Effect of electrochemical dissolution and deposition order on lithium dendrite formation: a top view investigation

2014 ◽  
Vol 176 ◽  
pp. 109-124 ◽  
Author(s):  
Wenjun Li ◽  
Hao Zheng ◽  
Geng Chu ◽  
Fei Luo ◽  
Jieyun Zheng ◽  
...  
Keyword(s):  
Carbon Nanotube ◽  
Electron Flow ◽  
Ex Situ ◽  
Surface Oxide Layer ◽  
Electrochemical Dissolution ◽  
Lithium Electrode ◽  
Metallic Lithium ◽  
Lithium Dendrites ◽  
Lithium Dendrite ◽  
Top View

Rechargeable metallic lithium batteries are the ultimate solution to electrochemical storage due to their high theoretical energy densities. One of the key technological challenges is to control the morphology of metallic lithium electrode during electrochemical dissolution and deposition. Here we have investigated the morphology change of metallic lithium electrode after charging and discharging in nonaqueous batteries by ex situ SEM techniques from a top view. Formation of the hole structure after lithium dissolution and the filling of dendrite-like lithium into the holes has been observed for the first time. In addition, an in situ SEM investigation using an all-solid Li/Li2O/super aligned carbon nanotube set-up indicates that lithium ions could diffuse across through the surface oxide layer and grow lithium dendrites after applying an external electric field. The growth of lithium dendrites can be guided by electron flow when the formed lithium dendrite touches the carbon nanotube.

Trace fluorinated-carbon-nanotube-induced lithium dendrite elimination for high-performance lithium–oxygen cells

Nanoscale ◽  
2020 ◽  
Vol 12 (5) ◽  
pp. 3424-3434 ◽  
Author(s):  
Hao Cheng ◽  
Yangjun Mao ◽  
Yunhao Lu ◽  
Peng Zhang ◽  
Jian Xie ◽  
...  
Keyword(s):  
Carbon Nanotube ◽  
High Performance ◽  
Dendrite Growth ◽  
Metallic Lithium ◽  
Lithium Dendrite ◽  
Fluorinated Carbon

Trace fluorinated-CNT-modified metallic lithium enables in situ LiF-rich SEI formation and effectively eliminates lithium dendrite growth.

scholarly journals Blocking Lithium Dendrite Growth in Solid-State Batteries with an Ultrathin Amorphous Li-La-Zr-O Solid Electrolyte

2021 ◽  
Author(s):  
Jordi Sastre ◽  
Moritz Futscher ◽  
Lea Pompizi ◽  
Abdessalem Aribia ◽  
Agnieszka Priebe ◽  
...  
Keyword(s):  
Solid State ◽  
Electronic Conductivity ◽  
High Capacity ◽  
External Pressure ◽  
Lithium Metal ◽  
Metallic Lithium ◽  
Lithium Dendrites ◽  
Lithium Garnet ◽  
Solid State Batteries ◽  
Lithium Dendrite

Abstract Lithium metal dendrites have become a roadblock in the realization of next-generation solid-state batteries with lithium metal as high-capacity anode. The presence of surface and bulk inhomogeneities with non-negligible electronic conductivity in crystalline electrolytes such as the lithium garnet Li7La3Zr2O12 (LLZO) facilitates the growth of lithium filaments, posing a critical safety risk. Here we explore the amorphous phase of LLZO (aLLZO) as a lithium dendrite shield owing to its grain-boundary-free microstructure, stability against metallic lithium, and high electronic insulation. We demonstrate that by tuning the lithium stoichiometry in sputtered aLLZO films, the ionic conductivity can be increased up to 10-7 S cm-1 while retaining an ultralow electronic conductivity of 10-14 S cm-1. In Li/aLLZO/Li symmetric cells, plating-stripping results in no degradation of the films and current densities up to 3.2 mA cm-2 can be applied with no signs of lithium penetration. The defect-free and conformal nature of the films enables microbatteries with an electrolyte thickness as low as 70 nm, which withstand charge-discharge at 0.2 mA cm-2 for over 500 cycles. Finally, we demonstrate that the application of aLLZO as a coating on crystalline LLZO lowers the interface resistance and significantly impedes the formation of lithium dendrites, increasing the critical current density of a symmetric cell up to 1.3 mA cm-2 at room temperature and without external pressure. The effectiveness of the amorphous Li-La-Zr-O as lithium dendrite blocking layer can accelerate the development of more powerful and safer solid-state batteries.

scholarly journals Lithium Dendrite Inhibition on Post-Charge Anode Surface: The Kinetics Role

2015 ◽  
Vol 1774 ◽  
pp. 31-39
Author(s):  
Asghar Aryanfar ◽  
Tao Cheng ◽  
Boris V. Merinov ◽  
William A. Goddard ◽  
Agustin J Colussi ◽  
...  
Keyword(s):  
Average Length ◽  
Anode Surface ◽  
Activation Barriers ◽  
Metallic Lithium ◽  
Molecular Dynamics Calculations ◽  
Lithium Dendrites ◽  
Experimental Activation Energy ◽  
Reaxff Force Field ◽  
Lithium Dendrite ◽  
Kinetics Of

ABSTRACTWe report experiments and molecular dynamics calculations on the kinetics of electrodeposited lithium dendrites relaxation as a function of temperature and time. We found that the experimental average length of dendrite population decays via stretched exponential functions of time toward limiting values that depend inversely on temperature. The experimental activation energy derived from initial rates as Ea∼ 6-7 kcal/mole, which is closely matched by MD calculations, based on the ReaxFF force field for metallic lithium. Simulations reveal that relaxation proceeds in several steps via increasingly larger activation barriers. Incomplete relaxation at lower temperatures is therefore interpreted a manifestation of cooperative atomic motions into discrete topologies that frustrate monotonic progress by ‘caging’.

scholarly journals Blocking Lithium Dendrite Growth in Solid-State Batteries with an Ultrathin Amorphous Li-La-Zr-O Solid Electrolyte

2021 ◽  
Author(s):  
Jordi Sastre ◽  
Moritz H. Futscher ◽  
Lea Pompizi ◽  
Abdessalem Aribia ◽  
Agnieszka Priebe ◽  
...  
Keyword(s):  
Solid State ◽  
Electronic Conductivity ◽  
High Capacity ◽  
External Pressure ◽  
Lithium Metal ◽  
Metallic Lithium ◽  
Lithium Dendrites ◽  
Lithium Garnet ◽  
Solid State Batteries ◽  
Lithium Dendrite

Lithium metal dendrites have become a roadblock in the realization of next-generation solid-state batteries with lithium metal as high-capacity anode. The presence of surface and bulk inhomogeneities with non-negligible electronic conductivity in crystalline electrolytes such as the lithium garnet Li<sub>7</sub>La<sub>3</sub>Zr<sub>2</sub>O<sub>12</sub> (LLZO) facilitates the growth of lithium filaments, posing a critical safety risk. Here we explore the amorphous phase of LLZO (aLLZO) as a lithium dendrite shield owing to its grain-boundary-free microstructure, stability against metallic lithium, and high electronic insulation. We demonstrate that by tuning the lithium stoichiometry in sputtered aLLZO films, the ionic conductivity can be increased up to 10<sup>-7</sup> S cm<sup>-1</sup> while retaining an ultralow electronic conductivity of 10<sup>-14</sup> S cm<sup>-1</sup>. In Li/aLLZO/Li symmetric cells, plating-stripping results in no degradation of the films and current densities up to 3.2 mA cm<sup>-2</sup> can be applied with no signs of lithium penetration. The defect-free and conformal nature of the films enables microbatteries with an electrolyte thickness as low as 70 nm, which withstand charge-discharge at 0.2 mA cm<sup>-2</sup> for over 500 cycles. Finally, we demonstrate that the application of aLLZO as a coating on crystalline LLZO lowers the interface resistance and significantly impedes the formation of lithium dendrites, increasing the critical current density of a symmetric cell up to 1.3 mA cm<sup>-2</sup> at room temperature and without external pressure. The effectiveness of the amorphous Li-La-Zr-O as lithium dendrite blocking layer can accelerate the development of more powerful and safer solid-state batteries.<div></div>

Lithium Dendrite Growth Process and Research Progress of its Inhibition Methods

2021 ◽  
Vol 1027 ◽  
pp. 42-47
Author(s):  
Hao Ran Zheng
Keyword(s):  
Growth Process ◽  
Specific Capacity ◽  
Development Trend ◽  
High Energy ◽  
High Energy Density ◽  
Research Progress ◽  
Future Research ◽  
Battery Life ◽  
Lithium Dendrites ◽  
Lithium Dendrite

Metal lithium anodes, with extremely high specific capacity, low density, and lowest potential, are considered to be the most promising anode materials for next-generation high-energy density batteries. However, in the process of repeated plating and stripping of lithium, lithium dendrites are easily grown on the surface of the metal lithium anode, which greatly reduces the capacity of the battery, even causes hidden safety risks and shortens the battery life. This paper reviews the modification methods of lithium anodes based on the growth process of lithium dendrites, and introduces several current modification methods, including electrolyte additives, artificial SEI and new structure of lithium anodes. Finally, the future research direction and development trend of metal lithium anodes are prospected.

scholarly journals Electric Field Induced Biomimetic Transmembrane Electron Transport using Carbon Nanotube Porins as Bipolar Electrodes

2021 ◽  
Author(s):  
Jacqueline M. Hicks ◽  
Yun-Chiao Yao ◽  
Sydney Barber ◽  
Aleksandr Noy ◽  
Nigel Neate ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Carbon Nanotube ◽  
Electron Transport ◽  
Electric Fields ◽  
Electron Flow ◽  
Transport Systems ◽  
Redox Systems ◽  
Bipolar Electrodes ◽  
Electrochemical Approach ◽  
Transmembrane Electron Transport

<p>Cells modulate their homeostasis through the control of redox reactions via transmembrane electron transport systems. These are largely mediated via oxidoreductase enzymes. Their use in biology has been linked to a host of systems including reprogramming for energy requirements in cancer. Consequently, our ability to modulate membrane redox systems may give rise to opportunities to modulate underlying biology. The current work aimed to develop a wireless bipolar electrochemical approach to form on-demand electron transfer across biological membranes. To achieve this goal, we show that using membrane inserted carbon nanotube porins that can act as bipolar nanoelectrodes, we could control electron flow with externally applied electric fields across membranes. Before this work, bipolar electrochemistry has been thought to require high applied voltages not compatible with biological systems. We show that bipolar electrochemical reaction via gold reduction at the nanotubes could be modulated at low cell-friendly voltages, providing an opportunity to use bipolar electrodes to control electron flux across membranes. Our observations present a new opportunity to use bipolar electrodes to alter cell behavior via wireless control of membrane electron transfer.</p>

scholarly journals In Situ Measurement of Carbon Nanotube Growth Kinetics in a Rapid Thermal Chemical Vapor Deposition Reactor With Multizone Infrared Heating

2020 ◽  
Vol 8 (1) ◽  
Author(s):  
Moataz Abdulhafez ◽  
Jaegeun Lee ◽  
Mostafa Bedewy
Keyword(s):  
Chemical Vapor Deposition ◽  
Carbon Nanotube ◽  
Vapor Deposition ◽  
Chemical Vapor ◽  
Infrared Heating ◽  
Ex Situ ◽  
Depth Of Field ◽  
Carbon Nanotube Growth ◽  
Nanotube Growth

Abstract Understanding and controlling the growth of vertically aligned carbon nanotube (VACNT) forests by chemical vapor deposition (CVD) is essential for unlocking their potential as candidate materials for next generation energy and mass transport devices. These advances in CNT manufacturing require developing in situ characterization techniques capable of interrogating how CNTs grow, interact, and self-assemble. Here we present a technique for real-time monitoring of VACNT forest height kinetics applied to a unique custom designed rapid thermal processing (RTP) reactor for CVD of VACNTs. While the integration of multiple infrared heating lamps enables creating designed spatiotemporal temperature profiles inside the reactor, they pose challenges for in situ measurements. Hence, our approach relies on contrast-adjusted videography and image processing, combined with calibration using 3D optical microscopy with large depth-of-field. Our work enables reliably measuring VACNT growth rates and catalytic lifetimes, which are not possible to measure using ex situ methods.

scholarly journals Reduction Mechanism of Solid Electrolyte Interphase Formation on Lithium Metal Anode: Fluorine-Rich Electrolyte

2021 ◽  
Author(s):  
Yu Wu ◽  
Qintao Sun ◽  
Yue Liu ◽  
Peiping Yu ◽  
Bingyun Ma ◽  
...  
Keyword(s):  
Solid Electrolyte ◽  
Rational Design ◽  
Coulombic Efficiency ◽  
Solid Electrolyte Interphase ◽  
Reduction Mechanism ◽  
Metal Anode ◽  
Formation Pathway ◽  
Metallic Lithium ◽  
Initial Reduction ◽  
Lithium Dendrites

Abstract Metallic lithium is considered a promising anode that can significantly increase the energy density of rechargeable lithium-based batteries, but problems like uncontrollable growth of lithium dendrites and formation of dead lithium impede its application. Recently, a low-concentration single-salt two-solvent electrolyte, 1M LiTFSI/FDMA/FEC, has attracted attention because a high coulombic efficiency can be achieved even after many cycles owing to the formation of a robust solid electrolyte interface (SEI). However, the reaction mechanism and SEI structure remain unclear, posing significant challenges for further improvement. Here, a hybrid ab initio and reactive force field (HAIR) method revealed the underlying reaction mechanisms and detailed formation pathway. 1 ns HAIR simulation provides critical information on the initial reduction mechanism of solvent (FDMA and FEC) and salt (LiTFSI). FDMA and FEC quickly decompose to provide F- that builds LiF as the major component of the inner layer of inorganic SEI, which has been demonstrated to protect Li anode. Decomposition of FDMA also leads to a significant nitrogen-containing composition, producing Li-N-C, LixN, and other organic components that increase the conductivity of SEI to increase performance. XPS analysis confirms evolution of SEI morphology consistent with available experiments. These results provide atomic insight into SEI formation, which should be beneficial for the rational design of advanced electrolytes

scholarly journals Lithium Dendrites: Inside or Outside: Origin of Lithium Dendrite Formation of All Solid‐State Electrolytes (Adv. Energy Mater. 40/2019)

2019 ◽  
Vol 9 (40) ◽  
pp. 1970155
Author(s):  
Fangjie Mo ◽  
Jiafeng Ruan ◽  
Shuxian Sun ◽  
Zixuan Lian ◽  
Sangpu Yang ◽  
...  
Keyword(s):  
Solid State ◽  
Dendrite Formation ◽  
Lithium Dendrites ◽  
Solid State Electrolytes ◽  
Lithium Dendrite ◽  
Energy Mater
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