Substituted Dioxaphosphinane as an Electrolyte Additive for High Voltage Lithium-Ion Cells with Overlithiated Layered Oxide

Chernyshov, Denis V.; Krachkovskiy, Sergey A.; Kapylou, Andrei V.; Bolshakov, Ivan A.; Shin, Woo Cheol; Ue, Makoto

doi:10.1149/2.100404jes

Cited by 22 publications

(18 citation statements)

References 37 publications

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“…[18][19][20][21][22][23] Among additives tested, vinylene carbonate, 21,24,25 phosphites, [26][27][28][29] fluorinated carbonates, 30,31 and borates 20,32 have shown evidence of decomposition on various high voltage cathode surfaces through a variety of surface characterization techniques, including attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS).…”

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The Role of Additives in Improving Performance in High Voltage Lithium-Ion Batteries with Potentiostatic Holds

Tornheim

et al. 2017

J. Electrochem. Soc.

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In this work, various electrolyte additives designed for enhanced performance at high voltages were evaluated with elevated temperature potentiostatic holds with LiNi 0.5 Co 0.2 Mn 0.3 /Li 4 Ti 5 O 12 full cells to determine their effect on the high voltage stability. Of the additives investigated, many showed increased oxidation current through the 60 hour potentiostatic holds test, and adversely affected both the capacity retention and interfacial impedance. Improved high voltage performance was observed with two additives, vinylene carbonate (VC) and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), which was attributed to two different mechanisms of improvement. This work investigates some conclusions in the available literature of an additive molecule that decomposes on the charged cathode surface and passivates the surface against electrolyte oxidation. With the goal of increasing battery energy density for transportation applications, layered transition metal oxides cathodes of the form LiMO 2 (M = Ni, Co, Mn) have received significant attention.1-7 While these cathode materials have a high theoretical gravimetric capacity of ∼280 mAh/g, 8 achieving the high capacity of these materials requires very high charging voltages (>4.5V vs. Li + /Li), 2-4 above the stability range of conventional carbonate electrolytes.9,10 Enabling the additional high voltage capacity of the cathode materials requires new electrolytes that provide additional stability at high voltages at the charged cathode surface.The approach to creating compatible electrolytes has mainly fallen along two separate paths: either increasing the intrinsic anodic stability of the electrolyte, [11][12][13][14][15][16][17] or using a sacrificial component in small amounts (an additive) to "passivate" the cathode surface and inhibit continual electrolyte oxidation.18 20,32 have shown evidence of decomposition on various high voltage cathode surfaces through a variety of surface characterization techniques, including attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS).However, this cathode "passivation" is conventionally inferred through a combination of experimental results, such as increased capacity retention, voltammetric methods indicating a lower anodic stability attributed to additive oxidation, changes to the XPS and/or FTIR spectra of the cathode that include components of the additive, and decreased impedance after cycling. While the results provided by the previously mentioned characterization methods can be reconciled with the conclusion that cathode "passivation" led to the improvement, this mechanistic process can be more accurately evaluated by monitoring the electrolyte oxidation current at a charged cathode surface through potentiostatic holds. A passivation layer will limit electron transfer from the electrolyte to the charged cathode surface. By this definition, this layer must have both a minimal electron conductivity as well as a minimal diffusio...

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The Role of Additives in Improving Performance in High Voltage Lithium-Ion Batteries with Potentiostatic Holds

Tornheim

et al. 2017

J. Electrochem. Soc.

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“…·0.5LiNi 0.44 Co 0.24 Mn 0.32 O 2 ) 41. Cells with substituted dioxaphosphinane-containing electrolyte could potentially have relatively low interfacial impedance, improved cycling stability, and thermally stable Li-rich cathodes.…”

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Tunable and Robust Phosphite-Derived Surface Film to Protect Lithium-Rich Cathodes in Lithium-Ion Batteries

Han

Lee

et al. 2015

ACS Appl. Mater. Interfaces

125

104

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A thin, uniform, and highly stable protective layer tailored using tris(trimethylsilyl) phosphite (TMSP) with a high tendency to donate electrons is formed on the Li-rich layered cathode, Li1.17Ni0.17Mn0.5Co0.17O2. This approach inhibits severe electrolyte decomposition at high operating voltages during cycling and dramatically improves the interfacial stability of the cathode. The TMSP additive in the LiPF6-based electrolyte is found to preferentially eliminate HF, which promotes the dissolution of metal ions from the cathode. Our investigation revealed that the TMSP-derived surface layer can overcome the significant capacity fading of the Li-rich cathode by structural instability ascribed to an irreversible phase transformation from layered to spinel-like structures. Moreover, the superior rate capability of the Li-rich cathode is achieved because the TMSP-originated surface layer allows facile charge transport at high C rates for the lithiation process.

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“…For additives that reportedly passivated the surface, there are additional explanations as to the mechanism of improvement -including HF scavenging and prevention of metal ion dissolution, which would lead to better capacity retention. 17,18 Additionally, there are pursuits of intrinsically stable electrolytes that will experience a lower decomposition rate due to a lower thermodynamic or kinetic driving force for the oxidation reaction. This pursuit has led to a variety of fluorinated solvents that show improved performance in cycling tests.…”

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Evaluation of Electrolyte Oxidation Stability on Charged LiNi_0.5Co_0.2Mn_0.3O₂Cathode Surface through Potentiostatic Holds

Tornheim

Trask

Zhang

2016

J. Electrochem. Soc.

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The electrolyte oxidation rate was measured at 4.6 V vs. Li + /Li for a NCM/LTO full cell at temperatures ranging from room temperature to 55 • C. A large (∼2.5) N/P ratio was used in electrode fabrication to enable a stable reference in the Li 4 Ti 5 O 12 electrode for both cycling and the potentiostatic hold regimes. LTO was used to prevent electrolyte reduction from contributing to the signal, as well as providing a stable impedance. For the alkyl carbonate electrolyte used, oxidation rate at room temperature to 45 • C approximately ranged from 1-2 μA, as measured during the terminal 4.2 hours of a 60 hour potentiostatic hold. Many cells aged at 55 • C indicated increasing, unstable currents. Upon the completion of the hold, the cells were cycled to evaluate the effect of the hold and analyzed with AC impedance spectroscopy. Higher temperatures during the potentiostatic hold led to lower capacities during post-aging cycling, as well as higher impedance as measured with EIS.In an effort to increase the energy density of batteries, high-voltage cathodes (V > 4.5 vs. Li/Li + ) are being explored as alternatives to the stable 4-V lithium manganese oxide spinel chemistry, including high voltage spinels, 1-3 nickel-cobalt-manganese layered oxides, 4-6 and olivines. 7,8 As the conventional carbonate electrolytes are traditionally thought to be stable up to 4.5 V vs. Li/Li + , improved electrolytes (either through passivating additives or intrinsically stable electrolytes) will have to be implemented to enable the higher performance of the high-voltage cathodes. 9,10 In the field of electrolyte research, there are many publications that report improved cycling performance with the addition of small amounts of novel molecules designed to 'passivate' the surface and inhibit electrolyte oxidation. 11-16 While these results are promising, the interfacial parameters are poorly constrained in these experiments, making a fundamental understanding of electrolyte anodic stability difficult to characterize. For additives that reportedly passivated the surface, there are additional explanations as to the mechanism of improvement -including HF scavenging and prevention of metal ion dissolution, which would lead to better capacity retention. 17,18 Additionally, there are pursuits of intrinsically stable electrolytes that will experience a lower decomposition rate due to a lower thermodynamic or kinetic driving force for the oxidation reaction. This pursuit has led to a variety of fluorinated solvents that show improved performance in cycling tests. 19,20 In order to enable high voltage battery chemistries, a more stable electrolyte system is necessary, and the comparison of new electrolyte compositions against a baseline anodic stability is critical to improving the high voltage limits of electrolyte systems. In this work, potentiostatic holds are performed on full cells with a lithium titanate (Li 4 Ti 5 O 12 ) anode to shed some light on the reaction rate of the conventional carbonate-based electrolyte at the charged cathode sur...

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Substituted Dioxaphosphinane as an Electrolyte Additive for High Voltage Lithium-Ion Cells with Overlithiated Layered Oxide

Cited by 22 publications

References 37 publications

The Role of Additives in Improving Performance in High Voltage Lithium-Ion Batteries with Potentiostatic Holds

The Role of Additives in Improving Performance in High Voltage Lithium-Ion Batteries with Potentiostatic Holds

Tunable and Robust Phosphite-Derived Surface Film to Protect Lithium-Rich Cathodes in Lithium-Ion Batteries

Evaluation of Electrolyte Oxidation Stability on Charged LiNi_0.5Co_0.2Mn_0.3O₂Cathode Surface through Potentiostatic Holds

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Substituted Dioxaphosphinane as an Electrolyte Additive for High Voltage Lithium-Ion Cells with Overlithiated Layered Oxide

Cited by 22 publications

References 37 publications

The Role of Additives in Improving Performance in High Voltage Lithium-Ion Batteries with Potentiostatic Holds

The Role of Additives in Improving Performance in High Voltage Lithium-Ion Batteries with Potentiostatic Holds

Tunable and Robust Phosphite-Derived Surface Film to Protect Lithium-Rich Cathodes in Lithium-Ion Batteries

Evaluation of Electrolyte Oxidation Stability on Charged LiNi0.5Co0.2Mn0.3O2Cathode Surface through Potentiostatic Holds

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Evaluation of Electrolyte Oxidation Stability on Charged LiNi_0.5Co_0.2Mn_0.3O₂Cathode Surface through Potentiostatic Holds