Ab initio study of the operating mechanisms of tris(trimethylsilyl) phosphite as a multifunctional additive for Li-ion batteries

Dong Young Kim; Hosang Park; Woon Ih Choi; Basab Roy; Jinah Seo; Insun Park; Jin Hae Kim; Jong Hwan Park; Yoon Sok Kang; Meiten Koh

doi:10.1016/j.jpowsour.2017.04.062

Ab initio study of the operating mechanisms of tris(trimethylsilyl) phosphite as a multifunctional additive for Li-ion batteries

Dong Young Kim, Hosang Park, Woon Ih Choi, Basab Roy, Jinah Seo, Insun Park, Jin Hae Kim, Jong Hwan Park, Yoon Sok Kang, Meiten Koh

Department of New Biology

Samsung

Research output: Contribution to journal › Article › peer-review

25 Scopus citations

Abstract

Tris(trimethylsilyl) phosphite (P(OSi(CH₃)₃)₃) is a multifunctional electrolyte additive for scavenging HF and forming a cathode electrolyte interphase (CEI). Systematic analysis of the HF reaction pathways and redox potentials of P(OSi(CH₃)₃)₃, OP(OSi(CH₃)₃)₃, P(OSiF₃)₃, and OP(OSiF₃)₃, and their reaction products, using ab initio calculations allowed us to elucidate the operating mechanism of P(OSi(CH₃)₃)₃ and verify the rules that determine its HF reaction pathways and electrochemical stability. While O[sbnd]Si cleavage is the predominant HF scavenging pathway for P(OSi(CH₃)₃)₃, O[sbnd]P cleavage is stabilized by replacing CH₃ with an electron-withdrawing group. Thus, P(OSiF₃)₃ scavenges HF mainly through O[sbnd]P cleavage to produce PF₃, which has high oxidation stability. However, the O[sbnd]Si cleavage pathway produces P(OSi(CH₃)₃)₂OH, P(OSi(CH₃)₃) (OH)₂, and P(OH)₃ sequentially, along with Si(CH₃)₃F. These PO₃ systems, which are oxidized earlier than carbonate solutions and form tightly bonded units following oxidation, act as seed units for compact CEI growth. Moreover, the HF scavenging ability of PO₃ systems is maintained during oxidation until all O[sbnd]Si bonds are broken. As a strategy for developing additives with enhanced functionality, modifying P(OSi(CH₃)₃)₃ by replacing CH₃ with an electron-donating group to exclusively utilize the O[sbnd]Si cleavage pathway for HF scavenging is recommended.

Original language	English
Pages (from-to)	154-163
Number of pages	10
Journal	Journal of Power Sources
Volume	355
DOIs	https://doi.org/10.1016/j.jpowsour.2017.04.062
State	Published - 2017

Bibliographical note

Publisher Copyright:
© 2017 Elsevier B.V.

Keywords

Additive
Electrolyte
HF
Mechanism
Phosphite
Solid electrolyte interphase

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

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10.1016/j.jpowsour.2017.04.062

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@article{00364ba5aa134658b55c627778893c7c,

title = "Ab initio study of the operating mechanisms of tris(trimethylsilyl) phosphite as a multifunctional additive for Li-ion batteries",

abstract = "Tris(trimethylsilyl) phosphite (P(OSi(CH3)3)3) is a multifunctional electrolyte additive for scavenging HF and forming a cathode electrolyte interphase (CEI). Systematic analysis of the HF reaction pathways and redox potentials of P(OSi(CH3)3)3, OP(OSi(CH3)3)3, P(OSiF3)3, and OP(OSiF3)3, and their reaction products, using ab initio calculations allowed us to elucidate the operating mechanism of P(OSi(CH3)3)3 and verify the rules that determine its HF reaction pathways and electrochemical stability. While O[sbnd]Si cleavage is the predominant HF scavenging pathway for P(OSi(CH3)3)3, O[sbnd]P cleavage is stabilized by replacing CH3 with an electron-withdrawing group. Thus, P(OSiF3)3 scavenges HF mainly through O[sbnd]P cleavage to produce PF3, which has high oxidation stability. However, the O[sbnd]Si cleavage pathway produces P(OSi(CH3)3)2OH, P(OSi(CH3)3) (OH)2, and P(OH)3 sequentially, along with Si(CH3)3F. These PO3 systems, which are oxidized earlier than carbonate solutions and form tightly bonded units following oxidation, act as seed units for compact CEI growth. Moreover, the HF scavenging ability of PO3 systems is maintained during oxidation until all O[sbnd]Si bonds are broken. As a strategy for developing additives with enhanced functionality, modifying P(OSi(CH3)3)3 by replacing CH3 with an electron-donating group to exclusively utilize the O[sbnd]Si cleavage pathway for HF scavenging is recommended.",

keywords = "Additive, Electrolyte, HF, Mechanism, Phosphite, Solid electrolyte interphase",

author = "Kim, {Dong Young} and Hosang Park and Choi, {Woon Ih} and Basab Roy and Jinah Seo and Insun Park and Kim, {Jin Hae} and Park, {Jong Hwan} and Kang, {Yoon Sok} and Meiten Koh",

note = "Publisher Copyright: {\textcopyright} 2017 Elsevier B.V.",

year = "2017",

doi = "10.1016/j.jpowsour.2017.04.062",

language = "English",

volume = "355",

pages = "154--163",

journal = "Journal of Power Sources",

issn = "0378-7753",

publisher = "Elsevier B.V.",

}

TY - JOUR

T1 - Ab initio study of the operating mechanisms of tris(trimethylsilyl) phosphite as a multifunctional additive for Li-ion batteries

AU - Kim, Dong Young

AU - Park, Hosang

AU - Choi, Woon Ih

AU - Roy, Basab

AU - Seo, Jinah

AU - Park, Insun

AU - Kim, Jin Hae

AU - Park, Jong Hwan

AU - Kang, Yoon Sok

AU - Koh, Meiten

PY - 2017

Y1 - 2017

N2 - Tris(trimethylsilyl) phosphite (P(OSi(CH3)3)3) is a multifunctional electrolyte additive for scavenging HF and forming a cathode electrolyte interphase (CEI). Systematic analysis of the HF reaction pathways and redox potentials of P(OSi(CH3)3)3, OP(OSi(CH3)3)3, P(OSiF3)3, and OP(OSiF3)3, and their reaction products, using ab initio calculations allowed us to elucidate the operating mechanism of P(OSi(CH3)3)3 and verify the rules that determine its HF reaction pathways and electrochemical stability. While O[sbnd]Si cleavage is the predominant HF scavenging pathway for P(OSi(CH3)3)3, O[sbnd]P cleavage is stabilized by replacing CH3 with an electron-withdrawing group. Thus, P(OSiF3)3 scavenges HF mainly through O[sbnd]P cleavage to produce PF3, which has high oxidation stability. However, the O[sbnd]Si cleavage pathway produces P(OSi(CH3)3)2OH, P(OSi(CH3)3) (OH)2, and P(OH)3 sequentially, along with Si(CH3)3F. These PO3 systems, which are oxidized earlier than carbonate solutions and form tightly bonded units following oxidation, act as seed units for compact CEI growth. Moreover, the HF scavenging ability of PO3 systems is maintained during oxidation until all O[sbnd]Si bonds are broken. As a strategy for developing additives with enhanced functionality, modifying P(OSi(CH3)3)3 by replacing CH3 with an electron-donating group to exclusively utilize the O[sbnd]Si cleavage pathway for HF scavenging is recommended.

AB - Tris(trimethylsilyl) phosphite (P(OSi(CH3)3)3) is a multifunctional electrolyte additive for scavenging HF and forming a cathode electrolyte interphase (CEI). Systematic analysis of the HF reaction pathways and redox potentials of P(OSi(CH3)3)3, OP(OSi(CH3)3)3, P(OSiF3)3, and OP(OSiF3)3, and their reaction products, using ab initio calculations allowed us to elucidate the operating mechanism of P(OSi(CH3)3)3 and verify the rules that determine its HF reaction pathways and electrochemical stability. While O[sbnd]Si cleavage is the predominant HF scavenging pathway for P(OSi(CH3)3)3, O[sbnd]P cleavage is stabilized by replacing CH3 with an electron-withdrawing group. Thus, P(OSiF3)3 scavenges HF mainly through O[sbnd]P cleavage to produce PF3, which has high oxidation stability. However, the O[sbnd]Si cleavage pathway produces P(OSi(CH3)3)2OH, P(OSi(CH3)3) (OH)2, and P(OH)3 sequentially, along with Si(CH3)3F. These PO3 systems, which are oxidized earlier than carbonate solutions and form tightly bonded units following oxidation, act as seed units for compact CEI growth. Moreover, the HF scavenging ability of PO3 systems is maintained during oxidation until all O[sbnd]Si bonds are broken. As a strategy for developing additives with enhanced functionality, modifying P(OSi(CH3)3)3 by replacing CH3 with an electron-donating group to exclusively utilize the O[sbnd]Si cleavage pathway for HF scavenging is recommended.

KW - Additive

KW - Electrolyte

KW - HF

KW - Mechanism

KW - Phosphite

KW - Solid electrolyte interphase

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U2 - 10.1016/j.jpowsour.2017.04.062

DO - 10.1016/j.jpowsour.2017.04.062

M3 - Article

AN - SCOPUS:85018496779

SN - 0378-7753

VL - 355

SP - 154

EP - 163

JO - Journal of Power Sources

JF - Journal of Power Sources

ER -

Ab initio study of the operating mechanisms of tris(trimethylsilyl) phosphite as a multifunctional additive for Li-ion batteries

Abstract

Bibliographical note

Keywords

UN SDGs

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