Formation, dynamics, and implication of solid electrolyte interphase in high voltage reversible conversion fluoride nanocomposites

Gmitter, Andrew J.; Badway, F.; Rangan, Sylvie; Bartynski, Robert; Halajko, Anna; Pereira, Nathalie; Amatucci, Glenn G.

doi:10.1039/b923908a

Cited by 99 publications

(108 citation statements)

References 24 publications

(30 reference statements)

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“…As such, if cathode dissolution and unfavorable interactions between active materials and electrolyte are avoided, conversion cathodes should be able to show very long cycle stability in cells. [16][17][18][19][20][21][22][23][24][25][26][46][47][48][49][50] The in situ CEI protection on the surface of the conversion cathodes has a promise to overcome such challenges as shown in Fig. 3(b).…”

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“…2(c)]. 49,51 For example, metal nanoparticles formed after the lithiation of MHs can catalyze the decomposition of some electrolytes, 49 resulting in the formation of thicker and more insulating surface layer on the cathode (which may be called a cathode electrolyte interphase (CEI), although its composition and formation mechanisms may be closer to anode SEI) [ Fig. 2(c), middle] and irreversible Li and active materials' losses, which similarly induce capacity fading and high voltage hysteresis (increasing polarization).…”

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“…[21][22][23]43,45 Similar to Li-chalcogen batteries, recent studies on various MHs also reported serious challenges of metal and halide dissolution during electrochemical conversion reactions. 16,17,[46][47][48][49][50] Nearly all conversion type cathode materials are somewhat soluble in polar organic solvents in at least some potential range. For example, CuF 2 -based cathodes suffer from severe Cu dissolution during charge before the reversible potential for the CuF 2 formation may be reached, which so far prevents having more than one electrochemical cycle of the unprotected CuF 2 .…”

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confidence: 99%

“…2(c), right]. 49 If the cracks formed inside the CEI due to the volume change, the exposed area will continue causing the electrolyte decomposition and cathode dissolution, which would result in SEI growth and irreversible Li and active material losses. Similarly, among Li-chalcogen chemistries, many chalcogenides are believed to be incompatible with both cyclic and linear carbonate solvents [such as ethylene carbonate (EC) and diethyl carbonate (DEC)] due to the irreversibly side reactions with polychalcogenides, which result in bad cycling stability.…”

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In situ surface protection for enhancing stability and performance of conversion-type cathodes

Borodin

Yushin

2017

MRS Energy & Sustainability

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Lithium and lithium-ion batteries (LBs and LIBs) are the most popular battery systems for electrochemical energy storage technologies. Commercial LIBs utilize intercalation-type cathode materials, mostly nickel (Ni)-based and cobalt (Co)-based cathodes, showing specific capacities of up to ∼200 mA h/g (theoretical capacity below 300 mA h/g), which limit the specific energy of batteries, and are additionally expensive and toxic. An EPA study showed that the Ni-and Co-containing batteries that use solvent-based electrode processing have the highest potential for negative environmental impacts. 1 These impacts include resource depletion, global warming, ecological toxicity, and human health impacts with the largest contributing processes include those associated with the production, processing, and use of cobalt and nickel metal compounds, which may cause adverse respiratory, pulmonary, and neurological effects in those exposed. 1 The study suggested cathode material substitution and solvent-less electrode processing to reduce these impacts. 1 The uneven distribution of Co in the earth crust 2 and the insufficient use of suitable personal protection equipment in many Co mining developing countries 3,4 created a major concern. For example, Amnesty International findings of major exploitations of children in Co mines and the related child sickness and deaths 3,4 demonstrate some of the most horrific examples of child labor, which international community should not tolerate and certainly should not encourage through growing market demands for Co. The growing Co contained-electronic waste ABSTRACTThe use of in situ formed protective layer on conversion cathodes was introduced as a cheap and simple strategy to shield these materials from undesirable interactions with liquid electrolytes.Conversion-type cathodes have been viewed as promising candidates to replace Ni-and Co-based intercalation-type cathodes for next-generation lithium (Li) and Li-ion batteries with higher specific energy, lower cost, and potentially longer cycle life. Typically, in conversion reactions two or three Li ions may be stored per just one atom of chalcogen (e.g., S or Se) or transition metal (e.g., Fe or Cu used in halides). Unfortunately, in conversion chemistries the active materials or intermediate charge/discharge products suffer from various unfavorable interactions and dissolution in organic electrolytes. In this mini-review article, we discuss the current interfacial challenges and focus on the protective layers in situ formed on the cathode surface to effectively shield conversion materials from undesirable interactions with liquid electrolytes. We further explore the mechanisms and current progress of forming such protective layers by using various salts, solvents, and additives together with the insight from molecular modeling. Finally, we discuss future opportunities and perspectives of in situ surface protection.Keywords: Li; S; F; coating; energy storage Review DiSCUSSiON POiNTS• Conversion-type cathodes have been viewed as promi...

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In situ surface protection for enhancing stability and performance of conversion-type cathodes

Borodin

Yushin

2017

MRS Energy & Sustainability

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“…We believe this is due to considerable resistance caused by the catalytic cathodic decomposition of the cyclic carbonates to form an extensive solid electrolyte interphase. 15 BiF 3 .-XRD results revealed two polymorphs of BiF 3 phases are formed from deposition: hexagonal tysonite (P3c1) and orthorhombic phase (Pnma) (Figure 6). After 7 days of chemical lithiation the orthorhombic BiF 3 disappears and reduce to Bi metal.…”

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Electronic Transport in Lithiated Iron and Bismuth Fluoride

Halajko

Parkinson

et al. 2014

J. Electrochem. Soc.

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Metal networks are formed during the lithiation of metal fluorides. Previous reports indicate that these networks are bi-continuous with the possibility to support electronic transport, though no quantitative analysis has been performed. In this study, thin films of FeF 2 and BiF 3 were chemically lithiated using n-butyllithium to form these metal networks. Direct current (DC) polarization and electrochemical impedance spectroscopy (EIS) were utilized to find electronic conductivity and results were compared to their pure metals. Results indicate films to have higher than expected conductivity value which indicates that these metal networks support electronic transport during lithiation. © The Author(s) 2014. Published by ECS. This is an open access article distributed under the terms of the Creative Commons Attribution Non-Commercial No Derivatives 4.0 License (CC BY-NC-ND, http://creativecommons.org/licenses/by-nc-nd/4.0/), which permits non-commercial reuse, distribution, and reproduction in any medium, provided the original work is not changed in any way and is properly cited. For permission for commercial reuse, please email: oa@electrochem.org. [DOI: 10.1149/2.0621501jes] All rights reserved. Lithium-ion batteries are the ubiquitous energy storage device for portable electronics. Historically, there has been a continuous quest for higher energy density chemistries in order to reduce the weight or volume in new innovative devices. Lithium conversion compounds are one of the promising alternatives for battery positive electrodes.1 The advantage is their ability to accommodate more than one lithium/electron per transition metal to achieve higher capacities than traditional intercalation compounds. Transition metal fluoride conversion materials have been a research focus because their highly ionic bonds allow reduction potentials approximately 1 V higher than the chalcogenides.2-5 As such, high capacity, low cost metal fluorides such as FeF 2 , FeF 3 and CuF 2 are of interest. FeF 2 has been extensively investigated as a potential electrode material due to its potential low cost and rutile structure which is common among the first row metal fluorides.6-8 The latter aspect makes it an excellent model material for fundamental studies. FeF 2 exhibits a single three phase reaction, FeF 2 + 2Li + + 2e − → Fe + 2 LiF, exhibiting a theoretical capacity of 571 mAh/g. During lithiation, most conversion materials of fluoride and dichacodenide chemistries form a bi-continuous network of nano metal and lithium salt (i.e. LiF, Li 2 O, etc.). This has been shown in a number of high resolution transmission electron microscopy studies and supported in part by molecular dynamic modeling.9,10 Although such networks visually appear to be electronic percolating (Figure 1) and may be the pathway for electron transport to the reaction front, there has been no data to suggest what order of magnitude the conductivity of this percolated network is. The goal of the effort presented herein is to establish quantitatively the electronic c...

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Lithium–Iron Fluoride Battery with In Situ Surface Protection

Borodin

Zdyrko

et al. 2016

Adv Funct Materials

113

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Lithium-metal fl uoride (MF) batteries offer the highest theoretical energy density, exceeding that of the sulfur-lithium cells. However, conversion-type MF cathodes suffer from high resistance, small capacity utilization at room temperature, irreversible structural changes, and rapid capacity fading with cycling. In this study, the successful application of the approach to overcome such limitations and dramatically enhance electrochemical performance of Li-MF cells is reported. By using iron fl uoride (FeF 2 ) as an example, Li-MF cells capable of achieving near-theoretical capacity utilization are shown when MF is infi ltrated into the carbon mesopores. Most importantly, the ability of electrolytes based on the lithium bis(fl uorosulfonyl)imide (LiFSI) salt is presented to successfully prevent the cathode dissolution and leaching via in situ formation of a Li ion permeable protective surface layer. This layer forms as a result of electrolyte reduction/oxidation reactions during the fi rst cycle of the conversion reaction, thus minimizing the capacity losses during cycling. Postmortem analysis shows the absence of Li dendrites, which is important for safer use of Li metal anodes. As a result, Li-FeF 2 cells demonstrate over 1000 stable cycles. Quantum chemistry calculations and postmortem analysis provide insights into the mechanisms of the passivation layer formation and the performance boost.

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Formation, dynamics, and implication of solid electrolyte interphase in high voltage reversible conversion fluoride nanocomposites

Cited by 99 publications

References 24 publications

In situ surface protection for enhancing stability and performance of conversion-type cathodes

In situ surface protection for enhancing stability and performance of conversion-type cathodes

Electronic Transport in Lithiated Iron and Bismuth Fluoride

Lithium–Iron Fluoride Battery with In Situ Surface Protection

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