• Journal of Electrochemical Science and Technology
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• v.12 no.1
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• pp.67-73
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• 2021

Nickel-rich lithium nickel-cobalt-manganese oxides (NCM) are viewed as promising cathode materials for lithium-ion batteries (LIBs); however, their poor cycling performance at high temperature is a critical hurdle preventing expansion of their applications. We propose the use of a functional electrolyte additive, triphenyl phosphate (TPPa), which can form an effective cathode-electrolyte interphase (CEI) layer on the surface of Ni-rich NCM cathode material by electrochemical reactions. Linear sweep voltammetry confirms that the TPPa additive is electrochemically oxidized at around 4.83 V (vs. Li/Li+) and it participates in the formation of a CEI layer on the surface of NCM811 cathode material. During high temperature cycling, TPPa greatly improves the cycling performance of NCM811 cathode material, as a cell cycled with TPPa-containing electrolyte exhibits a retention (133.7 mA h g-1) of 63.5%, while a cell cycled with standard electrolyte shows poor cycling retention (51.3%, 108.3 mA h g-1). Further systematic analyses on recovered NCM811 cathodes demonstrate the effectiveness of the TPPa-based CEI layer in the cell, as electrolyte decomposition is suppressed in the cell cycled with TPPa-containing electrolyte. This confirms that TPPa is effective at increasing the surface stability of NCM811 cathode material because the TPPa-initiated POx-based CEI layer prevents electrolyte decomposition in the cell even at high temperatures.

• Current Applied Physics
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• v.18 no.11
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• pp.1345-1351
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• 2018

To allow stable cycling of layered nickel-rich cathode material at high voltage, silyl-functionalized dimethoxydimethylsilane is proposed as a multi-functional additive. In contrast to typical functional additive, dimethoxydimethylsilane does not make artificial cathode-electrolyte interfaces by electrochemical oxidation because it is quite stable under anodic polarization. We find that dimethoxydimethylsilane mainly focuses on scavenging nucleophilic fluoride species that can be produced by electrolyte decomposition during cycling, leading to improving interfacial stability of both nickel-rich cathode and graphite anode. As a result, the cell cycled with dimethoxydimethylsilane-controlled electrolyte exhibits 65.7% of retention after 100 cycle, which is identified by systematic spectroscopic analyses for the cycled cell.

• Journal of Electrochemical Science and Technology
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• v.14 no.3
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• pp.272-282
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• 2023

Ni-rich layered oxides cathode has recently gained attention as an advanced cathode material due to their applicable energy density. However, as the Ni component in the layered site is increased, the high reactivity of Ni⁴⁺ results in parasitic reaction associated with decomposing electrolyte, which leads to a rapid decreasing the lifespan of the cell. The electrolyte additive triallyl borate (TAB) improves interfacial stability, leading to a stable cathode-electrolyte interphase (CEI) layer on the LNCM83 cathode. A multi-functionalized TAB additive can produce a uniformly distributed CEI layer via electrochemical oxidation, which implies an increase in long-term cycling performance. After 100 cycles at elevated temperature, the cell tested by 0.75 TAB retained 88.3% of its retention ratio, whereas the cell performed by TAB-free electrolyte retained 64.1% of its retention. Once the TAB additive formed CEI layers on the LNCM83 cathode, it inhibited the decomposition of carbonate-based solvents species in addition to the dissolution of transition metal components from the cathode. The addition of TAB to LNCM83 cathode material is believed to be a promising way to increase the electrochemical performance.

• Journal of Electrochemical Science and Technology
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• v.7 no.3
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• pp.214-217
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• 2016

In this study, we studied the enhancement of the energy densities of electrochemical capacitors by improving the working voltage range of the electrolyte. To prevent the decomposition of the electrolyte, stable SEI layers were formed by reductive degradation of additive materials such as fluoro-ethylene carbonate (FEC) and vinyl ethylene carbonate (VEC) before degradation of the base electrolyte. As a result, the solution resistance (R_s) of EC:DMC + SL 20 % + VEC 1 % electrolytes observed 1.47 Ω and the charge transfer resistance (R_ct) was 2.64 Ω at the open circuit voltage. Additionally, a cycle retention of 94 % was observed for EC:DMC + SL 20 % + VEC 1 % after 500 cycles at 3.5 V.

• Journal of the Korean Electrochemical Society
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• v.20 no.1
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• pp.13-17
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• 2017

In this study, we studied the organic electrolyte application to electrochemical capacitor for high operation voltage. For high operating voltage, 5 wt % of gamma butyroloctone (GBL) was added in the bare electrolyte. During the cycle performance, stable SEI layers were formed by reductive decomposition of additive GBL. As a result, columbic efficient of 1M $SBPBF_4$ in EC:DMC(1:1) with GBL composite was enhanced to 70% after the 2000th cycle at voltage range 0-3.5 V. Additionally, SEI layer protected the surface of electrode and prevent the side-reaction between electrolyte to electrode.

• Journal of the Korean Electrochemical Society
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• v.15 no.3
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• pp.190-197
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• 2012

We employed the vinyl ethylene carbonate (VEC) as an electrolyte additive and investigated the effect of the electrolyte additive on the electrochemical performance in hybrid capacitor. The activated carbon was adopted as cathode material, and the $Li_4Ti_5O_{12}$ oxide was used as anode material. The electrolyte was prepared with the $LiPF_6$ salt in the mixed solvent of ethylene carbonate (EC), dimethyl carbonate (DMC), and ethyl methyl carbonate(EMC). We evaluated the electrochemical performance of the hybrid capacitor with increasing the amount of the VEC electrolyte additive, which is known as the remover of oxygen functional group and the stabilizer of the electrode by reducing the surface of electrode, and obtained the superior performance data especially at the addition of the VEC electrolyte additive of around 0.7 vol%. On the contrary, the addition of the VEC more than 0.7 vol% in the electrolyte leads to the degradation in electrochemical performance of hybrid capacitor, suggesting the increase of the side reaction from the excessive VEC additive. X-ray photoelectron spectroscopy (XPS) revealed that the addition of the VEC suppressed the formation of LiF component, which is known as the insulator, on the surface of electrode. The optimized addition of VEC exhibited the improved capacity retention around 82.7% whereas the bare capacitors without VEC additive showed the 43.2% of capacity retention after 2500 cycling test.

• Carbon letters
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• v.15 no.3
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• pp.187-191
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• 2014

This study reports on the influence of N-butyl-N-methylpyrrolidinium tetrafluoroborate ($PYR_{14}BF_4$) ionic liquid additive on the conducting and interfacial properties of organic solvent based electrolytes against a carbon electrode. We used the mixture of ethylene carbonate/dimethoxyethane (1:1) as an organic solvent electrolyte and tetraethylammonium tetrafluoroborate ($TEABF_4$) as a common salt. Using the $PYR_{14}BF$ ionic liquid as additive produced higher ionic conductivity in the electrolyte and lower interface resistance between carbon and electrolyte, resulting in improved capacitance. The chemical and electrochemical stability of the electrolyte was measured by ionic conductivity meter and linear sweep voltammetry. The electrochemical analysis between electrolyte and carbon electrode was examined by cyclic voltammetry and electrochemical impedance spectroscopy.

• Bulletin of the Korean Chemical Society
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• v.32 no.1
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• pp.105-108
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• 2011

The cycling behavior of $Li_4Ti_5O_{12}$ electrode in the ionic liquid (IL)-based electrolytes containing 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide and a small amount of additive (vinylene carbonate, ethylene carbonate, fluoroethylene carbonate) was investigated. The $Li_4Ti_5O_{12}$ electrode in the IL electrolyte with an additive exhibited reversible cycling behavior with good capacity retention. Electrochemical impedance spectroscopy and FTIR studies revealed that an electrochemically stable solid electrolyte interphase was formed on the $Li_4Ti_5O_{12}$ electrode in the presence of vinylene carbonate and ethylene carbonate during cycling.

• Bulletin of the Korean Chemical Society
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• v.30 no.2
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• pp.319-322
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• 2009

Gel polymer electrolytes were prepared by immersing a porous poly(vinylidene fluoride-co-hexafluoropropylene) membrane in an electrolyte solution containing small amounts of polymerizable additive (3,4-ethylenedioxythiophene, thiophene, biphenyl). The organic additives were electrochemically oxidized to form conductive polymer films on the electrode at high potential. With the gel polymer electrolytes containing different organic additive, lithium-ion polymer cells composed of carbon anode and LiCo$O_2$ cathode were assembled and their cycling performances were evaluated. Adding small amounts of thiophene or 3,4-ethylenedioxythiophene to the gel polymer electrolyte was found to reduce the charge transfer resistance in the cell and it thus exhibited less capacity fading and better high rate performance.

• Journal of the Korean Electrochemical Society
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• v.17 no.3
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• pp.156-163
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• 2014

In this study, we tried to improve the cycling performance of lithium-ion batteries by suppressing decomposition of the electrolyte solution containing fluorsilane-based additive. Trifluoropropyltrimethoxysilane was electrochemically oxidized and reduced prior to the decomposition of the liquid electrolyte composed of lithium salt and carbonate-based organic solvent. Thus, the stable solid electrolyte interphase (SEI) layer on both negative electrode and positive electrode was formed, and it was confirmed that the cycling performance of lithium-ion batteries assembled with electrolyte solution containing 5 wt.% trifluoropropyltrimethoxysilane was the mostly enhanced. The products formed on electrodes were analyzed by the SEM and XPS analysis, and it was demonstrated that trifluoropropyltrimethoxysilane can be one of the promising SEI-forming additives.