Focus Review

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Electrolyte-Additive-Driven Interfacial
Engineering for High-Capacity Electrodes in
Lithium-Ion Batteries: Promise and Challenges
Koeun Kim,† Hyunsoo Ma,† Sewon Park,† and Nam-Soon Choi*
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sı Supporting Information

ABSTRACT: Electrolyte additives have been explored to attain significant

breakthroughs in the long-term cycling performance of lithium-ion batteries
(LIBs) without sacrificing energy density; this has been achieved through the
development of stable electrode interfacial structures and the elimination of
reactive substances. Here we highlight the potential and the challenges
raised by studies on electrolyte additives toward addressing the interfacially
induced deterioration of high-capacity electrodes with a focus on Ni-rich
layered oxides and Si, which are expected to satisfy the growing demands for
high-energy-density batteries. We also discuss issues with the design of
electrolyte additives for practical viability. A deep understanding of the roles
of existing electrolyte additives depending on their functional groups will aid
in the design of functional additive moieties capable of building robust
interfacial layers, scavenging undesired reactive species, and suppressing the
gas generation that causes safety hazards and shortened lifetimes of LIBs.

L ithium-ion batteries (LIBs) are considered the most

effective energy storage systems for portable electronics
in light of their favorable energy density and lifetime.
Power sources for electric vehicles and smart grids require
long-lasting batteries with high energy densities, reliable safety
instabilities such as microcracking and cation mixing, safety
concerns arising from a low thermal stability, and undesired
oxidative decomposition of electrolytes induced by highly
oxidized Ni4+.8,9 Si is a key anode material for improving the
energy density of batteries, as the high theoretical capacity of
performance, and competitive prices.1−4 With the advance- Li15Si4 surpasses that of carbonaceous anodes (3579 vs 372
ment of electrode materials, significant breakthroughs have mAh g−1 for LiC6).10,11 However, the incorporation of Si as a
been made with electrolyte additives to address the issues with major component into LIBs is restricted by the large Si volume
existing electrolytes that lead to poor cycling performance and changes that cause irrevocable damage to Si−electrolyte
undesired gas generation. The energy density of LIBs depends interfaces and extreme spatial rearrangement of Si anode
strongly on the operating voltage and capacity of the cathode particles leading to loss of electrical connection.12−14 In
and anode materials. However, although high-energy-density addition, the use of highly reactive electrodes and harsh battery
LIBs can be realized with the use of high-capacity electrode operating conditions such as high temperatures and voltages
materials and a high operating voltage, reversible battery exacerbates the gas generation problem in batteries.15,16 In
operation requires long-term electrode−electrolyte interfacial particular, Ni-rich cathodes produce reactive oxygen species
stability. Building electrochemically robust interfacial layers because of their structural instability, which leads to the
and preserving the interfacial structures of electrodes for high- decomposition of electrolyte components and the subsequent
performance LIBs using electrolyte additives will contribute to evolution of gas.17,18 The residual lithium compound Li2CO3
on Ni-rich cathodes produces CO2 gas via both electro-
achieving electrochemical reversibility in high-capacity electro-
des.
Ni-rich layered oxides (LiNixCoyMnzO2 or LiNixCoyAlzO2, x Received: February 28, 2020
+ y + z = 1, x ≥ 0.6) have received great interest as promising Accepted: April 7, 2020
cathode materials because they can deliver high reversible Published: April 7, 2020
capacities of >180 mAh g−1.5−7 However, Ni-rich cathodes
have certain critical problems, including the inclusion of
residual lithium compounds (Li2CO3 and LiOH), structural

© 2020 American Chemical Society https://dx.doi.org/10.1021/acsenergylett.0c00468

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chemical (2Li2CO3 → 4Li+ + 2CO2 + 3e− + O2•−) and advances that have been made with regard to electrolyte
chemical (Li2 CO 3 + 2HF → 2LiF + H 2 O + CO 2 ) additives, which have thus far been employed to overcome the
reactions.19,20 When the operating voltage exceeds the voltage degradation in battery performance that is induced by
limit of a conventional electrolyte, oxidative decomposition of instability at the electrode−electrolyte interface. Furthermore,
the carbonate electrolyte solvents occurs, leading to CO and we provide an in-depth discussion of the issues pertaining to
CO2 gas generation.21,22 High temperatures cause large gas generation that significantly affect battery performance as
amounts of HF to form in cells with LiPF6-based electrolytes, well as the use of electrolyte additives as an effective solution.
which impairs organic-based interfacial layers and causes the Understanding the interrelation between functional groups of
chemical decomposition of the electrolyte solvents, again electrolyte additives and their outcomes will lead to a variety of
producing gaseous species.23,24 Interfacial engineering using advantages, namely, stabilization of the Ni-rich cathode
electrolyte additives can enable high-performance LIBs without interface, mitigation of the interfacial deterioration induced
sacrificing energy density. by large volume changes in Si anodes during battery operation,
and alleviation of unwanted gas generation.
Interfacial engineering using electro- Incorporation of Electrolyte Additives for Interfacial Stability of
lyte additives can enable high-per- Ni-rich Cathodes. Interfacial Instabilities of Ni-rich Cathodes. Ni-
rich layered oxides such as LiNixCoyMnzO2 (x + y + z = 1, x ≥
formance LIBs without sacrificing en- 0.6, NCM) and LiNi1−a−bCoaAlbO2 (NCA) have been
ergy density. highlighted as high-capacity cathode materials for high-
energy-density LIBs.25−29 However, increasing the Ni content
In this Focus Review, we present the critical issues of high- of Ni-rich cathodes is hindered by several critical challenges:
capacity electrode materials with a focus on Ni-rich cathodes the inclusion of residual lithium compounds (LiOH and
and Si-based anodes, which have been demonstrated to have Li2CO3);19,30−34 the high reduction tendency of high-valence
significant advantages for manufacturing high-energy-density Ni4+ ions to lower oxidation states, which incites transition-
LIBs. Furthermore, this Focus Review highlights the recent metal (TM) dissolution;35−38 cation mixing of Ni2+ (r = 0.069

Figure 1. Critical issues of Ni-rich cathodes: (a) Residual lithium. Reproduced with permission from ref 43. Copyright 2013 Elsevier. (b) HF
formation and transmission metal (TM) dissolution. (c) Thermal instability. Reproduced with permission from ref 43. Copyright 2013
Elsevier. (d) Surface phase transition and (e) microcracking. Possible solutions from the viewpoint of an electrolyte with additives capable of
forming a cathode−electrolyte interface (CEI) and scavenging HF: (f) suppression of surface phase transition, (g) inhibition of
microcracking, and (h) elimination of HF and suppression of TM dissolution.

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nm) and Li+ (r = 0.076 nm), which results in Li/Ni site TM dissolution and damage to the interfacial structure of Ni-
exchange and capacity loss;39,40 and the thermal instability of rich cathodes. Representative structures of electrolyte additives
delithiated Ni-rich cathodes, which causes increased safety acting as HF scavengers contain isocyanate groups (NC
concerns (Figure 1a−d).41 High-valence Ni4+ ions formed in a O),49 silane derivatives (Si−O),53,54,66 and phosphonites
fully delithiated state are easily reduced to Ni3+ and Ni2+ ions, (P(OR)2R)60 (Figure 2a). These structures actively react
which deprives the contacting electrolyte of electrons and with fluorine sources such as HF and PF5 or the proton from
results in the accumulation of resistive byproducts from HF. p-Toluenesulfonyl isocyanate (PTSI) forms a CEI through
electrolyte decomposition on the cathode particles (Figure the radical polymerization of the NCO group on the
1d). Functional additives are a promising strategy to address LiNi0.5Co0.2Mn0.3O2 (NCM523) cathode surface and captures
the undesirable reduction of Ni4+ to Ni2+ ions with oxygen loss, trace amounts of water and HF in the electrolyte (Figure
which leads to a decreased Li storage capability and structural 2b).49 The SO group of PTSI as a weak base site
nonstoichiometry of Ni-rich cathodes arising from cation coordinates with Lewis acid PF5, alleviating HF generation.
mixing. Furthermore, inhomogeneous lithiation and delithia- Another type of HF scavenger, diphenyldimethoxysilane
tion of Ni-rich secondary particles lead to anisotropic volume (DPDMS), has the multifunctional capability of forming a
changes, which induce microcracking and continued electro- CEI and eliminating HF, as depicted in Figure 2b. Si−O
lyte decomposition at the newly exposed cathode surface species observed from Si 2p X-ray photoelectron spectroscopy
(Figure 1e).44−46 The use of additives to build a uniform analysis of the cycled cathode indicate that DPDMS
participates in CEI formation, and the appearance of the Si−
The use of additives to build a uniform F species shows that DPDMS is conducive to scavenging HF.66
Dimethoxydimethylsilane (DODSi), which selectively scav-
cathode−electrolyte interface (CEI) and enges HF through SN2 substitution by F− and readily loses
to scavenge the reactive HF and PF5 electrons, suppresses the TM dissolution of NCM811 cathodes
species has been considered to main- and forms a thin, uniform CEI.53,54
tain the stable electrochemical per- The ability of DODSi to scavenge HF was confirmed by the
reaction between DODSi and tetra-butylammonium fluoride as
formance of Ni-rich cathodes in lithium a fluorine source. 1H nuclear magnetic resonance (NMR)
hexafluorophosphate (LiPF6)-based revealed that the peaks corresponding to −CH3 (Δδ = −0.22)
electrolytes. and −OCH3 (Δδ = −0.35) of DODSi shifted toward the
upfield, indicating the replacement of −OCH3 with −F. The
enhanced cycle stability of NCM811/graphite full cells with
cathode−electrolyte interface (CEI) and to scavenge the DODSi as an additive also evidenced that its HF scavenging
reactive HF and PF5 species has been considered to maintain ability is effective for improving the battery performance. The
the stable electrochemical performance of Ni-rich cathodes in phosphorus core of diethyl phenylphosphonite (DEPP), which
lithium hexafluorophosphate (LiPF6)-based electrolytes. The is prone to protonation, captures HF in Li/Li-
HF and PF5 species produced by such electrolytes cause fatal Ni0.8Co0.15Al0.05O2 (NCA) half cells.60 Density functional
interfacial damage to Ni-rich cathodes in LIBs and TM theory calculations have shown that the absolute value of the
dissolution from the cathode (Figure 1f−h).42 combined energy of HF with DEPP (−44.04 kJ mol−1) is
Film-forming additives oxidize on the surface of Ni-rich higher than that with EC (−34.88 kJ mol−1), ethyl methyl
cathodes prior to the decomposition of electrolyte solvents carbonate (EMC) (−35.13 kJ mol−1), and diethyl carbonate
such as ethylene carbonate (EC), dimethyl carbonate (DMC), (DEC) (−36.19 kJ mol−1), indicating a stronger interaction
and Li salt, forming a homogeneous CEI. The presence of a between DEPP and H+ in HF. Furthermore, it has been
uniform CEI can inhibit side reactions of the electrolyte at the demonstrated that the high affinity of DEPP toward Ni3+ ions
cathode as well as interfacial degradation induced by the facilitates the formation of a DEPP-derived CEI on the surface
irreversible phase transition of Ni-rich cathodes and micro- of NCA. Tris(trimethylsilyl)phosphite (TMSPi), which has
cracks inside the LiNi0.8Co0.1Mn0.1O2 (NCM811) secondary been frequently adopted as an additive for NCM111,
particles (Figure 1f,g). NCM523, NCM622, and NCA cathodes, also scavenges HF
Elimination of Corrosive HF in LiPF6-based Electrolytes. and constructs a stable CEI to ensure battery performance
Residual lithium compounds such as LiOH anchored on the such as a long cycle lifetime and high rate capabil-
Ni-rich cathode surface react with LiPF6 to produce HF, which ity.56,58,59,67−69 However, TMSPi suffers from parasitic
is regarded as a key cause of the TM dissolution of reactions in LiPF6-based electrolytes due to the high reactivity
cathodes.62,63 Although the additives form a CEI to protect of phosphite and TMS moieties.67,69 The reactivity of
the Ni-rich cathode, HF leads to fatal CEI damage upon phosphites in TMSPi can be regulated by binding electron-
cycling or storage at elevated temperatures, resulting in withdrawing groups to the phosphite core, thereby reducing
deterioration of the cathode interfacial structure.62,64,65 The the activity of the lone pair of electrons on phosphorus.
amount of residual LiOH increases with Ni content, for Building Protective Interfacial Layers. In addition to HF
example, 2593 ppm for LiNi0.6Co0.2Mn0.2O2 (NCM622) and scavengers, interfacial engineering to form a CEI is also
10 996 ppm for LiNi0.8Co0.1Mn0.1O2 (NCM811).43 This regarded as a competitive strategy for the long-term interfacial
implies that Ni-rich cathodes with Ni contents >60% possibly stability of Ni-rich cathodes and improved battery perform-
generate more HF from the reaction of LiOH with LiPF6. In ance. Additive-driven interfacial layers that prevent direct
this regard, the use of additives for HF elimination must be contact between reactive Ni-rich cathodes (NCM and NCA)
considered to mitigate HF-driven problems. Electrolyte and the electrolyte circumvent the following issues: TM
additives with a high affinity toward F and high probability dissolution by HF attack, undesired reduction of high-valence
of protonation effectively capture HF, which is responsible for Ni4+ ions, irrevocable surface phase transition from layer
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Figure 2. Representative additives for Ni-rich cathodes, their oxidation potentials, and their reaction mechanisms. (a) Functional motifs of
electrolyte additives for Ni-rich cathodes. Trimethyl boroxine (TMB),47 triethyl borate (TEB),48 p-toluenesulfonyl isocyanate (PTSI),49
[4,4′-bi(1,3,2-dioxathiolane)]2,2′-dioxide (BDTD),50 diphenyldimethoxysilane (DPDMS),51 triisopropyl borate (TIB),52 dimethoxydime-
thylsilane (DODSi),53,54 succinic anhydride (SA),55 tris(trimethylsilyl) phosphite (TMSPi),56−59 diethyl phenylphosphonite (DEPP),60 and
allylboronic acid pinacol ester (ABAPE).61 Open-circuit voltage indicates the potential difference between the cathode and anode before
charging. (b) Possible mechanisms for cathode−electrolyte interface (CEI) formation and HF elimination by PTSI,49 DPDMS,51 and
TMSPi.68,69 Adapted with permission from ref 49. Copyright 2017 Elsevier. Reproduced with permission from ref 51. Copyright 2017
Elsevier. Reproduced with permission from ref 68. Copyright 2014 RSC Publishing. Reproduced with permission from ref 69. Copyright
2015 Elsevier.

(R3̅m) to NiO-like rock-salt (Fm3̅m) phases, and damage to Li+ ions at the cathode under an electrical field. Furthermore,
the interfacial cathode structure. The highest occupied polar groups in the CEI provide ion paths and assist in the
molecular orbital (HOMO) energy levels reflect the electron- removal of solvent molecules from Li ions in the vicinity of the
donating characteristics and have been used as an important cathode surface during the discharge (relithiation) process.
indicator to determine appropriate electrolyte additives for Electrolyte additives for Ni-based cathodes with different Ni
CEI formation. The CEI generally contains inorganic (LiF) contents and their electrolyte performance are presented in
and organic (ether-containing polymeric compounds and Figure 2a and in Tables S1−S6. Film-forming additives
carbonates) species.2,21 Because a resistive LiF-based CEI possessing boron,47,48,70,71 sulfur,50,72,73 fluorine,74,75 and
may impede Li ion transport, the formation of ionically phosphorus 76−78 atoms have been reported for Li-
permeable layers with Li ion-containing species and polar Ni1/3Co1/3Mn1/3O2 (NCM111) and NCM523 cathodes,
groups such as P−O and C−O is desirable for better cathode which have relatively low Ni contents (Figure 2a). The
kinetics. The presence of Li ions in the CEI reduces the Ohmic boron-containing additives trimethyl boroxine (TMB),47
resistance of the cathode and greatly facilitates the migration of triethyl borate (TEB),48 tris(trimethylsilyl)borate (TMSB),70
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and lithium difluoro(oxalato)borate (LiDFOB) have been used occur because the Mn dissolution from NCM701515 is more
to improve the electrochemical performance of NCM111 severe than the Al dissolution from NCA, potentially leading to
cathodes.71 TMB oxidizes at a relatively low potential of 4.15 V more pronounced parasitic reactions of electrolytes at
vs Li/Li+ compared with additive-free electrolytes with an NCM701515 cathodes.
anodic limit of 4.32 V vs Li/Li+. The TMB-derived CEI, which Incorporation of Electrolyte Additives for Interfacial Stability of
contains less LiF and LixPOyFz, effectively inhibits the Si Anodes. Challenges of Si-based Anodes. Si has been highlighted
irreversible phase transformation of NCM111 cathodes upon as a key anode material to realize high-energy-density batteries.
repeated cycling. The sulfur-containing additive [4,4′-bi(1,3,2- Si as an anode material leads to the formation of Li15Si4, which
dioxathiolane)]2,2′-dioxide (BDTD) electrochemically oxi- delivers a high reversible capacity of 3579 mAh g−1,
dizes prior to oxidative decomposition of electrolyte approximately 10 times higher than that of graphite anodes
components to form a stable CEI. BDTD-derived CEIs are (372 mAh g−1) after charging (lithiation).81,82 Si also provides
composed of Li-rich inorganic species such as Li2SO3 and reasonably low lithiation potentials (<0.4 V vs Li/Li+), which
ROSO2Li (R = alkyl), which facilitate Li-ion migration and can boost the energy density of batteries,83 and it is abundant
improve the rate capability of Li/NCM523 half cells.50 in the earth, which enables competitive costs (U.S. $/Wh).84
Fluorine-containing additives have been explored for However, the severe volume changes of Si during the lithiation
NCM523 cathodes with a relatively high operating voltage of and delithiation processes negatively affect the volumetric
4.6 V vs Li/Li+ because fluorination lowers the HOMO energy, energy density of batteries and cause uncontrollable swelling,
thereby improving the oxidation durability at high voltages.79 consumable electrolyte decomposition on newly exposed Si,
The fluorine-containing additives methyl 2,2,2-trifluoroethyl and rapid decay of battery lifetime.12,82,85
carbonate (FEMC) and ethyl difluoroacetate (DFEAc) have Crystalline Si transforms to an amorphous phase in Li−Si
been combined with fluoroethylene carbonate (FEC) to serve alloys, causing an extreme volume expansion of 300% because
as an electrolyte solvent as well as a film-forming additive the bonds between the host Si atoms are broken to form new
(Table S3).74,75 The combination of DFEAc and FEC reduces bonds with Li ions.12 In the case of spherical particles of
the oxidation current at 4.5 V Li/Li+ in Li/NCM523 half cells crystalline Si, lithiated Si is generated from the surface to the
owing to the less resistive and stable CEI with polar C−F bulk of the Si particles during lithiation, and the region
species that allows for facile Li+ ion migration. In addition, the occupied by the lithiated Si shell becomes larger with
phosphorus center of 2-(2,2,2-trifluoroethoxy)-1,3,2-dioxa- increasing lithiation level.13 This Si shell undergoes compres-
phospholane-2-oxide (TFEOP) can be attacked by the sive plastic deformation in the hoop direction, and this hoop
nucleophilic oxygen of NCM523 cathodes to generate OH− tensile stress at the surface shell causes particle fracture.13 With
P−O-containing intermediates attached on the cathode surface repeated cycles, Si continues to inflate and contract, resulting
along with proton transfer, generating a protonated inter- in pulverization of the electrodes, blocking of the percolation
mediate. This intermediate undergoes a further proton transfer routes of electron transfer within the electrodes, and
to form polyphosphoester species as a CEI constituent on the plummeting battery capacities.14 Although porous Si anode
NCM523 cathode.77 A Si−O-containing CEI has been materials with sufficient free volume for Si to expand86 and
reported to improve the electrochemical performance of composite anodes with a volumetric buffer matrix have been
NCM622,58,66 NCM811,53,54 and NCA cathodes59 because developed,87 the uniformity of the volumetric expansion of the
the Si−O moiety in the additives not only forms polymeric Si segment depending on the lithiation degree is hard to
species (−O−Si−O−) but also scavenges HF owing to the control, leading to a much shorter service life than graphite
strong affinity of Si toward fluorine (Figure 2b).66 Boron- anodes due to structural degradation.88 Because Si has a lower
containing additives have yielded good performance in Ni-rich lithiation potential (<0.4 V vs Li/Li+) than the cathodic
cathodes, such as triisopropyl borate (TIB)52 for NCM622 and voltage limits of conventional electrolytes, the reductive
allylboronic acid pinacol ester (ABAPE)61 for NCA. TIB is an decomposition of the electrolyte at the anode occurs prior to
effective film-forming additive and improved the cycling the lithiation of Si.2 Importantly, the native oxide (SiO2) layer
performance of NCM622 cathodes in the voltage range of on the Si anode material forms Li2O and LixSiOy species
3.0 to 4.5 V.52 The unsaturated group (−CC−) of ABAPE through the reaction with Li ions.89−91 This native oxide layer
contributed to the formation of a B−O-based CEI, which probably hinders a pronounced formation of LiF by the
reduced the impedance and TM dissolution of the NCA reductive decomposition of LiPF6 above 1.0 V Li/Li+ near the
cathode.52 Succinic anhydride (SA) improved the cycling surface of the Si anode material, and thus a small quantity of
performance of NCM811 cathodes over 400 cycles at 2.8 to LiF species are observed on the oxide layer, Li2O, and
4.3 V at a 1 C rate by building a uniform CEI with polymeric LixSiOy.92 Furthermore, the active surface of Si is continuously
species (poly(carbonate)), which improved the structural exposed to the electrolyte owing to the severe fluctuation of
integrity of NCM811 secondary particles.55 It has been the Si volume and structural deterioration from massive crack
demonstrated that microcracks inside secondary particles and generation to pulverization of the Si particles. In repeated
the degree of irreversible transformation from the H2 to H3 charge/discharge processes, continuous electrolyte decom-
phase are alleviated by an SA-derived CEI. Therefore, position at the exposed Si anode surface forms a porous
polymeric species can clearly accommodate the anisotropic organic solid electrolyte interphase (SEI) layer on the Si anode
volumetric stress induced by the phase transition from H2 to that increases in thickness toward the surface of the Si anode
H3 and lithiation/delithiation, thereby enhancing the struc- material, with inorganic SEI species occupying the void space
tural stability of Ni-rich cathodes. Importantly, NCA is more within the porous layer. Accordingly, a multilayer SEI
stable in contact with electrolytes at high voltages and elevated comprising a compact inorganic inner layer (LixSiOy, SiOxFy,
temperatures compared with NCM cathodes, despite the and LiF) and a more porous organic outer layer (lithium
higher Ni content in NCA.80 The low degree of surface ethylene decarbonate, Li2CO3, and ROLi (R = alkyl)) is found
reconstruction and less TM dissolution of NCA cathodes likely for cycled Si anodes.93 These repetitive reactions lead to
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Figure 3. Solid electrolyte interphase (SEI) building strategies to passivate the surface of Si-based anodes by forming (a) LiF,94 (b)
polymeric and organic compounds,95 (c) siloxane network structures,96 and (d) coadditives with fluoroethylene carbonate (FEC).97 (e)
Degradation mechanism of Si-based anodes and SEI.

depletion of the electrolyte and the eventual termination of the LiF-based SEI. In general, SEI formation occurs in the early
battery service life.14 stage of the lithiation process, followed by Li−Si alloying,
Structuring Interfacial Layers. The large volume changes in which imposes considerable tensile stress on the SEI (Figure
the SEI formed on high-capacity Si-based anodes cause 3e). The SEI layers experience tensile stress from Si swelling
additional challenges to those with graphite anodes, which upon lithiation. The bond breaking of LiF in the SEI that
have no irreversibility issues induced by volume expansion causes cracking of Si can be regulated by controlling the rate
upon lithiation. To create a structurally stable SEI on a Si and level of Si lithiation.98 In the case of fast charging, which
anode, the use of film-forming additives with a high reduction does not provide enough time for SEI relaxation and structural
probability has been considered. Film-forming additives reconstruction, or a high level of lithiation, the function of the
favorably adsorb on the anode and undergo reduction to SEI layers becomes unsustainable despite the establishment of
accept electrons and produce a compositionally homogeneous a mechanically robust LiF-based SEI on the Si anode.
SEI prior to electrolyte consumption, thereby minimizing the Haruta et al. reported that a Si thin-film electrode with a 4
anisotropic volume changes of Si caused by nonuniform nm LiF coating layer had improved Coulombic efficiency,
decreased impedance at 0.1 V vs Li/Li+ in the second charge
lithiation and delithiation, and stably maintain the morphology
process, and a uniform surface with fewer deposits formed by
and electronic connection of Si within the anode without
indiscrete electrolyte decomposition.99 A “glue effect” of LiF
severe rearrangement. In addition, the structure of the SEI on
on organic species in the SEI has also been demonstrated by an
the Si anode must be mechanically stable to alleviate fracturing ab initio study.94 LiF exhibits strong adhesion to organic
during cycling. To improve the chemical, electrochemical, and species on the SEI, which enables a stable and robust SEI with
mechanical stability of the SEI for Si-based anodes, the LiF and organic components. Furthermore, LiF can form
following four strategies have been applied (Figure 3): (1) chemical bonds with Li on lithiated Si, and LiF aggregates can
using fluorinated additives that undergo a F-transfer reaction to stably adsorb at the surface of lithiated Si; these adsorbed LiF
form a F-enriched SEI or a LiF-based SEI; (2) using aggregates act as a glue with organic SEI film components, thus
polymerizable organic additives to produce an SEI with building a robust SEI (Figure 3a). FEC, which has been
polymeric species; (3) using Si-containing additives to commonly used for SEI formation to prevent the degradation
construct a siloxane network structure via reactions with of Si-based anodes, has a relatively low lowest unoccupied
native silanol groups on the Si surface; and (4) using molecular orbital (LUMO) energy, indicating a high electron
coadditives showing synergic effects with FEC as effective acceptance ability due to the electron-withdrawing effect of
film-forming additives for Si anodes. fluorine; this leads to the formation of LiF-containing SEIs.85
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Fluorine-donating additives such as tris(pentafluorophenyl)- construct the SEI of Si-based anodes.108,109 The reduced free
borane100 and trifluoropropylene carbonate101 have been volume in VC-derived SEIs inhibits the solvent molecules from
reported to form LiF-based SEIs on the surface of Si-based accessing the active Si, which alleviates electrolyte decom-
anodes (Table S7). Salt-type fluorinated additives such as position and extends the service life at moderate C rates.
LiDFOB102 and lithium trifluoro(perfluoro-tert-butyloxyl)- However, at high C rates, the densely structured VC-derived
borate favorably form LiF-rich SEIs that are effective for the SEI hampers the Li-ion transport, leading to poor kinetics in
protection of high-capacity anodes.103,104 Si-based anodes. Electrolyte additives that form organic-
SEI with Polymeric and Organic Compounds. Polymeric and enriched SEIs to protect Si-based anodes usually have fragile
organic compounds, which are flexible enough to endure the ring structures or terminal vinyl groups. Lithium bis(oxalato)-
tensile stress from the volume expansion of Si, enable the borate (LiBOB), which has a ring structure with a boron core,
reversible deformation of LiF-based SEIs without serious forms a polar oxalate-containing SEI on Si thin-film anodes.110
damage at a high level of Si lithiation.99 Binder-free Si anodes SA forms Li2CO3 and a hydrocarbon-based SEI that protect Si
cycled in EC-based electrolytes have been covered with and suppress salt decomposition.100,111 Pentafluorophenyl
dilithium ethylene dicarbonate ((CH2OCO2Li)2; Li2EDC), isocyanate polymerizes to form fluorinated polymer species,
LiF, and LixSiOy species.105 which accommodate the large volume changes of Si (Figure
Because Li2EDC produced by EC reduction may be soluble 3b).96 Methylene ethylene carbonate (MEC) polymerizes to
in electrolyte solvents such as EC and DMC under an electric poly(MEC) to suppress the cracking of Si and the
field and elevated temperatures, it is not a desirable SEI decomposition of carbonate solvents (Table S7).112
component (Figure 4a). Interestingly, FEC-based electrolytes Siloxane Network-based SEI. Silane-based functional addi-
generate LiF, LixSiOy, and insoluble polymeric species such as tives, such as vinyl tris(2-methoxyethoxy)silane (VTMS)113
poly(alkene)106 and poly(carbonate)107 as SEI constituents and (2-cyanoethyl)triethoxysilane (TEOSCN),96 preferentially
(Figure 4b). Vinylene carbonate (VC), which forms react with native silanol groups on the surface of Si-based
structurally dense poly(VC), has been frequently used to anodes to build organosilicon or siloxane networks (Figure
3c).114 This type of SEI has a high shear modulus that mitigate
damages, thus providing high chemical/electrochemical
stability.
Synergic Ef fects of Coadditives with FEC. To address the
insufficient passivation capability of EC-derived SEIs, FEC,
which forms an SEI composed of mechanically robust LiF and
flexible polymeric/organic species, is commonly used to
mitigate the interfacial deterioration of Si-based anodes.
However, FEC has inferior thermal stability because it is
prone to defluorination by Lewis acids such as PF5 to form
reactive acid species (HF, HPO2F2, H3OPF6, H2PO3F, and
H3PO4). These acids cause severe damage to the SEI on Si-
based anodes, resulting into shortened battery lifetimes.115 To
minimize the detrimental effects of FEC on battery perform-
ance, an optimal FEC content should be introduced because
excess FEC produces undesirable and corrosive species such as
HF. To attain superior FEC-rich electrolytes, the use of
coadditives with complementary functions is recommended.
The coadditives di(2,2,2-trifluoroethyl)carbonate,116 1,3-pro-
panediolcyclic sulfate, 117 and lithium fluoromalonato-
(difluoro)borate (LiFMDFB),97 which exhibit synergistic
effects with FEC, have been proposed to form stress-tolerant
SEIs by suppressing Si cracking and electrolyte decomposition
during cycling (Figure 3d). The combination of FEC with
LiFMDFB can form an FEC+LiFMDFB-originated SEI
because the FMDFB anion coordinates with FEC molecules
to decrease the FEC LUMO energy level and promote its
reductive decomposition. To circumvent the inadequacies of
FEC-derived SEIs such as their poor mechanical properties,
because they do not adopt the large volume changes of Si-
based anodes, and incapacity, because they do not inhibit the
consumable decomposition of electrolytes during cycling, the
Figure 4. (a) Solid electrolyte interphase (SEI) formation development of coadditives to compensate for the short-
mechanism of ethylene-carbonate (EC)-based electrolytes on the comings of FEC is indispensable.
surface of Si-based anodes. Reproduced with permission from ref
Gas Generation in Li-Ion Batteries and Possible Solutions.
110. Copyright 2012 ECS - The Electrochemical Society. (b) SEI
formation mechanism of fluoroethylene-carbonate (FEC)-based Causes of Gas Generation in Batteries. Gas generation in
electrolyte on the surface of Si-based anodes. Reprinted from ref operating batteries interferes with the movement of Li ions
107. Copyright 2011 American Chemical Society. Reproduced between the cathode and anode. This hindrance to the
with permission from ref 106. Copyright 2011 ECS - The reversible electrochemical reaction leads to a decay in battery
Electrochemical Society. capacity and increases the internal pressure of the battery, thus
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Figure 5. Gas generation mechanism in batteries. (a) Reductive decomposition of ethylene carbonate (EC). (b) Oxidative decomposition of
EC. Reproduced with permission from ref 22. Copyright 2017 Electrochemical Society. (c) Schematic illustration of solid electrolyte
interphase (SEI) and cathode−electrolyte interface (CEI) destruction. (d) H2O decomposition. (e) Residual lithium compound
decomposition. (f) Evolution of oxygen from cathodes and attack by reactive oxygen species (1O2 or O2•−). Reproduced with permission
from ref 20. Copyright 2017 Electrochemical Society. Reprinted from ref 124. Copyright 2011 American Chemical Society.

distorting the packing structure of the electrodes. Eventually, EC + 2Li+ + 2e− → Li 2CO3 ↓ + C2H4↑ (3)
this causes battery explosion by a short circuit through contact
between the anode and cathode. Gas evolution is attributable The oxidative decomposition of EC at the cathode surface
to the chemical and electrochemical decomposition of generates large amounts of CO2 and small amounts of CO gas
electrolytes under harsh conditions such as high voltages and at 4.5 V vs Li/Li+ (Figure 5b).22 The radical cation EC•+
temperatures. Carbonate-based electrolyte solvents commer- formed by the one-electron oxidation of EC more readily
cially used for LIBs chemically decompose into dialkyl ether produces CO2 compared with CO due to the low activation
and CO2 in the presence of catalysts such as PF5, which are energy.125 The formation of SEI and CEI layers to stabilize the
produced by the equilibrium decomposition of LiPF 6 electrode−electrolyte interface involves gas evolution, and thus
(R1CO3R2 → R1−O−R2 + CO2↑).118 The thermal decom- commercial battery manufacturing systems include a degassing
position of DMC and EMC produces CO2, CH4, CH3OH, H2, process. However, if the SEI and CEI layers are not stably
CO, CH3OCH3, and C2H4 at high temperatures. In the case of maintained at the electrode−electrolyte interface, then gas
EMC, C2H6 and C2H5OH are also generated.119 In addition, generation by continued electrolyte decomposition at the
EC contributes to gas generation by reacting with a small damaged SEI and CEI and interfacial degradation of electrodes
amount of H2O while producing CO2 and ethylene glycol (EC cannot be avoided under high-temperature and high-voltage
+ H2O → C2H4(OH)2 + CO2↑).120 Importantly, SEI conditions. Accordingly, the safe behavior and high perform-
formation on the anode by the reductive decomposition of ance of batteries cannot be assured. The structural breakdown
the electrolyte produces gaseous components. In particular, of the SEI and CEI is susceptible to acid attacks as well as high
EC, which has a low LUMO energy compared with other temperatures. Conventional electrolytes containing LiPF6
linear carbonate solvents, leads to the formation of CO and comprise acid compounds such as PF5, HF, and fluorophos-
C 2 H 4 gases while generating insoluble Li 2 EDC phoric acid originating from the hydrolysis of LiPF6 in the
((CH2OCO2Li)2), (CH2OLi)2, and Li2CO3 species as SEI presence of trace amounts of water.23 Corrosive HF reacts with
components (Figure 5a and eqs 1−3).121−123 organic species in the CEI and SEI to generate CO2 according
to eqs 4 and 5 (Figure 5c),24,126 and strong Lewis acid PF5 and
2EC + 2Li+ + 2e− → (CH 2OCO2 Li)2 ↓ + C2H4↑ (1) highly reactive POF3 trigger the decomposition of carbonate-
based solvents to generate CO2.23,127,128

EC + 2Li+ + 2e− → (CH 2OLi)2 ↓ + CO↑ (2) Li 2CO3 + 2HF → 2LiF ↓ + H 2O + CO2 ↑ (4)

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Figure 6. (a) Gas generation in a pouch containing LiCoO2 (LCO), LiNi0.8Co0.1Mn0.1O2 (NCM811), or graphite with LiPF6-carbonate-based
electrolyte depending on state of charge (SOC). Reproduced with permission from ref 129. Copyright 2004 Elsevier. (b) Schematic
illustration of nucleophilic attack of oxygen on ethylene carbonate (EC): The later the transition metal (TM) oxide is formed, the smaller
the difference between the Fermi level (EF) and the O p band and the more unstable the oxygen energy level, which improves the
nucleophilicity of the oxygen on the electrode surface. Reprinted from ref 21. Copyright 2015 American Chemical Society. (c) Possible
mechanism and schematic illustration of oxidative decomposition of EC to generate CO2 and CO protic species, which easily produce
protons that are then reduced to H2 at the graphite anode. Reproduced with permission from ref 130. Copyright 2016 Electrochemical
Society.

LiOCO2 R + HF → LiF ↓ + ROH + CO2 ↑ decomposition of residual H2O (H2O + e− → OH− + 2 H 2↑,
(5) 1

Damaged SEI and CEI layers cause continuous electrolyte Figure 5d) and the reduction of protic species (R−H+) that
form by electrolyte oxidation at the cathode and anode (Figure
decomposition at the electrode−electrolyte interface, resulting
6c).18,130
in severe gas generation.
The residual lithium compounds (Li2CO3 and LiOH) in Ni-
The state of charge (SOC) and electrode materials also
rich cathodes can provoke gas generation through chemical
affect the gas evolution in batteries. When LiCoO2 (LCO),
reactions with LiPF6-based electrolytes (Figure 5e). Li2CO3
LiNi0.8Co0.1Mn0.1O2 (NCM811), and graphite were separately produces CO2 (eq 4), and LiOH generates LiOCO2R via a
stored at 90 °C at different SOCs, the gas generation reaction with ROCO2R in the CEI, which triggers CO2
significantly increased with increasing SOC, whereas the evolution by reacting with H2O (eqs 6−8)19
NCM811 cathodes showed the greatest swelling (Figure
6a).129 A high SOC implies a high level of delithiation of the ROCO2 R + LiOH → LiOCO2 R + ROH (6)
cathode, indicating a strong tendency toward electron-
2LiOCO2 R + H 2O → Li 2CO3 ↓ + 2ROH + CO2 ↑ (7)
accepting that may cause oxidative decomposition of the
electrolytes. The difference between the Fermi level (EF) and LiOCO2 R + H 2O → LiOH + ROH + CO2 ↑ (8)
the O p band becomes smaller for late TM oxides; thereby, the
oxygen energy levels destabilize, resulting in enhanced Li2CO3 is not suitable as a CEI component because it oxidizes
nucleophilicity of the oxygen ions on the surface of the Ni- to CO2 and O2•− (eq 9).17
based cathode (Figure 6b).21 The nucleophilicity of oxygen 2Li 2CO3 → 4Li+ + 2CO2 ↑ + 3e− + O2•− (9)
ions is reported to be higher on the surface of Ni-based LiNiO2
cathodes than on Co-based LCO cathodes and through higher A possible solution to suppress the gas generation caused by
impedance induced by nucleophilic reactions between LiNiO2 residual lithium compounds is to introduce a washing process.
and the electrolyte solvents.21 Therefore, it is thought that The washing of LiNi0.85Co0.12Al0.03O2 (NCA) cathodes greatly
nucleophilic attacks on solvent molecules such as EC, which reduced the gas generation from ∼2.5 to ∼0.75 cc/g after
provoke gas generation, are intensified for Ni-based cathodes. storing in a fully charged state with electrolyte at 85 °C for 32
The main gases that evolve through the reductive decom- h.131 TM oxide cathode materials can generate oxygen gas
position of EC at the graphite anode are CO, C2H4, and H2, according to their characteristics: (i) Li2MnO3 activation of Li-
whereas CO and CO 2 evolve through the oxidative rich cathodes involves O 2 evolution (Li 2−x MnO 3 →
y
decomposition of EC at the LCO or NCM cathode (Figure Li2−xMnO3−y + 2 O2 ↑),132 and (ii) the structural instability of
6c).127,128 H2 generation is attributable to the reductive layered metal oxide cathode materials such as LCO and NCM
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Figure 7. (a) In situ differential electrochemical mass spectrometry (DEMS) analysis of O2 and CO gas generation during the first charging
of Li-rich/Li half cells with and without lithium fluoromalonato(difluoro)borate (LiFMDFB) additive and schematic illustration of removing
O2 and suppressing electrolyte decomposition, which produces CO. Reproduced with permission from ref 97. Copyright 2018 RSC
Publishing. (b) Reaction mechanism of O2 scavenging by phosphite moiety. Reproduced with permission from ref 135. Copyright 2013
Elsevier. (c) Possible reduction reactions of 1,3-propane sultone (1,3-PS) to produce solid-state ionic compounds, Li2SO3 and LiO3S−
(CH2)6−SO3Li, without severe gas generation. Reproduced with permission from ref 139. Copyright 2012 RSC Publishing.

at a high level of delithiation provokes O2 evolution because of O2 from the Li-rich cathode.97 Moreover, in situ differential
the oxygen anion is oxidized by the repulsive force between the electrochemical mass spectrometry (DEMS) has shown that
oxygen atoms of the metal oxide (MO2) layer. As a result, the evolution of gaseous components from a Li-rich cathode
rapid contraction occurs along the c axis, which leads to a was suppressed by the oxygen-scavenging and blocking effects
phase transition (LixMO2(layered) → of a LiFMDFB-derived CEI, as shown in Figure 7a.
x+1 1 − 2x Phosphite (P(III)) compounds with lone-pair electrons
Li3−(3/(x+1))M3/(x+1)O4(spinel) + 3 O2 ↑and LixMO2(layered)
3 scavenge O 2 to form phosphine oxide (Figure 7b).
1−x
→ (x + 1)Li1−(1/(x+1))M1/(x+1)O(rock‑salt) + 2 O2 ↑).20,133 Triphenylphosphine (PPh3), ethyl diphenylphosphinite (P-
Oxygen gas can accept electrons and be converted into (Ph)2(OEt)), and triethyl phosphite (P(OEt)3) as electrolyte
reactive oxygen radicals (O2•−) that attack the CH2 moiety of additives preferentially react with O2 generated from a
EC through an SN2 reaction mechanism to produce CO2 Li1.167Ni0.233Co0.1Mn0.467Mo0.033O2 cathode during the charging
(Figure 5f).23,124 In addition, O2•− may react with generated process, as illustrated by 31P NMR spectroscopy.135 Notably,
CO2 gas in a battery to finally produce Li2CO3 (eqs 10 and the reactivity of battery components increases at elevated
11)17,125 temperatures, which accelerates side reactions and gas
generation. It has been reported that nitrile (CN)-136 and
2O2•− + 2CO2 → C2O6 2 − + O2 ↑ (10) sulfur-based137,138 additives suppress gas generation at high
temperatures owing to the high thermal stability of the
C2O6 2 − + O2•− + 4Li+ → 2Li 2CO3 ↓ +2O2 ↑ (11) additive-derived SEI or CEI (Table S8). Pouch-type LCO/
graphite full cells at a fully charged state with a succinonitrile
It has been demonstrated that the oxygen generated from (SN)-containing electrolyte reduce the amount of gas
layered metal oxide cathodes such as Ni-rich and Li-rich generated at both 80 and 90 °C, delay the exothermic reaction
cathodes is in the form of highly reactive singlet oxygen (1O2), of delithiated LCO (Li1−xCoO2, charged to 4.2 V in a LCO/
which is released at SOCs >80% regardless of Ni content or graphite full cell) in the presence of electrolyte, and prevent
voltage.134 1O2 attacks EC molecules, resulting in the the thermal runaway of fully charged full cells at 150 °C due to
generation of CO2 and CO gases and the formation of the strong complex formation between the Li1−xCoO2 cathode
undesirable H2O (Figure 5f).20 and CN groups of the SN additive.137 1,3-Propane sultone
Additives for Suppressing Gas Generation in Batteries. Because (1,3-PS) suppresses the gas evolution of LiNi0.5Mn1.5O4/
high-capacity cathodes (Ni-rich, Li-rich, high-voltage cath- graphite full cells at a fully charged state and 90 °C because the
odes) for high-energy-density batteries inevitably generate 1,3-PS-derived SEI protects the lithiated graphite anode at an
reactive oxygen species, O2 scavenging is a promising method elevated temperature.138 Because 1,3-PS contributes to the
to mitigate gas-related issues. Boron97 and phosphite135 formation of SEIs based on ionic species such as Li2SO3 and
effectively scavenge reactive oxygen species (Table S8). LiO3S−(CH2)6−SO3Li without gas generation (Figure 7c),139
LiFMDFB, which has been used as an electrolyte additive to it can be employed as an electrolyte additive to repair damaged
construct a stable CEI on Li-rich cathodes before the activation SEIs at high temperatures and form an ionically permeable SEI.
of Li2MnO3, has been shown to incorporate electrophilic Summary and Outlook. The battery performance degradation
boron atoms into the CEI, which scavenged reactive oxide induced by the interfacial instabilities of Ni-rich cathodes and
radicals and acted as a physical barrier to suppress the release Si-based anodes can be successfully repressed by the adoption
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of electrolyte additives that form protective surface layers on compounds to form the CEI on the cathode occurs at high
electrodes (Table S9) and capture evolved gas and reactive voltages of above ∼4.2 V vs Li/Li+. For cathodes with a mild
substances. A greater understanding of the action mechanisms charge cutoff voltage of 4.2 V vs Li/Li+, these salt-type
compounds will not work effectively as CEI formers.
A greater understanding of the action Importantly, Ni-rich cathodes with high-valence Ni4+ ions in
a fully delithiated state deprive the electrolyte of electrons at
mechanisms of the functional motifs in mild voltages of 4.2 V vs Li/Li+. In this situation, salt-type
electrolyte additives allows for the compounds, which are not consumed to form the SEI on the
development of suitable additive com- anode in a full cell, can properly construct the CEI. To be
binations that help appropriately reg- largely concentrated in the CEI formation on the cathode, the
reductive decomposition rate of salt-type compounds should
ulate the interfacial structures of high- be reduced by structural modification such as changing the
capacity electrodes to meet the multi- oxalate group of LiDFOB to the malonate moiety of
ple requirements for practical applica- LiFMDFB.97 Another effective approach to ensuring high-
tions. performance Ni-rich cathodes is to maintain stable interface
structures by scavenging HF species that leach TM ions from
the cathode. For the rational design of electrolyte additives
of the functional motifs in electrolyte additives allows for the with a high affinity toward Brønsted-acidic HF, leaving groups
development of suitable additive combinations that help produced by heterolytic bond cleavage in an additive molecule,
appropriately regulate the interfacial structures of high-capacity functional moieties that capture F− anions from HF, and a
electrodes to meet the multiple requirements for practical conjugated acid that receives a proton from HF should afford
applications. reasonable electrochemical stability in battery operation and
The high probability of electron uptake of high-valence Ni4+ positively affect the interfacial structures of high-capacity
ions aggravates the structural deterioration of Ni-rich cathodes electrodes. An optimal content of scavenging materials is
from a layered to spinel-like/rock-salt phase and generates a needed to minimize their negative effects, such as the
nonuniform CEI. The Ni2+ ions formed by the irreversible hindrance offered in interface modification by film-forming
reduction of Ni4+ ions are prone to migrating to Li slabs, additives and the problem of gas generation by unnecessary
resulting in the loss of Li+ storage ability of the Ni-rich decomposition at the electrodes. Phosphite derivatives
cathode. Because this undesired circumstance can be belonging to tricoordinate phosphorus(III) compounds
surmounted by the formation of interfacial layers to block possess lone-pair electrons with nucleophilicity and basicity
the electron-transfer path between the Ni-rich cathode and and are thereby prone to forming phosphate via the reaction
electrolyte, the use of sacrificial electrolyte additives that with singlet oxygen. When phosphorus(III)-based additives are
readily donate electrons is required to develop a desirable incorporated into LiPF6-based electrolytes, they scavenge HF
physical shield. Materials designed for the suppression of the via the protonation of phosphite-based additives. For instance,
phase transformation of Ni-rich cathodes are required to form TMSPi, which has been explored as an effective additive for
a chemically, electrochemically, and thermally robust CEI HF scavenging and CEI formation, is highly volatile because of
without any gas generation. Electron-deficient boron-based its low boiling point (Tb) of 78 °C, and thus its widespread use
compounds have some limitations (relatively low electron- is limited despite its outstanding performance in LIBs. Another
releasing character and insufficient oxidation kinetic at applied issue is the generation of highly flammable gaseous
charge rates) with regard to forming a suitable CEI on Ni-rich fluorotrimethylsilane (Tb = 16−18 °C) by the reaction with
cathodes in a valence state compared with lone-pair electron- HF, causing concerns about the safety of the electrolyte.
containing phosphorus(III)-based compounds.48,61 Impor- Tuning pendant groups by the introduction of a longer chain
tantly, electron-deficient boron-based compounds may con- bound to Si without flammable gas production and the design
tribute to SEI formation along with CEI formation because of core structures with high affinity toward unwanted species
they have lower LUMO energy than phosphorus(III)-based such as HF is required. These materials can be commercially
compounds (TMSB (1.013 eV) < TMSPi (1.152 eV)). Where applied only when the previously mentioned problems are
the electron-deficient boron-based compounds have unwanted addressed. Minimal amounts of highly reducible salt-type
secondary effects on the Si-based anodes, they should be boron-based additives such as LiBOB and LiDFOB are often
combined with reducible compounds possessing F-donating incorporated in high-energy-density LIBs to minimize the
character to build more effective F-enriched SEIs for the undesired reduction of additives with the ability for HF
protection of the Si-based anodes. CEIs that are composed of scavenging at the anode during the initial charge. The excessive
Li ion-containing species can be considered desirable for use of LiBOB and LiDFOB is not recommended because it
facilitating fast Li-ion transport at the physically blocked provokes the increase in cell impedance, thus hampering the
cathodes. Among the candidate boron- and phosphorus-based power density of batteries. LiDFP has been widely used as an
compounds, salt-type compounds such as LiDFOB,71 electrolyte additive in current batteries for electric vehicles
LiBOB,71 lithium difluorophosphate (LiDFP, LiPO2F2),140 because it can form Li-ion-containing polar interfacial layers
and lithium difluoro(bisoxalato)phosphate (LiDFBP)141 have that facilitate fast charge transport; moreover, it does not
been explored as CEI formers for Ni-rich cathodes. When salt- generate gases due to the absence of organic groups. However,
type compounds are introduced as electrolyte additives in full the application of LiDFP for high-energy-density batteries with
cells, they undergo nontrivial reductive decomposition at the Si-based anodes and Ni-rich cathodes is questionable.
anode in the early stage of charging due to their low LUMO Si anode materials lead to a dramatic increase in battery
energy and thereby do not form a suitable CEI on the cathode. capacity; nevertheless, they suffer from large volume changes
Another critical issue is that the oxidation of salt-type upon cycling that decrease the interfacial layer durability.
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Interfacial architectures that are partially adjustable to cycling and cause undesirable electrolyte decomposition; as a
accommodate such volumetric stress have allowed for the result, the battery performance is further improved. In
incorporation of Si in high-capacity anodes. Homogenous and addition, 1,3-PS, which can repair the damaged SEI with less
mechanically deformable interfacial layers that enable a gas generation, has been widely employed for the high-
uniform lithiation process and avoid a continuous filming temperature storage performance of LIBs. However, the use of
process without delamination of the interfacial layers have smaller amounts of 1,3-PS than is required is beneficial for
potential for further significant improvements to the long-term energy-storage devices for electric vehicles owing to its
performance of Si-based anodes. Synergistic effects along with carcinogenicity. Additives such as 1-propene 1,3-sultone142
the significant advancements of Si anode materials and and 1,3,2-dioxathiane 2,2-dioxide143 have been considered for
polymeric binders will be achieved by developing electrolyte the replacement of 1,3-PS, but they have a high price and form
additives for the construction of interfacial layers with resistive interfacial layers; therefore, further structural mod-
mechanical robustness (elastic deformation in organic species ification is required.
and mutual interaction between inorganic species, in particular, There has been extensive research and development of
strong attraction between F− of LiF and Li+ of Li ion- electrolyte additives for high-energy-density LIBs with Si-based
containing species) and full coverage to prevent direct contact anodes and Ni-rich cathodes, with great potential identified.
of the electrolyte components with active Si. Thus far, LUMO To be applied commercially in LIBs, developed electrolyte
energy levels of electrolyte additives have been utilized as an additives should meet the following industrial requirements:
important index to determine suitable reductive additives for (1) desired cost of <$164 (U.S.)/kg; (2) less gas generation
the formation of stable SEIs for the interfacial protection of Si- upon repeated cycling or during high-temperature storage; (3)
based anodes. Among the available additives that comprise in the case of LIBs for electric vehicles, low cell impedance, in
relatively low LUMO energy levels, fluorinated compounds particular, at temperatures <25 °C; and (4) room-temperature
with a high F-donating character can be regarded as potential storage stability without color changes for at least 6 months.
candidates to fabricate LiF-based or F-enriched SEIs for the The optimal content and cost-effective synthesis of electrolyte
interfacial stabilization of Si-based anodes. Because the level of additives can minimize the rise in electrolyte costs. The
fluorination has a significant effect on the molecular energy molecular design of inorganic-based additives should be
levels, the addition of fluorine into a molecule needs to be considered because organic species such as −CO2− groups
optimized to avoid unwanted oxidative decomposition at the that form by the side reactions with HF in the electrolyte give
cathode. Furthermore, the reductive decomposition rate of rise to the evolution of CO2 gas. For highly effective organic-
electrolyte additives should be as high as possible to achieve based additives, the structural stability of the resulting
the formation of a compositionally and structurally stable SEI interfacial layers can be preserved by formulation with HF
in the initial stage of the cycle. The rational design of scavenging additives. More importantly, ionically permeable
functional groups of electrolyte additives can overcome the and thin interfacial layers (CEI and SEI) must be formed on
trade-off relationship that exists between the battery perform- the electrodes to realize high-power-density batteries. Assuring
ance factors (such as the cycle life and the rate capability) and the chemical stability of developed additives in current LIB
the high-temperature storage performance. Among the electrolytes avoids the failure of their desired roles (film
described additives, VC and FEC are commonly used as SEI formation and HF scavenging). Our examination of the recent
forming agents. Their appropriate amounts are determined by progress in interfacial electrode engineering and O2 scavenging
the Si content in the anode of LIBs. For Si-containing anodes, with electrolyte additives offers valuable insights into recent
the use of FEC or the combination of FEC and VC is still trends and future routes in the development of high-
considered, despite the fact that defluorination of FEC impairs performance LIBs.
the thermal stability of LiPF6-based electrolytes. This is
because the few additives that surpass the electrochemical
performances of FEC and VC do not meet the prices required
■
*
ASSOCIATED CONTENT
sı Supporting Information
by the market.
The Supporting Information is available free of charge at
Gas generation in batteries is attributable to the formation of
https://pubs.acs.org/doi/10.1021/acsenergylett.0c00468.
interfacial layers on pristine electrode surfaces during the initial
cycle, decomposition of components in the interfacial layers Tables showing electrochemical performances of Ni-
during cycling or storage at high temperatures, and continuous based cathodes and Si-based anodes with various
electrolyte decomposition at newly exposed active electrode electrolyte additives and additives for inhibiting gas
surfaces in operating batteries. These gas-related issues can be generation in Li-ion batteries (PDF)
mitigated by employing film-forming additives to accompany
the decomposition path with less gas evolution and
constructing thermally stable interfacial layers composed of
heat-resistant inorganic species such as P−O and S−O
■ AUTHOR INFORMATION
Corresponding Author
moieties. From a site-specific viewpoint, the lone electron Nam-Soon Choi − School of Energy and Chemical Engineering,
pair on the phosphorus atom in triorganophosphites and the Ulsan National Institute of Science and Technology (UNIST),
electron-deficient boron atom with a high reactivity toward Ulsan 44919, Republic of Korea; orcid.org/0000-0003-
oxygen favorably capture reactive oxygen species generated 1183-5735; Email: [email protected]
from the cathodes, thus alleviating the associated increase in
battery internal pressure. Increasing the Lewis basicity of active Authors
sites of scavengers by attaching electron-donating groups can Koeun Kim − School of Energy and Chemical Engineering,
lead to stronger interactions with reactive substances that Ulsan National Institute of Science and Technology (UNIST),
otherwise impair the interfacial structures of electrodes upon Ulsan 44919, Republic of Korea
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Hyunsoo Ma − School of Energy and Chemical Engineering, (6) Schipper, F.; Erickson, E. M.; Erk, C.; Shin, J.-Y.; Chesneau, F.
Ulsan National Institute of Science and Technology (UNIST), F.; Aurbach, D. Review-Recent Advances and Remaining Challenges
Ulsan 44919, Republic of Korea for Lithium Ion Battery Cathodes I. Nickel-Rich, LiNixCoyMnzO2. J.
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https://pubs.acs.org/10.1021/acsenergylett.0c00468 (8) Manthiram, A.; Knight, J. C.; Myung, S. T.; Oh, S. M.; Sun, Y. K.
Nickel-Rich and Lithium-Rich Layered Oxide Cathodes: Progress and
Author Contributions Perspectives. Adv. Energy Mater. 2016, 6 (1), 1501010.
†
K.K., H.M., and S.P. contributed equally to this work (9) Kim, J.; Lee, H.; Cha, H.; Yoon, M.; Park, M.; Cho, J. Prospect
Notes and Reality of Ni-Rich Cathode for Commercialization. Adv. Energy
The authors declare no competing financial interest. Mater. 2018, 8, 1702028.
(10) Goriparti, S.; Miele, E.; De Angelis, F.; Di Fabrizio, E.; Proietti
Biographies Zaccaria, R.; Capiglia, C. Review on Recent Progress of Nano-
Koeun Kim received her Ph.D. degree from the School of Energy and structured Anode Materials for Li-Ion Batteries. J. Power Sources 2014,
Chemical Engineering at the Ulsan National Institute of Science and 257, 421−443.
Technology, South Korea, under the supervision of Prof. Nam-Soon (11) Sun, Y.; Liu, N.; Cui, Y. Promises and Challenges of
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Hyunsoo Ma is currently an M.S.−Ph.D. integrated course student in
Anniversary Article: Understanding the Lithiation of Silicon and
the School of Energy and Chemical Engineering at the Ulsan National Other Alloying Anodes for Lithium-Ion Batteries. Adv. Mater. 2013,
Institute of Science and Technology under the supervision of Prof. 25 (36), 4966−4985.
Nam-Soon Choi. His research focuses on the development of (13) Obrovac, M. N.; Krause, L. J. Reversible Cycling of Crystalline
electrolytes for lithium batteries containing Ni-based cathodes. Silicon Powder. J. Electrochem. Soc. 2007, 154 (2), A103−A108.
Sewon Park is currently a Ph.D. candidate in the School of Energy (14) Chae, S.; Ko, M.; Kim, K.; Ahn, K.; Cho, J. Confronting Issues
and Chemical Engineering at the Ulsan National Institute of Science of the Practical Implementation of Si Anode in High-Energy Lithium-
and Technology, South Korea, under the supervision of Prof. Nam- Ion. Batteries. Joule 2017, 1, 47−60.
Soon Choi. His research focuses on the development of functional (15) Li, T.; Yuan, X.-Z.; Zhang, L.; Song, D.; Shi, K.; Bock, C.
Degradation Mechanisms and Mitigation Strategies of Nickel-Rich
electrolyte additives for lithium-ion batteries containing Si-based
NMC-Based Lithium-Ion Batteries. Electrochem. Energy Rev. 2020, 3,
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43−80.
Nam-Soon Choi is currently an Associate Professor in the School of (16) Wen, J.; Yu, Y.; Chen, C. A Review on Lithium-Ion Batteries
Energy and Chemical Engineering at the Ulsan National Institute of Safety Issues: Existing Problems and Possible Solutions. Mater.
Science and Technology, South Korea. Her current research includes Express 2012, 2, 197−212.
the mechanistic analysis of electrode−electrolyte interfaces and the (17) Hong, J.; Lim, H. D.; Lee, M.; Kim, S. W.; Kim, H.; Oh, S. T.;
development of electrolyte additives for lithium batteries. Homepage: Chung, G. C.; Kang, K. Critical Role of Oxygen Evolved from Layered
http://surfchem.unist.ac.kr/. Li-Excess Metal Oxides in Lithium Rechargeable Batteries. Chem.

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Mater. 2012, 24 (14), 2692−2697.
(18) Galushkin, N. E.; Yazvinskaya, N. N.; Galushkin, D. N.
ACKNOWLEDGMENTS
Mechanism of Gases Generation during Lithium-Ion Batteries
This work was supported by the Korea Institute of Energy Cycling. J. Electrochem. Soc. 2019, 166 (6), A897−A908.
Technology Evaluation and Planning/IT R&D program of the (19) Kim, Y. Mechanism of Gas Evolution from the Cathode of
Ministry of Trade, Industry & Energy (MOTIE/KETEP) Lithium-Ion Batteries at the Initial Stage of High-Temperature
under Project Number 20172410100140 and by the Storage. J. Mater. Sci. 2013, 48 (24), 8547−8551.
Technology Development Program to Solve Climate Changes (20) Jung, R.; Metzger, M.; Maglia, F.; Stinner, C.; Gasteiger, H. A.
of the National Research Foundation (NRF), funded by the Oxygen Release and Its Effect on the Cycling Stability of
Ministry of Science, ICT & Future Planning LiNixMnyCozO2(NMC) Cathode Materials for Li-Ion Batteries. J.
(2018M1A2A2063341). Electrochem. Soc. 2017, 164 (7), A1361−A1377.

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(21) Gauthier, M.; Carney, T. J.; Grimaud, A.; Giordano, L.; Pour,
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