New low temperature electrolytes with thermal runaway inhibition for lithium-ion rechargeable batteries

Mandal, Braja K.; Padhi, A. K.; Zhong, Shengwen; Chakraborty, Sudipto; Filler, Robert

doi:10.1016/j.jpowsour.2006.06.053

Cited by 68 publications

(58 citation statements)

References 4 publications

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“…[50][51][52] To standardize the measurement, 70 µL electrolyte was used in each coin cell. The electrolyte used was 1 m LiTFSI in cosolvent of DOL and DME (volume ratio: 1:1) with 1% LiNO 3 as electrolyte solution.…”

Section: Methodsmentioning

confidence: 99%

N‐Doped Graphene Modified 3D Porous Cu Current Collector toward Microscale Homogeneous Li Deposition for Li Metal Anodes

Zhang

Wen

Wang

et al. 2018

Advanced Energy Materials

170

105

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standard hydrogen electrode). [6][7][8][9][10] Unfortunately, the uneven plating/stripping of Li metal causes uncontrolled Li dendrite growth, which induces a series of problems. First, the continuous growth of Li dendrites may puncture the separator and cause short circuit, consequently resulting in serious safety issues. [11][12][13][14] Second, Li dendrite growth can consume electrolyte and dendritic Li may lose its electronic contact with electrode (called "dead Li") during Li stripping process, accordingly reducing the Coulombic efficiency (CE) and leading to capacity fading. [15][16][17] In addition, different from the other anode materials, the relative volume change of Li metal anodes is infinite due to its "hostless" nature, leading to internal pressure changes and interfacial fluctuations. The solid electrolyte interface (SEI) layer on the surface of the electrodes, which may not accommodate the volume change, will be repeatedly break and form during continuous cycling. [18][19][20] Moreover, the broken SEI will greatly exacerbate the uneven Li electrodeposits nucleate and accelerate the growth of Li dendrites. [21,22] These severe problems impede the practical applications of Li metal anodes and the approach to solve these multifaceted problems would be imperative.To tackle these critical issues, tremendous efforts have been taken to improve the stability of Li metal anodes and the SEI from different perspectives. In order to stabilize the SEI layer, various electrolyte additives, such as Cs + and Rb + ions, LiF, Li 2 S 8 , and LiNO 3 , were used. [23][24][25] Introducing nanoscale interfacial layers has also been intensively investigated (such as interconnected carbon nanospheres [26] and hexagonal boron nitride [27] ), where repeated deposition/stripping of Li under the layers exhibited stable CE. However, the above-mentioned methods based on Li foil (2D Li metal anodes) could not effectually prevent the huge volume change upon stripping/plating of Li metal. Thus, the internal pressure changes and interfacial fluctuations still happened during cycling. [28] To solve this problem, the 3D porous current collectors were used as host structures for Li metal in recent studies, such as 3D porous copper current collectors, [29][30][31][32][33] 3D nickel foam host, [34] and graphene [35,36] electrode. As a major part of Li metal batteries, the current collector has direct influence Lithium metal is the most promising anode material for high-energy-density batteries due to its high specific capacity of 3860 mAh g −1 and low reduction potential of −3.04 V versus standard hydrogen electrode. However, huge volume change, safety concerns, and low efficiency impede the practical applications of Li metal anodes. Herein, it is shown that the nitrogen-doped graphene modified 3D porous Cu (3DCu@NG) current collector can mitigate the above problems. The N-doped graphene, coating on the surface of 3D current collector, not only contributes to a uniform Li + flux, but also leads to a scattered distribution of electrons t...

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Section: Methodsmentioning

confidence: 99%

N‐Doped Graphene Modified 3D Porous Cu Current Collector toward Microscale Homogeneous Li Deposition for Li Metal Anodes

Zhang

Wen

Wang

et al. 2018

Advanced Energy Materials

170

105

View full text Add to dashboard Cite

show abstract

“…In the conventional electrolyte, EC is essential to forming solid electrolyte interphase (SEI) film. But a high EC content is problematic when the temperature is lowered below 0°C because the low temperature solidification of EC can lead to a sharp reduction in electrolyte conductivity [18,19]. In the present work, the proportion of EC is lessened to avoid the electrolyte solidification in low temperature; simultaneously, ethyl methyl carbonate (EMC) and propylene carbonate (PC) are used as cosolvents with EC to reinforce electrolyte conductivity at low temperature.…”

Section: Introductionmentioning

confidence: 96%

Enhanced electrochemical performance of LiFePO4 cathode with the addition of fluoroethylene carbonate in electrolyte

Ren

et al. 2012

J Solid State Electrochem

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The effect of the fluoroethylene carbonate (FEC) addition in electrolyte on LiFePO 4 cathode performance was investigated in low-temperature electrolyte LiPF 6 /EC/PC/EMC (0.14/0.18/0.68). Cyclic voltammetry, electrochemical impedance spectroscopy, and charge/discharge tests were conducted in this work. In the presence of FEC, the polarization of LiFePO 4 electrode decreased both at room and low temperatures. Meanwhile, the exchange current density increased. The rate capability of LiFePO 4 electrode was greatly enhanced as well. The morphology of the solid electrolyte interphase (SEI) on LiFePO 4 surface was modified with the addition of FEC as confirmed by scanning electron microscopy measurement. A compact film with small impedance was formed on LiFePO 4 surface compared to the case of FEC-free. The compositions of the film were analyzed by X-ray photoelectron spectroscopic measurement. The contents of Li x PO y F z , LiF, and the carbonate species generated from solvents decomposition were reduced.The modified SEI promoted the migration of lithium ion through the electrode/electrolyte interphase and enhanced the electrochemical performance of the cathode.

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“…3 Thus, when exploring organic carbonates for low temperature applications, the approach of decreasing the EC content and utilizing linear esters as the major solvent components was taken to lower the freezing point as well as the viscosity of the electrolyte. 3 Linear aliphatic carbonates (DMC, EMC, and DEC) have been demonstrated to be well-suited as co-solvents due to their low reactivity. However, it was still crucial for the electrolyte to provide favorable chemistries for the formation of stable electrode/electrolyte interphases and reasonably facile charge transfer kinetics.…”

mentioning

confidence: 99%

“…The EC content was reduced but not eliminated because it was necessary for the formation of a stable electrode/electrolyte interphase. 8 As opposed to making ternary 3,4,9 or quaternary blends 7 of organic carbonates, we sought to use EMC as the principal solvent in the electrolyte. 5 Regarding the charge transfer process, lithium tetrafluoroborate (LiBF 4 ) was measured to have a lower activation energy than LiPF 6 at −20 • C. 6 The charge transfer resistance of lithium bis(trifluoromethylsulfonyl)imide (LiTFSI) was also lower relative to LiPF 6 .…”

mentioning

confidence: 99%

High Concentration Dinitrile, 3-Alkoxypropionitrile, and Linear Carbonate Electrolytes Enabled by Vinylene and Monofluoroethylene Carbonate Additives

Gmitter¹,

Plitz²,

Amatucci³

2012

J. Electrochem. Soc.

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Li-ion batteries intended to operate over extremes in temperature or at cell voltages approaching 5 V exceed the fundamental capabilities of the electrolytes presently available. The most promising solvents that do meet the fundamental requirements exhibit exceptional instability at the low potentials found with negative electrodes of Li-ion batteries today. Herein, nitrile and linear carbonate electrolytes were stabilized with only the use of a small percentage of additives to enable formulations that may be of use for low temperature and high voltage operating conditions, respectively. In this work, the electrochemical characteristics of Li-ion cells were explored for a variety of electrolytes, with promising performance identified in systems composed predominantly of ethyl methyl carbonate (EMC), 3-methoxypropionitrile (3MPN), or adiponitrile (ADN). Vinylene carbonate (VC) and monofluoroethylene carbonate (FEC) were added in low concentrations (≤5 vol%) to stabilize the interface of the carbon negative electrode and the electrolyte, with FEC proving to be effective across all electrolytes examined herein. The fluoride decomposition products of FEC contributing to the SEI have been identified for the first time without the presence of lithium hexafluorophosphate (LiPF6) in the electrolyte, thereby leading to a clearer explanation of its exceptional protective effect within the SEI.

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New low temperature electrolytes with thermal runaway inhibition for lithium-ion rechargeable batteries

Cited by 68 publications

References 4 publications

N‐Doped Graphene Modified 3D Porous Cu Current Collector toward Microscale Homogeneous Li Deposition for Li Metal Anodes

N‐Doped Graphene Modified 3D Porous Cu Current Collector toward Microscale Homogeneous Li Deposition for Li Metal Anodes

Enhanced electrochemical performance of LiFePO4 cathode with the addition of fluoroethylene carbonate in electrolyte

High Concentration Dinitrile, 3-Alkoxypropionitrile, and Linear Carbonate Electrolytes Enabled by Vinylene and Monofluoroethylene Carbonate Additives

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