Recent Progress in Research on High‐Voltage Electrolytes for Lithium‐Ion Batteries

Shi, Tan; Ji, Yi; Zhang, Zhong R.; Yang, Yong

doi:10.1002/cphc.201402175

Cited by 239 publications

(181 citation statements)

References 150 publications

Supporting

Mentioning

172

Contrasting

Unclassified

Order By: Relevance

“…SL is a by-product of the oil industry, thus cheap and produced by tons [24]. Its high potential of oxidation, as well as those of linear sulfones [25], above 5 V vs. Li/Li + has recently attracted interest as a high voltage electrolyte solvent [26].…”

Section: Introductionmentioning

confidence: 99%

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Zhang

Porcher

Paillard

2018

Journal of Power Sources

View full text Add to dashboard Cite

Abstract:Sulfolane (tetramethylene sulfone, SL) is known for leading to Li-ion electrolytes with high anodic stability. However, the operation of graphite electrodes in alternative electrolytes is usually challenging, especially when ethylene carbonate (EC) is not used as co-solvent. Thus, we study here the influence of the lithium salt on the physico-chemical and electrochemical properties of EC-free SL-based electrolytes and on the performance of graphite electrodes based on carboxymethyl cellulose (CMC). SL mixed with dimethyl carbonate (DMC) leads to electrolytes as conductive as state-of-theart alkyl carbonate-based electrolytes with wide electrochemical stability windows. The compatibility with graphite electrodes depends on the Li salt used and, even though cycling is possible with most salts, lithium difluoro-oxalato borate (LiDFOB) is especially interesting for graphite operation.LiDFOB electrolytes are conductive at room temperature (ca. 6 mS cm -1 ) with an anodic stability slightly below 5 V vs. Li/Li + on particulate carbon black electrodes. In addition, it allows cycling graphite electrodes with steady capacity and high coulombic efficiency without any additive. The testing of graphite electrodes in half-cells is, however, problematic with SL:DMC mixtures and, by switching the Li metal counter electrode for LiFePO4, the graphite electrode achieves better practical performance in terms of rate capability.

show abstract

Section: Introductionmentioning

confidence: 99%

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Zhang

Porcher

Paillard

2018

Journal of Power Sources

View full text Add to dashboard Cite

show abstract

“…Future LIBs/SIBs, however, will require novel electrolytes displaying i) wider electrochemical stability windows to allow cycling of high energy capacity cathodes and especially at higher voltages e.g. up to 5 V vs. Li + /Li° [11], ii) compatibility with these and other new electrode chemistries [5], iii) better thermal stability to withstand wider operational temperatures [12], and iv) surface and bulk structures and dynamics that allow for faster charge/discharge, i.e., cation desolvation and solvation [13].…”

Section: Introductionmentioning

confidence: 99%

Solvation structure in dilute to highly concentrated electrolytes for lithium-ion and sodium-ion batteries

Flores

Åvall

Jeschke

et al. 2017

Electrochimica Acta

View full text Add to dashboard Cite

The solvation structure of several lithium and sodium based electrolytes are explored as a function of salt concentration over a wide range via a detailed PM7 computational study.The cation coordination shells are found to be well-defined and solvent rich for dilute electrolytes, while disordered and anion rich for the more concentrated electrolytes. The Nabased electrolytes display larger cation coordination shells with a more pronounced presence of fluorine as compared to the Li-based electrolytes. The origins of the structural differences are discussed as well as their consequences for properties of battery electrolytes and battery usage -especially targeting the current large interest in highly concentrated electrolytes.

show abstract

“…[18][19][20] The usefulness of P-based additives for HV applications has been recently reported. 11,21,22 2 ], also referred to as LiBFEP; see E in Scheme 1) has been used as a coordinationpolymer-based gel electrolyte in our recent work. 32 LiBFEP forms a viscous gel in EC/DMC (1/1 g:g) at 0.5 M with a rather low conductivity of 41.8 μS·cm −1 at room temperature.…”

mentioning

confidence: 99%

Lithium Bis(2,2,2-trifluoroethyl)phosphate Li[O₂P(OCH₂CF₃)₂]: A High Voltage Additive for LNMO/Graphite Cells

Milien

Beyer

Beichel

et al. 2018

J. Electrochem. Soc.

View full text Add to dashboard Cite

The fluorinated phosphate lithium bis (2,2,2-trifluoroethyl) phosphate (LiBFEP) has been investigated as a film-forming additive employed to passivate the cathode and hinder continuous oxidation of the electrolyte. Cyclic voltammetry (CV) and linear sweep voltammetry coupled with online electrochemical mass spectrometry (LSV-OEMS) on a conductive carbon electrode (i.e., a C65/PVDF composite) showed that LiBFEP decreases electrolyte oxidation (CV and LSV) and LiPF 6 decomposition at high potentials. Incorporation of LiBFEP (0.1 and 0.5 wt%) into LiPF 6 in ethylene carbonate (EC)/ethyl methyl carbonate (EMC) (3:7 wt) results in improved coulombic efficiency and capacity retention for LNMO/graphite cells. Ex-situ surface analysis of the electrodes suggests that incorporation of LiBFEP results in the formation of a cathode electrolyte interface (CEI) and modification of the solid electrolyte interface (SEI) on the anode. The formation of the CEI mitigates electrolyte oxidation and prevents the decomposition of LiPF 6 , which in turn prevents HF-induced manganese dissolution from the cathode and destabilization of the SEI. The passivation of the cathode and stabilization of the SEI is responsible for the increased coulombic efficiency and capacity retention. Since their debut in 1991, lithium ion batteries (LIB) have become the universal power source for consumer electronics.1 Larger format LIBs such as those needed to power electric vehicles (EVs), an important future market, have amassed considerable interest; however higher specific energy densities are required for larger format LIBs.1,2 The practical way to increase energy density is to employ cathode materials with increased theoretical capacities and/or high discharge plateaus, and thus high energy (HE) or high voltage (HV) cathodes are required in order for LIBs to meet the demands of the EV market.3 While both HE and HV cathodes have been implemented, current research efforts are focused on overcoming the caveats associated with these materials. The oxidative instability of carbonate-based electrolytes is a central limitation for cells with various cathode chemistries operated above 4.4 V. [3][4][5][6][7] In addition to the instability of the electrolyte, cathodes such as nickel-rich layered oxides (LiNi x Mn y Co z O 2 ), lithium-rich layered oxides (0.6 Li 2 MnO 3 • 0.4 Li(Ni 1/3 Co 1/3 Mn 1/3 )O 2 ), and HV spinel (LiNi 0.5 Mn 1.5 O 4 ) (LNMO) all suffer from structural instability when operated at high potentials.5-11 While the layered oxides are capable of delivering higher practical energy densities, the lack of cobalt in LNMO alleviates the issues of cost and resource limitations.7 As the higher energy densities associated with HE materials can only be obtained at higher cutoff potentials, oxidation of the electrolyte is a universal problem to both HE and HV cathodes. This work focuses on improving the performance of LNMO/Graphite cells.The capacity fading observed in LNMO/Graphite cells is due to continuous oxidation of the electrolyte and transition...

show abstract

Recent Progress in Research on High‐Voltage Electrolytes for Lithium‐Ion Batteries

Cited by 239 publications

References 150 publications

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Solvation structure in dilute to highly concentrated electrolytes for lithium-ion and sodium-ion batteries

Lithium Bis(2,2,2-trifluoroethyl)phosphate Li[O₂P(OCH₂CF₃)₂]: A High Voltage Additive for LNMO/Graphite Cells

Contact Info

Product

Resources

About

Recent Progress in Research on High‐Voltage Electrolytes for Lithium‐Ion Batteries

Cited by 239 publications

References 150 publications

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Towards practical sulfolane based electrolytes: Choice of Li salt for graphite electrode operation

Solvation structure in dilute to highly concentrated electrolytes for lithium-ion and sodium-ion batteries

Lithium Bis(2,2,2-trifluoroethyl)phosphate Li[O2P(OCH2CF3)2]: A High Voltage Additive for LNMO/Graphite Cells

Contact Info

Product

Resources

About

Lithium Bis(2,2,2-trifluoroethyl)phosphate Li[O₂P(OCH₂CF₃)₂]: A High Voltage Additive for LNMO/Graphite Cells