid-state lithium-ion electrolytes show promise for use in small-sized autonomous power sources for micro- and nanoelectronic elements. The high rate of vacuum-plasma synthesis (~0.5 μm/h) of lithium phosphor-oxynitride (LiPON) films with an ionic conductivity of ~2·10−6 S/cm is achieved through anodic evaporation of Li3PO4 in a low-pressure arc. The microstructure and ionic conductivity of LiPON films are influenced by the proportion of free lithium in the vapor flow. This paper presents the results of a study on the plasma composition during anodic evaporation of Li3PO4 in a discharge with a self-heating hollow cathode and a crucible anode. A method is proposed for adjusting the free lithium concentration in the gas-vapor (Li3PO4 + N2/Ar) discharge plasma based on changing the frequency of collisions of electrons with Li3PO4 vapor in the anodic region of the discharge. It is demonstrated that an increase in the proportion of free lithium in the flow of deposited particles leads to an enhancement in the concentration and mobility of lithium ions in the deposited films and, subsequently, an improvement in the ionic conductivity of LiPON films.
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35

Li, Bo-Quan, Xiao-Ru Chen, Xiang Chen, Chang-Xin Zhao, Rui Zhang, Xin-Bing Cheng y Qiang Zhang. "Favorable Lithium Nucleation on Lithiophilic Framework Porphyrin for Dendrite-Free Lithium Metal Anodes". Research 2019 (6 de enero de 2019): 1–11. http://dx.doi.org/10.34133/2019/4608940.

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Lithium metal constitutes promising anode materials but suffers from dendrite growth. Lithiophilic host materials are highly considered for achieving uniform lithium deposition. Precise construction of lithiophilic sites with desired structure and homogeneous distribution significantly promotes the lithiophilicity of lithium hosts but remains a great challenge. In this contribution, a framework porphyrin (POF) material with precisely constructed lithiophilic sites in regard to chemical structure and geometric position is employed as the lithium host to address the above issues for dendrite-free lithium metal anodes. The extraordinary lithiophilicity of POF even beyond lithium nuclei validated by DFT simulations and lithium nucleation overpotentials affords a novel mechanism of favorable lithium nucleation to facilitate uniform nucleation and inhibit dendrite growth. Consequently, POF-based anodes demonstrate superior electrochemical performances with high Coulombic efficiency over 98%, reduced average voltage hysteresis, and excellent stability for 300 cycles at 1.0 mA cm−2, 1.0 mAh cm−2 superior to both Cu and graphene anodes. The favorable lithium nucleation mechanism on POF materials inspires further investigation of lithiophilic electrochemistry and development of lithium metal batteries.
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36

Li, Bo-Quan, Xiao-Ru Chen, Xiang Chen, Chang-Xin Zhao, Rui Zhang, Xin-Bing Cheng y Qiang Zhang. "Favorable Lithium Nucleation on Lithiophilic Framework Porphyrin for Dendrite-Free Lithium Metal Anodes". Research 2019 (6 de enero de 2019): 1–11. http://dx.doi.org/10.1155/2019/4608940.

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Lithium metal constitutes promising anode materials but suffers from dendrite growth. Lithiophilic host materials are highly considered for achieving uniform lithium deposition. Precise construction of lithiophilic sites with desired structure and homogeneous distribution significantly promotes the lithiophilicity of lithium hosts but remains a great challenge. In this contribution, a framework porphyrin (POF) material with precisely constructed lithiophilic sites in regard to chemical structure and geometric position is employed as the lithium host to address the above issues for dendrite-free lithium metal anodes. The extraordinary lithiophilicity of POF even beyond lithium nuclei validated by DFT simulations and lithium nucleation overpotentials affords a novel mechanism of favorable lithium nucleation to facilitate uniform nucleation and inhibit dendrite growth. Consequently, POF-based anodes demonstrate superior electrochemical performances with high Coulombic efficiency over 98%, reduced average voltage hysteresis, and excellent stability for 300 cycles at 1.0 mA cm−2, 1.0 mAh cm−2 superior to both Cu and graphene anodes. The favorable lithium nucleation mechanism on POF materials inspires further investigation of lithiophilic electrochemistry and development of lithium metal batteries.
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37

Kim, Kwiyong, Yifu Chen, Jong-In Han, Hyung Chul Yoon y Wenzhen Li. "Lithium-mediated ammonia synthesis from water and nitrogen: a membrane-free approach enabled by an immiscible aqueous/organic hybrid electrolyte system". Green Chemistry 21, n.º 14 (2019): 3839–45. http://dx.doi.org/10.1039/c9gc01338e.

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38

Su, Laisuo, Harry Charalambous, Zehao Cui y Arumugam Manthiram. "Correction: High-efficiency, anode-free lithium–metal batteries with a close-packed homogeneous lithium morphology". Energy & Environmental Science 15, n.º 4 (2022): 1694. http://dx.doi.org/10.1039/d2ee90015g.

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Correction for ‘High-efficiency, anode-free lithium–metal batteries with a close-packed homogeneous lithium morphology’ by Laisuo Su et al., Energy Environ. Sci., 2022, 15, 843–854, DOI: 10.1039/D1EE03103A.
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39

Nanda, Sanjay y Arumugam Manthiram. "Lithium degradation in lithium–sulfur batteries: insights into inventory depletion and interphasial evolution with cycling". Energy & Environmental Science 13, n.º 8 (2020): 2501–14. http://dx.doi.org/10.1039/d0ee01074j.

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Anode-free full cells enable a quantitative estimate of lithium inventory loss rates, which is correlated with the growth of an electrolyte decomposition layer, even as metallic lithium stays intact with cycling.
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40

Hoashi, Eiji, Hirokazu Sugiura, Sachiko Yoshihashi-Suzuki, Takuji Kanemura, Hiroo Kondo, Nobuo Yamaoka y Hiroshi Horiike. "ICONE19-44185 Study on Surface Wave Characteristics of Free Surface Flow of Lithium for IFMIF". Proceedings of the International Conference on Nuclear Engineering (ICONE) 2011.19 (2011): _ICONE1944. http://dx.doi.org/10.1299/jsmeicone.2011.19._icone1944_58.

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41

Rodriguez, Rodrigo, Ruth A. Edison, Ryan M. Stephens, Ho-Hyun Sun, Adam Heller y C. Buddie Mullins. "Separator-free and concentrated LiNO3 electrolyte cells enable uniform lithium electrodeposition". Journal of Materials Chemistry A 8, n.º 7 (2020): 3999–4006. http://dx.doi.org/10.1039/c9ta10929c.

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Imaging of lithium electrodepositions revealed that in the absence of a compressed porous separator, achieved via a plastic washer, dendrite-free lithium was deposited from glyme solutions of 1 M LiNO3.
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42

Li, Zhen, I.-Chun Chen, Li Cao, Xiaowei Liu, Kuo-Wei Huang y Zhiping Lai. "Lithium extraction from brine through a decoupled and membrane-free electrochemical cell design". Science 385, n.º 6716 (27 de septiembre de 2024): 1438–44. http://dx.doi.org/10.1126/science.adg8487.

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The sustainability of lithium-based energy storage or conversion systems, e.g., lithium-ion batteries, can be enhanced by establishing methods of efficient lithium extraction from harsh brines. In this work, we describe a decoupled membrane-free electrochemical cell that cycles lithium ions between iron-phosphate electrodes and features cathode (brine) and anode (fresh water) compartments that are isolated from each other yet electrochemically connected through a pair of silver/silver-halide redox electrodes. This design is compatible with harsh brines having magnesium/lithium molar ratios of up to 3258 and lithium concentrations down to 0.15 millimolar, enabling the production of battery-grade (>99.95% pure) lithium carbonate. Energy savings of up to ~21.5% were realized by efficiently harvesting the osmotic energy of the brines. A pilot-scale cell with an electrode surface area of 33.75 square meters was used to realize lithium extraction from Dead Sea brine with a recovery rate of 84.0%.
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43

Fan, Austin, Zhuo Li y Kelsey Hatzell. "Operando Quantification of Dynamic Lithium Active Area Growth in Zero-Excess-Lithium Solid-State Batteries". ECS Meeting Abstracts MA2024-02, n.º 4 (22 de noviembre de 2024): 418. https://doi.org/10.1149/ma2024-024418mtgabs.

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Growing demands for electric vehicles motivate the need for energy-dense battery technologies that can enable enhanced driving ranges on a single charge [1]. Zero-excess-lithium solid-state batteries operate with no excess lithium at the anode, instead fully cycling all the lithium within the cell during each cycle. Removing excess lithium significantly increases the specific and volumetric energy density, improves battery safety, and reduces manufacturing costs [2]. However, zero-excess-lithium solid-state batteries suffer from poor coulombic efficiency and lithium dendrite formation [3] resulting from non-uniform lithium deposition onto the anodic current collector [4]. Optical microscopy is a promising operando technique for examining the electro-chemo-mechanics of lithium nucleation and growth during lithium deposition in a zero-excess-lithium solid-state battery [4]. In this work, we investigate the lithium nucleation and growth behavior on a current collector substrate using a custom cell conducive to operando optical microscopy. The transparent components of the cell allow for direct, real-time observation of lithium plating behavior. In particular, quantifying the dynamic in-plane lithium growth as a function of operating conditions such as current density, temperature, and thermal gradients provides crucial insight into the lithium growth mechanism. Optical data is complemented with mapped synchrotron diffraction data that elucidate the vertical growth of lithium into the solid electrolyte pellet by measuring the relative intensities of lithium. These results enable comprehensive characterization of lithium growth regimes, including in-plane-growth dominant and vertical-growth dominant regimes, at successive capacities of lithium plated. Understanding these lithium growth regimes guides strategies to attain more lateral, uniform lithium deposition, with long-term implications in achieving stable, high-capacity zero-excess-lithium solid-state battery operation. References: [1] Yang-Kook Sun. Promising All-Solid-State Batteries for Future Electric Vehicles. ACS Energy Lett. 2020, 5, 3221-3223. [2] Christian Heubner, Sebastian Maletti, Henry Auer, Juliane Hüttl, Karsten Voigt, Oliver Lohrberg, Kristian Nikolowski, Mareike Partsch, and Alexander Michaelis. From Lithium-Metal toward Anode-Free Solid-State Batteries: Current Developments, Issues, and Challenges. Adv. Func. Mater. 2021, 31(51), 2106608. [3] Yuan Tian, Yongling An, Chuanliang Wei, Huiyu Jiang, Shenglin Xiong, Jinkui Feng, and Yitai Qian. Recently advances and perspectives of anode-free rechargeable batteries. Nano Energy. 2020, 78, 105344. [4] Eric Kazyak, Michael J. Wang, Kiwoong Lee, Srinivas Yadavalli, Adrian J. Sanchez, M.D. Thouless, Jeff Sakamoto, and Neil P. Dasgupta. Understanding the electro-chemo-mechanics of Li plating in anode-free solid-state batteries with operando 3D microscopy. Matter. 2022, 5(11), 3912-3934.
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44

Wang, Jian, Hongzhen Lin y Stefano Passerini. "Construction of Dendrite-Free Metallic Lithium Anodes: From Static Lithiophilic Adsorption to Dynamic Electrochemical Diffusion Kinetics". ECS Meeting Abstracts MA2023-02, n.º 5 (22 de diciembre de 2023): 831. http://dx.doi.org/10.1149/ma2023-025831mtgabs.

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Lithium metal batteries (LMBs) possess high theoretical energy density, becoming a promising next-generation energy storage system.1, 2 However, the applications of Li metal anodes are restricted by the Li dendrite formation, repeated formation and fracturing of solid electrolyte interphase (SEI), and large volume expansion, resulting in severe “dead lithium” and subsequent short circuiting.3, 4 Herein, differing from conventional interfacial engineering or current-collector designs with numerous lithiophilic site, fundamental novel insights of Li plating kinetics via using single-atomic catalyst (SAC) activators to boost Li diffusion behaviors is proposed to realize delocalized deposition.5, 6 Specifically, via the aid of series of characterizations and theoretical simulations, the SACs have the ability in decreasing barriers of desolvation, Li ion transport or Li atom diffusion and we have unambiguously depicted that the SACs serve as kinetic activators in propelling the surface spreading and lateral redistribution of the lithium atoms for achieving dendrite-free plating morphology. Reference: Wang, J.; Hu, H.; Zhang, J.; Li, L.; Jia, L.; Guan, Q.; Hu, H.; Liu, H.; Jia, Y.; Zhuang, Q.; Cheng, S.; Huang, M.; Lin, H. Hydrophobic lithium diffusion-accelerating layers enables long-life moisture-resistant metallic lithium anodes in practical harsh environments. Energy Storage Mater. 2022, 52, 210-219. Zhang, J.; He, R.; Zhuang, Q.; Ma, X.; You, C.; Hao, Q.; Li, L.; Cheng, S.; Lei, L.; Deng, B.; Li, X.; Lin, H.; Wang, J. Tuning 4f-Center Electron Structure by Schottky Defects for Catalyzing Li Diffusion to Achieve Long-Term Dendrite-Free Lithium Metal Battery. Adv. Sci. (Weinh) 2022, 9, (23), e2202244. Wang, J.; Li, L.; Hu, H.; Hu, H.; Guan, Q.; Huang, M.; Jia, L.; Adenusi, H.; Tian, K. V.; Zhang, J.; Passerini, S.; Lin, H. Toward Dendrite-Free Metallic Lithium Anodes: From Structural Design to Optimal Electrochemical Diffusion Kinetics. ACS Nano 2022, 16, 17729−17760. Zhang, J.; You, C.; Lin, H.; Wang, J. Electrochemical Kinetic Modulators in Lithium–Sulfur Batteries: From Defect‐Rich Catalysts to Single Atomic Catalysts. Energy & Environmental Materials 2022, 5, (3), 731-750. Wang, J.; Zhang, J.; Cheng, S.; Yang, J.; Xi, Y.; Hou, X.; Xiao, Q.; Lin, H. Long-Life Dendrite-Free Lithium Metal Electrode Achieved by Constructing a Single Metal Atom Anchored in a Diffusion Modulator Layer. Nano Lett. 2021, 21, (7), 3245-3253. Wang, J.; Zhang, J.; Duan, S.; Jia, L.; Xiao, Q.; Liu, H.; Hu, H.; Cheng, S.; Zhang, Z.; Li, L.; Duan, W.; Zhang, Y.; Lin, H. Lithium Atom Surface Diffusion and Delocalized Deposition Propelled by Atomic Metal Catalyst toward Ultrahigh-Capacity Dendrite-Free Lithium Anode. Nano Lett. 2022, 22, (19), 8008-8017.
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45

Weldeyohannes, Haile Hisho, Wei-Nien Su y Bing-Joe Hwang. "Regulating Lithium Metal Deposition for Safe Cell Operation and to Extend Cyclic Performance of an Anode-Free Lithium Metal Battery". ECS Meeting Abstracts MA2022-01, n.º 2 (7 de julio de 2022): 426. http://dx.doi.org/10.1149/ma2022-012426mtgabs.

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Using the ideal Lithium metal (Li) as an anode material for Lithium metal batteries (LMBs) displays considerable potential in enlightening energy density and power density than conventional lithium-ion batteries (LIBs). Nevertheless, the low Coulombic efficiency, significant volume changes during operation, which reduces electrode mechanical stability, and Lithium (Li) dendrites formed and growth from nonuniform Li deposition during cell operation causes safety issues and limits potential uses of Li as an anode material for LMBs. Recently, anode free (Lithium free) lithium metal batteries (AFLMBs) protocol have got great attention due to their higher energy density, reduces cell weight, costs effectiveness, easy fabrication, and safety during the process of cell manufacture. Nevertheless, in AFLMBs, the uncontrolled plating of lithium on bare copper foil imposes a more severe lithium dendrite growth. Hence, planning proper design on an anode current collector which is appropriate for AFLMBs is essential. Herein, we handle the growth of lithium dendrite by guiding lithium metal deposition site to the backside of the gold-sputtered perforated polyimide film (PI@Au), which used as an anode current collector. Hence, metallic lithium (Li) starts to plate on the modified PI@Au surface, and sequentially, growth of Li takes place in the direction away from the separator face (ASF). This backside deposition and growth approach allow the battery to operate safely, even when lithium dendrite exists. . Surprisingly, the dendrite-free surface on the separator-facing side (SF) of PI@Au anode reveals significantly improved cycling stability. As a result PI@Au//Li cell (2 mAh/cm2 and 0.5 mA/cm2) offers stable cycling performance for 1400 h without significant voltage polarization. Conversely, Cu//Li cell cycling with results higher voltage hysteresis and face short-circuit below 600 h at same working conditions. Besides, PI@Au//LFP anode-free full cell configuration maintained 20 % capacity retention (CR) with average Coulombic efficiency of 98.7 % after 340 cycles (0.5 mA/cm2). On the contrary, the Cu//LFP full cell runs only for 165 cycles under the same value of CR. Guiding the plating of Li to the backside of perforated polyimide film insights into an innovative technique for developing ultra-safe AFLMBs and also proves the viability of the electrical insulator substrates as anode current collectors by improving their conductivity and lithiophilicity.
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46

Ahmad, Zeeshan, Zijian Hong y Venkatasubramanian Viswanathan. "Design rules for liquid crystalline electrolytes for enabling dendrite-free lithium metal batteries". Proceedings of the National Academy of Sciences 117, n.º 43 (9 de octubre de 2020): 26672–80. http://dx.doi.org/10.1073/pnas.2008841117.

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Dendrite-free electrodeposition of lithium metal is necessary for the adoption of high energy-density rechargeable lithium metal batteries. Here, we demonstrate a mechanism of using a liquid crystalline electrolyte to suppress dendrite growth with a lithium metal anode. A nematic liquid crystalline electrolyte modifies the kinetics of electrodeposition by introducing additional overpotential due to its bulk-distortion and anchoring free energy. By extending the phase-field model, we simulate the morphological evolution of the metal anode and explore the role of bulk-distortion and anchoring strengths on the electrodeposition process. We find that adsorption energy of liquid crystalline molecules on a lithium surface can be a good descriptor for the anchoring energy and obtain it using first-principles density functional theory calculations. Unlike other extrinsic mechanisms, we find that liquid crystals with high anchoring strengths can ensure smooth electrodeposition of lithium metal, thus paving the way for practical applications in rechargeable batteries based on metal anodes.
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47

Kraszewska, Agnieszka, Ewa Ferensztajn-Rochowiak y Janusz Rybakowski. "The effect of including other psychotropic medications into a long-term bipolar disorder lithium treatment on thyroid function". Pharmacotherapy in Psychiatry and Neurology 35, n.º 2 (2019): 111–19. http://dx.doi.org/10.33450/fpn.2019.08.001.

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Background/Aims. Long-term bipolar disorder (BD) treatment with lithium exerts a significant effect on thyroid structure and function. Compared with BD patients who do not take lithium, patients treated with lithium have higher concentrations of thyroid-stimulating hormone (TSH) and free thyroxine (FT4), lower concentrations of free triiodothyronine (FT3), higher thyroid volume and higher occurrence of goitre. The aim of the study was to compare thyroid structure and function in relation to the inclusion of other mood stabilisers and antidepressants into a lithium treatment. Method. The studied group consisted of eighty BD patients (27 male, 53 female) aged 24–85 years, receiving a prophylactic lithium treatment for the average of 19 ± 9 years. Fifteen patients underwent lithium monotherapy; in 17, lithium was administered concurrently with carbamazepine; in 17, concurrently with quetiapine; and in 11, concurrently with valproate. In 20 subjects, lithium was administered concurrently with antidepressants. Results. In comparison with patients on lithium monotherapy, in patients who took lithium and antidepressant drugs, the concentrations of TSH were significantly higher, while in patients who took lithium and carbamazepine the concentrations of FT4 were lower. The concentrations of thyroid peroxidase antibodies (TPOAb) were significantly higher in patients who took lithium concurrently with antidepressants and concurrently with valproate. The highest frequency of goitre (70%) was observed in patients who took lithium concurrently with antidepressants. Conclusions. The obtained results may suggest a significant effect of including other mood stabilisers and antidepressants into a long-term lithium treatment on thyroid structure and function. A limitation of the study is the small size of the groups.
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48

Bhargav, Amruth, Wei Guo y Yongzhu Fu. "Chemically synthesized lithium peroxide composite cathodes for closed system Li–O2 batteries". Chemical Communications 52, n.º 33 (2016): 5678–81. http://dx.doi.org/10.1039/c6cc01547f.

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49

Lee, Dongsoo, Seho Sun, Hyunjung Park, Jeongheon Kim, Keemin Park, Insung Hwang, Yongmin Jung, Taeseup Song y Ungyu Paik. "Stable artificial solid electrolyte interphase with lithium selenide and lithium chloride for dendrite-free lithium metal anodes". Journal of Power Sources 506 (septiembre de 2021): 230158. http://dx.doi.org/10.1016/j.jpowsour.2021.230158.

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50

Gaillard, C. A., H. A. Koomans, A. J. Rabelink y E. J. Mees. "Effects of indomethacin on renal response to atrial natriuretic peptide". American Journal of Physiology-Renal Physiology 253, n.º 5 (1 de noviembre de 1987): F868—F873. http://dx.doi.org/10.1152/ajprenal.1987.253.5.f868.

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We studied the effect of alpha-human natriuretic peptide (ANP, 100 micrograms iv) on renal sodium handling in eight healthy subjects before and after 7 days of indomethacin (50 mg 3 times a day). Sodium intake was 100 mmol/day. Prior to indomethacin, ANP caused a fourfold rise in sodium excretion over the first 20 min and a threefold rise in fractional sodium excretion. The clearance studies, performed during maximal water diuresis, showed increased fractional free water clearance and lithium clearance. Indomethacin caused marked sodium retention. Complete escape did not occur until the sixth day, when cumulative balance was 244 mmol (range 176-337). By this time renin and aldosterone were suppressed and fractional lithium and free water clearance reduced. The natriuretic effect of ANP was not attenuated, and the fractional excretion of sodium and chloride rose even more than without indomethacin. The reduction in lithium and free water clearance under indomethacin tended to be reversed by ANP. These data suggest that the natriuretic effect of ANP is not mediated by or dependent on renal prostaglandins. Indomethacin and ANP appear to have opposite effects on sodium excretion, maximal free water clearance, and lithium clearance.
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