Review

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Lithium Batteries and the Solid Electrolyte Interphase

(SEI)—Progress and Outlook
Henry Adenusi, Gregory A. Chass, Stefano Passerini, Kun V. Tian,* and Guanhua Chen*

those being implemented in solving

Interfacial dynamics within chemical systems such as electron and ion global challenges remain accompanied
transport processes have relevance in the rational optimization of electro- by an energy reliance on non-renewable
chemical energy storage materials and devices. Evolving the understanding fossil fuels. The accelerated depletion of
stocks of these energy sources, together
of fundamental electrochemistry at interfaces would also help in the under-
with their associated pollution drives the
standing of relevant phenomena in biological, microbial, pharmaceutical, need to expedite establishment of robust
electronic, and photonic systems. In lithium-ion batteries, the electrochemical renewable alternatives. Often termed
instability of the electrolyte and its ensuing reactive decomposition proceeds “renewables” or “clean energy,” these
at the anode surface within the Helmholtz double layer resulting in a buildup power sources have a perennial temporal-
availability and thus have greater need for
of the reductive products, forming the solid electrolyte interphase (SEI). This
energy repositories than non-renewables.
review summarizes relevant aspects of the SEI including formation, compo- Hence, prompt optimization of energy
sition, dynamic structure, and reaction mechanisms, focusing primarily on storage-delivery devices is crucial to the
the graphite anode with insights into the lithium metal anode. Furthermore, sustainable development, scaling, com-
the influence of the electrolyte and electrode materials on SEI structure mercial delivery, and global establishment
and properties is discussed. An update is also presented on state-of-the- of reliable clean energy.[1,2]
Batteries and electrochemical devices
art approaches to quantitatively characterize the structure and changing
have most often filled the majority of
properties of the SEI. Lastly, a framework evaluating the standing problems power-storage and are ubiquitous as
and future research directions including feasible computational, machine energy mediation devices, capable of
learning, and experimental approaches are outlined. harnessing large amount of energy for
various applications including the aero-
space, travel and transport, and electronics
1. Introduction industries, among others.[3–6] The future of batteries lies with
devices produced from ever-more sustainable components that
The ever more pervasive technological advancements in modern can offer improved safety, transportability, extended battery life,
society, industry, manufacturing, and agriculture, as well as have short recharge times as well as low production costs and

H. Adenusi, G. Chen G. A. Chass, K. V. Tian

Hong Kong Quantum AI Lab Faculty of Land and Food Systems
17 Science Park West Avenue, Hong Kong, China The University of British Columbia
E-mail: ghc@everest.hku.hk Vancouver V6T 1Z4, Canada
G. A. Chass S. Passerini
Department of Chemistry Department of Chemistry
School of Physical and Chemical Sciences Sapienza University of Rome
Queen Mary University of London Rome 00185, Italy
London E1 4NS, UK S. Passerini
G. A. Chass, K. V. Tian Helmholtz Institute Ulm
Department of Chemistry and Biological Chemistry Helmholtzstrasse 11, 89081 Ulm, Germany
McMaster University S. Passerini
Hamilton L8S 4L8, Canada Karlsruhe Institute of Technology
E-mail: kun.tian@uniroma1.it P.O. Box 3640, D-76021 Karlsruhe, Germany
The ORCID identification number(s) for the author(s) of this article K. V. Tian
can be found under https://doi.org/10.1002/aenm.202203307. Department of Chemistry and Chemical sciences of Pharmacy
Sapienza University of Rome
© 2023 The Authors. Advanced Energy Materials published by Wiley- Rome 00185, Italy
VCH GmbH. This is an open access article under the terms of the G. Chen
Creative Commons Attribution-NonCommercial-NoDerivs License, Department of Chemistry
which permits use and distribution in any medium, provided the original The University of Hong Kong
work is properly cited, the use is non-commercial and no modifications Hong Kong, China
or adaptations are made.

DOI: 10.1002/aenm.202203307

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good recyclability,[7–13] which together with carbon utilization

(e.g., mineralization and carbonation) offer potential solutions
to reducing atmospheric carbon.
Lithium-ion batteries (LIBs), which use lithium cobalt oxide
LiCoO2, lithium nickel cobalt manganese oxide, lithium nickel
cobalt aluminum oxide or lithium iron phosphate LiFePO4 as
the positive electrode (cathode) and graphite as the negative
electrode (anode), have dominated the commercial battery
market since their introduction in the 1990s.[14–16] LIBs pos-
sess the highest gravimetric and volumetric energy-density
amongst current commercially viable battery systems, hence
they have been widely implemented in portable electronics,
such as mobile phones, where space and weight limitations
are paramount.[17,18] Recently, the use of LIBs has also risen in
the automotive industry due to the increased production and
proliferation of electric vehicles which are predicted to lead
the overall mass market in the near future.[19] However, the
application of LIBs is restricted by poor performance in var-
ying climates (especially extreme cold), limited cycle life, liquid
electrolyte safety risks (gas generation, leakage, fire, and even
explosion), poor transportability, and high cost as well as finite
lithium reserves.[20–22] These factors are underpinned by the
role of the electrolyte, which modulates the primary function Figure 1. Schematic of a conventional LIB detailing the SEI layer with a
of the LIBs in terms of performance, operative lifetime, and snapshot of the initial SEI structure formed on graphite electrode inter-
face which is primarily composed of lithium ethylene dicarbonate (LEDC)
safety.[23]
and lithium fluoride (LiF).
The developmental history of their predecessor lithium metal
batteries (LMBs) is far more extensive, though their commer-
cialization has been hampered primarily by safety issues,[24,25] However, despite extensive research over the past three dec-
in particular with respect to the dendritic and mossy metal ades, the exact formation, composition, and functional mecha-
deposits on the working lithium metal anodes which can cause nisms of the SEI remain one of the most ambiguous issues in
internal short circuiting, triggering fires as well as explosions.[26] battery science.[40] This is due to the spatially and temporally
Further, the lithium dendrite formation on the interfacial layer dynamic nature of this interfacial layer which forms during the
between electrolyte and anode can significantly reduce the Cou- initial charging process and grows in thickness over time as well
lombic efficiency. In contrast to the intercalation chemistry of as the changing surface mechanisms due to the continual reac-
LIBs, LMBs also suffer from stability (and cyclability) problems. tions forming a complex, structurally-disordered polydispersive
Alternative cathode materials, such as oxygen and sulfur uti- mixture.[47] What is known is that the SEI, being ≈10–50 nm
lized in lithium-oxygen and lithium-sulfur batteries respectively, thick, contains electrolyte decomposition products including
are unstable[27,28] and due to the low standard electrode potential both organic and inorganic species. Typically, the multi-layered
of Li/Li+ (−3.040 V versus 0 V for standard hydrogen electrode), SEI consists of an organic outer layer which is heterogeneous,
nearly all lithium metal can be consumed during cycling and porous, and permeable to both Li+ and electrolyte solvent spe-
almost no electrolyte remains thermodynamically stable against cies at the SEI/electrolyte interface, while the inorganic inner
metallic lithium.[25] As a result, LMBs possess inferior cycle life layer near the electrode/SEI interface allows Li+ transport.[43] SEI
and safety profiles with respect to LIBs.[29–32] formation is highly influenced by the reactivity of the electrodes
The electrode/electrolyte interface is an important electro- with the electrolytes.[37,43] A complete and stable SEI can restrict
chemical juncture where reactions proceed involving lithium electron tunneling and prevent electrolyte reduction toward
ions and electrons.[33] To achieve high energy densities, the maintaining (electro)chemical stability of the battery, whereas
electrodes in LIBs are designed to function at extreme poten- an evolving SEI can continually consume electrolytes along
tials, thus electrolytes must operate beyond their thermody- with active lithium ions inducing increased battery resistance,
namic stability limits.[34] The kinetic stability of electrolytes is capacity fading, and poor power density,[40,42,48] eventually pro-
attained when trace amounts decompose to form the solid elec- moting thermal runaway events leading to battery failure.[49–53]
trolyte interphase (SEI) (Figure 1). The SEI is a complex het- In the first few battery charge cycles, graphite undergoes a
erogeneous structurally-disordered passivation layer that forms limited volume change that slightly damages the SEI, expediting
in situ, on the negative electrode.[35–39] SEI generation is essen- the loss of lithium. Such volume changes are prominent in the
tial for LIBs to reversibly charge and discharge, effectively ena- next-generation high-capacity anode materials such as silicon as
bling long-term cycling, a necessity for numerous applications, well as lithium metal.[54,55] Additionally, the SEI layer on lithium
especially for electric vehicles.[40–45] Importantly, this interphase metal is typically unstable and poorly understood with the rela-
layer functions to inhibit further electrolyte degradation while tive volume change of lithium metal being effectively infinite.
facilitating lithium-ion transport through the layer onto the Further, the presence of dendrites widely detected in LMBs is a
negative electrode.[46] core challenge for characterization of the SEI on lithium metal

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anode. To construct superior and safer batteries, a fundamental in the Helmholtz model and the ion diffusion driven by con-
description of the SEI at the molecular level and its interfacial centration gradients caused by the electrical potential gradients
chemistry over extended time domains is requisite. (i.e., the electric field). The oppositely charged ions with respect
This review summarizes SEI formation, composition, and to the electrode are distributed in an area of thickness greater
reaction mechanisms pertinent to this intricate layer, with foci than H. Nevertheless, the Gouy-Chapman model overestimates
primarily on the graphite anode with insights into the lithium the EDL capacitance as it treats ions as point-charges leading to
metal anode. Furthermore, a discussion on the influence of predictions of unrealistically elevated ion concentrations at the
electrolyte and electrode materials is provided along with a electrode surface.[63]
recap of the state-of-the-art approaches to investigate and char- In 1924, Stern merged the Helmholtz and Gouy–Chapman
acterize the SEI. Lastly, a framework evaluating the standing models to explicitly define the Stern layer, the inner region of H
problems and future research directions including feasible (Figure 2c).[67] In the diffuse layer, the Gouy–Chapman model
computational, machine learning (ML), and experimental applies whereby the ions are mobile under the coupled influ-
approaches are outlined. ence of electrostatic forces and ion diffusion.
The presence of charged interfaces in batteries has now been
correlated with the electrolyte structure within EDL, especially
2. A Brief History ion arrangements in the Stern layer.[68–71] Initially, before the
inception of the SEI model, the Butler–Volmer equation was
The electrical properties of charged interfaces are affected by the assumed, in which direct electron transfer from electrode to
characteristics of specific electrolyte ions in aqueous solutions. lithium cations in the solution ensued.[75] However, this was
It has been established that both the surface charge densities later proved incorrect because the electron transfer from the
and the electrical potentials depend on the species (solvents, electrode to the electrolyte causes rapid self-discharge in the
salts, additives, etc.) present in the electrolyte solution.[56–59] active materials. The first observation of the passivation layer
These standard observations are known as specific ion effects, was made by Dey in the 1970s.[72,73] Peled in 1979 first intro-
though the exact microscopic origins of these effects are com- duced the now widely accepted SEI model, applicable for all
plex thus driving research directions.[60,61] The concept of the alkali metals and alkaline earth metals in non-aqueous bat-
electrical double layer (EDL) was first proposed by Helmholtz tery systems.[74] Soon after, Peled proposed a double-layer SEI
who suggested that a charged surface immersed in an electro- structure which is composed of a thin compact layer near the
lyte solution repels ions of like charges yet attracts their counte- electrode and a thick and porous secondary layer near the elec-
rions.[62] The EDL consists of a layer of electronic charges at the trolyte.[75] The first compositional information was determined
electrode surface and a layer of counterions in the electrolyte, by Nazri and Muller who detected the presence of lithium car-
separated by a small distance (H) (Figure 2a).[63,64] bonate (Li2CO3) and oligomers on lithium surfaces.[76,77] Later,
The Helmholtz model was revised by Gouy and Chapman Aurbach et al. discovered lithium alkyl carbonates, in addition
(Figure 2b) who concluded that ions are mobile in the electro- to Li2CO3 formed due to solvent decomposition.[78]
lyte solution and thus their distribution should be continuous, The formation of the passivation film on graphite was con-
following the Boltzmann distribution.[65,66] This model accounts firmed in 1990 by Fong et al.[79] Additionally, Kanamura et al.
for the combined effects of the electrostatic forces considered discovered that the compact layer near the lithium surface was

Figure 2. Representation of the electrical double layer structures as proposed by a) the Helmholtz model; b) the Gouy–Chapman model and c) the
Gouy–Chapman–Stern model. H is the double layer distance in the Helmholtz model and Stern layer thickness; Ψs is the potential at the electrode
surface. Inspired by Pilon et al.[70]

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Figure 3. Schematic of the multilayer model on lithium electrode introduced by Aurbach et al. and the “mosaic” disordered poly-heterogenous micro-
phase SEI model on lithium or carbon electrode as proposed by Peled et al.[82–84]

comprised of lithium fluoride (LiF) and lithium oxide (Li2O), complicated by the fact that the electrolyte is a multi-component
with the porous layer above this consisting of LiF along with system consisting of solvents, salts, and additives, engaging in a
organic compounds.[80,81] These led to Aurbach's multilayer myriad of interactions with the electrode surfaces, the strength,
model of the Li-solution interphase, highlighting the division and nature of which are determined by configurational and con-
of the various layers (Figure 3).[82] Peled et al. amalgamated formational arrangements of the components.[71,91–95]
previous results into the widely accepted “mosaic structure” of The HOMO-LUMO energy level is derived from approxi-
the SEI (Figure 3),[83,84] wherein the SEI is composed of both mated electronic structure theory exploring electronic prop-
organic and inorganic products from electrolyte decomposition: erties of isolated species, hence their energy levels are not
specifically near the lithium surface, compact layers of inor- indicative of molecules participating in redox reactions. It has
ganic species such as Li2CO3, LiF and Li2O are thermodynami- been established that the redox potentials are directly related
cally stable against lithium,[78,80,84] whereas, near the electrolyte, to the Gibbs free energy difference between the reactants and
the layers consist primarily of organic species like polyolefins reaction products. However, it is essential to understand that
and semicarbonates.[78,80,84] In 1999, Aurbach et al. illustrated using such concepts alone can lead to erroneous descrip-
the SEI formation processes commencing from electrolyte tions.[43,92] For example, the calculated HOMO energies of bat-
reduction on electrode surfaces.[85] Since the turn of the last tery solvents have led to overestimation of electrolyte stability
century, further evidence of the multi-layered SEI on lithium neglecting H- and F-transfer reactions arising from electrolyte
and graphite electrodes was substantiated by Edström as well decomposition; the presence of other species also impacts the
as Cresce et al. using in situ and synchrotron techniques.[35,86] redox potentials of solvents, which may lead to an offset as high
as 4 eV from the HOMO energies.[68,96] This is exemplified by
the oxidation of isolated ethylene carbonate (EC) which occurs
3. Current Progress at ≈2 V higher and its HOMO energies ≈4 eV lower than the
energy levels where the oxidation of the solvent transpires.[97]
3.1. Electrochemical Stability of Battery Electrolytes Thus, Peljo and Girault suggested that it is more correct to
define the electrochemical stability of electrolytes as the poten-
Advances in understanding the electrode/electrolyte interface tial of electrolyte reduction at negative potentials and the poten-
stem from thermodynamic considerations of electrolyte reac- tial of solvent oxidation at positive potentials (Figure 4).[92]
tivity in terms of reduction and oxidation at positive and negative The development of superior battery chemistry depends
potentials.[8,36,43,87] The widely accepted concept first introduced on the stabilization of electrode/electrolyte interfaces; recent
by Goodenough and Kim states that the SEI layer forms when quantum chemical (QC) electronic structure calculations high-
the redox potential of the electrodes in a battery lies outside of light the influence of electrolyte redox stability.[71,98,99] This is
the electrolyte electrochemical window. In this case, the stability governed by solvent-salt partitioning within the EDL near the
window of a battery electrolyte is represented with the energy electrolytes as well as the number of lithium cations com-
levels of the highest occupied molecular orbital (HOMO) and plexing the solvents or anions (Figure 4). Consequently, these
the lowest unoccupied molecular orbital (LUMO) of the solvent intricate phenomena impact the SEI formation and its structure
molecules. This concept of where electrolyte redox reactions take and properties, which are further complicated by the coupling
place is prevalent in the battery literature defining that at elec- of electronic and ionic degrees of freedom in the layer. To a cer-
tron energies higher than the LUMO, the solvent-electrolyte is tain extent, the electronic insulation capability of the SEI com-
reduced, and at electron energy levels lower than the HOMO, the ponents that can be quantified by the LUMO-HOMO gap may
solvent-electrolyte is oxidized.[88–90] Electrolyte stability is further aid the understanding of the structure-property relationship at

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Figure 4. (Top) Example of interfacial electrolyte structure as solvated Li (in this example Li is coordinated to EC in the presence of PF6 anion) diffuses and
intercalates on the anode surface. The multi-component nature of the electrolyte highlights the complexity of the electrode/electrolyte interface in terms
of electrochemical stability, structure, and dynamics. (Bottom) Electrochemical stability window of battery electrolytes; inspired by Peljo and Girault.[92]

the interface.[98] Such insights provide the foundation for the dissolve at normal operating temperatures.[103] While organic
establishment of guiding principles for interphase formation. SEI components such as ROLi or ROCO2Li (R = alkyl group
with a low molecular weight)[104] are among the most soluble
compounds and the presence of such moieties can cause the
3.2. SEI Formation, Composition, and Structure diffusion of inorganic products into the electrolyte. Thus, an
SEI containing Li2CO3 is preferred over one containing meta-
The formation of the SEI is influenced by the cathode and stable organic species, such as ROLi or ROCO2Li.
anode materials along with the electrolyte composition.[46,100,101] Dahn et al. first demonstrated that the lithium ions inter-
The SEI formation completes under fast kinetics prior to the calate reversibly on graphitic carbon in liquid electrolytes that
onset of the intercalation reaction, provided that the decompo- contains EC, due to the generation of the SEI,[79] and when pro-
sition reaction potentials for the SEI formation are more posi- pylene carbonate (PC) is utilized, irreversible lithium interca-
tive than the anode lithium ion intercalation potential.[41] Most lation ensues, relevant to graphite exfoliation. Influentially, the
high purity electrolyte solvents have a decomposition potential difference of a single methyl group between EC and PC signifi-
of 4.6–4.9 V versus Li/Li+, close to the preferred potential of cantly alters the SEI composition and thus the effects of these
5 V for LIBs.[102] A complete SEI should possess high lithium- distinctions have been the focus of numerous studies.[40,98,105,106]
ion conductivity and negligible electronic conductivity to limit This highlights the importance and chemical specificity of the
further reduction of the electrolyte on the graphite surface.[41] generated SEI which is regulated by its electrolyte precursor
Whereas the ion conductive property facilitates the permea- constituents as well as the resultant reactivity. The SEI forma-
tion of lithium ions, offering a pathway for ion intercalation tion on graphite in the presence of EC is highly stable, con-
in the graphite layers. Ideally, the SEI layer should be strong sisting predominantly of LEDC ((CH2OCO2Li)2).[104,107–110] The
and flexible enough to withstand volume change due to expan- morphological evolution of the SEI has been further elucidated
sion during charging and contraction during discharging of the with scanning electron microscopy (SEM),[49,111,112] suggesting
anode throughout the cycling process. that the SEI in the initial formation stages is comprised of
To reduce the loss of irreversible capacity and lithium in the loosely bound organic polymers, in contrast to the more com-
initial cycles, the SEI chemical composition should be com- pact inorganic salt structures as the potential decreased.
prised of stable, insoluble, and compact compounds, as the Further, the chemical composition, structure, and thickness
solubility of the decomposed SEI components is a key physical of the SEI are also affected by the electrode surfaces.[113,114] A
property for electrolytes to ensure a high-capacity retention. study by Zane et al. highlights the dependence of electrode per-
Studies on the heat of salt dissolution in EC:DMC (ethylene formances on their surface chemistry in solutions.[113] The SEI
carbonate: dimethyl carbonate) have highlighted that inor- morphology was altered with differing cycle times and tempera-
ganic compounds such as Li2CO3 are endothermic and hard to tures (Figure 5). In addition, differences also arise between layers

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Figure 5. SEM micrographs (≈50 µm × 50 µm) of a surface SEI film on a graphite electrode in LiBF4 EC/PC 3/1 solution: a) after the first discharge;
b) after prolonged cycling at room temperature; c) after cycling at T = 55 °C. Reproduced with permission.[113] Copyright 2001, Elsevier Science. (Bottom
right) Schematic representation of the edge and basal planes of highly ordered pyrolytic graphite (HOPG).

formed at graphite basal and edge planes (Figure 5).[115,116,119] For an electrolyte comprised of 1 m LiPF6 in EC:DMC and
The basal plane is the surface parallel to the graphene planes highly ordered graphite, the SEI on the edge plane is believed
whereas the perpendicular surface is called the edge plane.[117] to be several nanometers thicker than on the basal plane, in
At basal planes, the SEI formed must be electronically insu- line with the observation of higher reaction current at the edge
lating and impermeable to other electrolyte components, yet plane.[122–124] Nevertheless, the depicted SEI structure is influ-
ionic conductivity is not requisite. Lithium cannot intercalate enced by the analyzing conditions, as even when the same
into graphene layers across basal planes thus SEI formation at electrodes and electrolytes were used the compositions varied.
these sites should be reduced to avoid loss of lithium inventory. While the underlying cause of the differences between SEIs
The differing characteristics of the layers generated at basal and formed on HOPG basal and edge surfaces requires further
edge planes mean that true SEI formation potentials cannot be examination in order to provide a fundamental and rigorous
obtained by traditional electrochemical measurements. understanding of SEI formation, due to various hypotheses
The compositions of the SEI formed on the basal and edge having been put forth to elucidate the molecular interactions at
planes of highly oriented pyrolytic graphite (HOPG) (Figure 5) play between solvated complexes and graphite. An early study
are also different.[116,118] The basal plane manifests atomic flat- by Besenhard et al. suggests solvated lithium complexes inter-
ness and low defect density while the edge plane contains dan- calate between graphene layers which then decompose to form
gling bonds, defects, sp3 sites as well as functional groups due to the SEI at the edge.[125] This was supported by Shkrob et al.’s
the sudden termination of the lattice.[117] Thus, with more reac- finding that the EC derived SEI layer is polymeric, passivating
tive sites on the edge planes, a denser and more homogeneous the electrode surface.[126] Nevertheless, contradictions arise
SEI layer is most often formed[119,120] and predominantly com- when PC is used as a network of linear polymers that does not
prised of inorganic species of carbonates and semicarbonates[117] hinder additional electrolyte decomposition.[126,127]
due to salt reduction, while on the basal plane, the SEI is com- Another hypothesis is that lithium ions desolvate, thus
prised mostly of organic species of oligomers[117] due to solvent they intercalate in between graphite layers at edge sites with
reduction. This was further confirmed by Argon sputtering of remaining salt anions (which were previously bound to Li)
the SEI depth profile.[117] On edge planes, the SEI thickness does decomposing to form inorganic species such as LiF.[115,128–131] In
not vary considerably after the first cycle, as determined by in contrast, the basal planes are exposed to fewer (free) salt anions,
situ atomic force microscopy (AFM) measurements.[119,121] This but more unbound solvent molecules, hence a larger number
suggests the SEI generated on the edge in the initial cycle is of organic compounds are produced. However, the fast charge
already both electronically insulating and ionically conducting. transfer kinetics on the edge plane can promote electrolyte

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decomposition via electron transfer ring opening reactions of The reactions are driven by various factors, such as the
cyclic carbonates, producing radicals.[128,129] Such reactions may lithium ion radius and the solvating power of the specific sol-
explain the larger proportion of alkoxides and carbonates iden- vent used in the electrolyte which is related to its dielectric
tified on the edge plane than on the basal plane.[36,115] constant.[93,148] Lithium ions tend to be strongly solvated by
In terms of properties, the model (ideal) SEI layer should solvent molecules, with solvents preferentially coordinating to
be chemically stable against lithium, electronically insulating, lithium outcompeting anions. The concentration polarization
ionically conductive and it must prevent lithium-electrolyte causes solvated lithium ions to diffuse toward the graphite sur-
contact. Electron tunneling proceeds when the SEI thickness face (edge sites) which then transform into the site for reduc-
is <1 nm.[25] Although the electron tunneling during the initial tive decomposition reactions.[98] This is a critical step where
SEI formation cycles is more pronounced as the primitive SEI competitive solvation of lithium by anion or solvent molecules
layer is thin, once the thickness increases beyond this ≈1 nm dictates whether an electrolyte is destined to form a stable
threshold, electron transfer via electron tunneling is minimal. protective interphase. Yan et al. proposed several reaction path-
The ionic conductivity of the SEI is correlated with the species ways including 1) intercalation of desolvated lithium ions into
present in the multiphase layer, though the nanometer thick- the graphene layers, 2) heterogeneous transfer of electrons
ness and complex morphology render the determination of the from the graphite electrode to the solvent molecules, 3) co-
ionic conductivity and Li+ transport mechanism difficult using intercalation of the solvent molecules and the solvated lithium
experimental techniques. Hence, theoretical methods along ions into the graphene layers and 4) heterogeneous transfer of
with indirect experimental observations were adopted focusing electrons from the graphite electrode to the salt anions.[149]
on the SEI structure and its individual components such as LiF The most spontaneous reaction is when desolvated lithium
and lithium alkyl carbonates.[132–137] ions intercalate into the graphene layers at a potential more nega-
tive than the other competing reactions during cathodic polariza-
tion. Electron transfer from the graphite electrode to the solvent
3.3. SEI Formation Mechanism: Reduction and Decomposition molecules as well as co-intercalation of solvated lithium ions into
the graphene layers are the most debated pathways in the bat-
Under extreme battery operating conditions, such as high tem- tery literature. The reduction of carbonate solvents follows either
perature (>60 °C), high charge rate, and extended electrochem- a one-electron or two-electron reduction process. In the one-
ical cycles, results in either the growth of the SEI thickness or the electron reduction process a carbonate solvent, for example, ethyl
loss of its protective ability, leading to performance deterioration methyl carbonate (EMC), produces an anionic intermediate spe-
via numerous aging mechanisms.[46,121,138] With the omission of cies [CH3CH2O(C•-O−)OCH3] which subsequently reacts with Li+
PC, carbonate solvents utilized with the conventional electrolyte to produce CH3CH2OLi; whereas in the two-electron reduction
salt of LiPF6 form stable robust passivating layers.[139,140] Though process, for example, DMC, the reduction process involves the
PC does perform well at low temperatures (<−10 °C) when used transfer of two-electrons and Li+ to produce lithium carbonate
in conjunction with additives.[141] Further, the SEI layer formed and a gas.[150,151] In the case of EC, due to its high dielectric con-
on carbon-based anodes, such as graphite, has favorable micro- stant and high polarity, it is reduced in a one-electron transfer
structuring and properties with respect to other anode mate- process at the graphite surface[79,126,127] to form an intermediate
rials.[142–145] Several reduction processes compete on the carbon/ radical anion that then undergoes additional decomposition to
graphite surface during charging. Typically, the reactants are sol- form LEDC; a reactive species which reacts with trace water in
vents, salts, additives, and trace air impurities (e.g., water). The the electrolyte to produce Li2CO3.[104,110]
electrochemical reaction rates vary depending on their inherent However, it is proposed that EC actually undergoes a two-
properties, such as exchange current density, reduction activation electron transfer reaction with Li+ to form Li2CO3 and C2H4
energy, reductive potential as well as the identity of the reaction (Figure 6).[72,125,152–157] The solvated lithium ions co-intercalate
sites, basal or edge.[122,146,147] Hence, analyses of the SEI forma- into the graphene layers forming intermediate graphite interca-
tion mechanism remain a core challenge due to the varying bat- lated compounds (GICs) which are then reduced to form the SEI.
tery conditions and differing electrolytes employed. Alternative reaction pathways involve the PF6− anion's attack on
Generally, carbonates from the electrolyte solvent precipitate the EC molecule forming CH2FCH2OCOOPF3O− and PF5.[158–160]
with lithium ions to form Li2CO3, lithium alkyl carbonates, or The LiPF6 salt is thermodynamically unstable thus readily reacts
other organic compounds while the salt (LiPF6) forms LiF after with Li2CO3 to produce LiF, POF3 and CO2. The trace impurities
reduction.[41] The standard reaction scheme for the reduction of such as H2O and CO2 in solution react with Li+ to form Li2CO3,
cyclic carbonates is presented in Figure 6. Most reduction pro- LiOH, and Li2O, which form part of the SEI.[161–163] These spe-
cesses occur in the range of 0.8 V and 0.2 V versus Li/Li+ on cies can accumulate on the electrode surface and may crack due
highly ordered graphite. The SEI formation process comprises of to differing coefficients of thermal expansion of the deposit layer
two steps, though the exact mechanism remains assiduously dis- and the graphite.[164] Also, LiPF6 reacts with water contamina-
puted.[41] In the first step, the graphite electrode is polarized, with tions in the battery electrolyte releasing HF and HPO2F2 which
the species in the organic electrolyte undergoing reductive decom- are harmful species in case of leakage; whilst also detrimentally
position generating new compounds. In the second step, the new decreasing battery performance.[160,165] Hence, why it is impera-
compounds precipitate to form the SEI till all the graphite surface tive to keep impurity level in the electrolyte to a minimum.
sites are covered. Most studies focus on the reduction pathways The initial SEI components formed from conventional elec-
of solvent molecules particularly of carbonate-based solvents with trolytes are determined by the reduction products of EC and
LiPF6 as these are the conventional electrolytes used in LIBs. LiPF6. The formation and growth of the SEI cause continual

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Figure 6. (Top) Putative reaction scheme for the reduction of cyclic carbonates and the formation of SEI components. Q represents the OCO3−Li+
group. Inspired by Shkrob et al.[126] (Bottom) The EC decomposition and precipitation pathway including the radical anion formation believed to be
the rate-determining step (reaction scheme 1), formation of the ethylene dicarbonate anion (reaction schemes 2 and 3), and the precipitation of solid
LEDC (reaction scheme 4).

changes in its composition, specifically an increase in the con- The insoluble species include LiF, Li2CO3, Li2O, lithium car-
centration of inorganic species, such as LiF and Li2CO3, and boxylates, lithium alkoxides, and lithium fluorophosphates,
a decline in the concentration of organic compounds (lithium while the typical gaseous species are CO2 and ethylene.[48]
alkyl carbonates).[48] The initial SEI compounds are also The presence of acidic impurities, for example, HF and PF5,
unstable at the graphite anode and decompose to produce a or transition metals, may catalyze these thermal decomposi-
mixture of species with mixed solubility in the electrolyte and tions, which are proposed to be the culprit for the disparate
gaseous species. Due to the decrease of insoluble compounds SEI compositions reported by different research groups. The
the SEI becomes progressively more porous over time. In LIBs varying conditions the cells are cycled in, as well as the higher
using standard carbonate-based electrolytes the soluble species ratio of electrolyte to electrode material utilized in experimental
include ethers, fluorophosphates, and oligoethylene oxides. cells relative to commercial cells may result in an elevated

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proportion of impurities accelerating the decomposition of the SEI is mainly comprised of solvent reduction products. Overall,
initial SEI components.[48,162,166] the heterogeneous polydispersity of the SEI stems from the
A mechanism for the evolution of the SEI during aging was decomposition reactions of the initial products.
proposed by Heiskanen et al. (Figure 7) detailing the progres- In addition to the growth-decomposition mechanisms in con-
sion of the SEI composition following decomposition reac- ventional electrolytes, more modernized electrolyte mediums
tions.[48] In addition, the primary decomposition reactions of have been formulated by tuning the solvation structure of the
the SEI components are reported as follows: LEDC, a major electrolyte; this is achieved by increasing the amount of lithium
component of the initial SEI (other than LiF), is unstable thus salt to achieve near-saturation concentrations. These systems
decomposes into a complex mixture of products (Figure 7).[167] differ in that Li+ ions coordinate not only to solvents (as in con-
With the SEI becoming progressively more porous, the electro- ventional electrolytes), but they are also bound to anions. Con-
lyte can access the surface of the graphite electrode facilitating sequently, the Li+-anion-(solvating solvents)n ion sheath can
additional reduction of the electrolyte to produce LEDC and participate in the SEI formation process. Such electrolytes are
LiF, forming the outer SEI layer. And with continued cycling categorized as high concentration electrolytes (HCEs) and local-
further EC reduction and decomposition reactions take place ized high concentration electrolytes (LHCEs).[168,169] As a result,
leading to thickening of the layer, as well as more stable inor- the SEIs formed using these modern electrolytes predominantly
ganic species concentrating near the surface. Consequently, the consist of anion-based decomposition products, with the resultant
inner SEI consists primarily of inorganic species and the outer SEIs formed deemed to be ionically more conductive.[170]

Figure 7. (Top) Initial SEI evolution on graphite showcasing the structure, thickening, and subsequent decomposition. Due to recent advancements
in the characterization of the SEI components, lithium ethylene mono-carbonate (LEMC) has been included in this SEI representation.[171] This figure
is inspired by Heiskanen and co-workers.[48] (Bottom) Primary decomposition reactions of the SEI species LEDC and Li2CO3.

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3.4. SEI Evolution on Lithium Metal Anode graphitic anodes, due to their similar reduction potentials, how-
ever, the electrochemical and thermodynamic stability of the SEI
Works have shown that the SEI governs the practical application components differ.[178] If the initial SEI layer on a lithium anode
of LMBs, wherein: the SEI is responsible for transporting lithium is rich in inorganic species, it will prevent further Li metal-
ions as well as protecting metallic lithium from parasitic reac- electrolyte reactions, thus slowing down the SEI growth.[173] The
tions with electrolytes.[24,25,32,45,172,173] Conversely, lithium plating/ inverse occurs when the SEI layer is abundant in organic species,
stripping is dictated by the composition, morphology, and thick- whereby a faster SEI growth rate is observed. Jiao et al. reported
ness of the SEI which are related to the cycling stability of LMBs. that the composition of the SEI layers in the same electrolyte
However, due to the difficulty in the in situ and operando study varied with the Li capacity utilization and charge/discharge condi-
of the electrochemical reactions occurring in an enclosed battery, tions.[179] The SEI layer on the lithium metal anode surface can
including LMB, the exact features of the SEI remain unresolved. be described as having three components. Firstly, the initial inor-
Owing to the high reactivity of lithium metal, it reacts with elec- ganic compounds formed before the anode are exposed to the
trolytes forming the native SEI layer, which is usually fragile, organic electrolyte. Secondly, the insoluble inorganic and organic
non-uniform, and unstable, together with the driving force of the species are produced via chemical reactions between Li metal and
order-disorder transition ongoing in the SEI phase. In this case, organic electrolytes when the anode is saturated in organic elec-
the initially ordered system (electrodes, homogeneous electrolyte, trolyte. Thirdly, the insoluble and partially soluble compounds are
etc.) evolves to a disordered phase with the formation of the SEI, generated via the electrochemical reduction reactions of the elec-
itself highly disordered from nano-through to mesoscopic scales. trolyte components. The SEI features on lithium metal anodes are
The SEI itself has a gradient structuring from the anode and out- contingent on the cycling conditions and electrolyte composition.
ward into the electrolyte bulk, one that is functional and requi- Dendrite formation is the main hindrance to the practical
site for high efficacy. Such disordering contributes to the rise of application of LMBs. Non-uniform lithium deposition promotes
side-reactions and the formation of disordered lithium dendritic uncontrollable needle-like dendritic electroplating causing poor
structures.[174,175] This native layer is easily eroded by the stress cycling efficiency and safety risks.[25,173] Heterogeneous lithium
caused by electrode volume change and uneven lithium plating/ plating side reactions can occur caused by Li deposition/dis-
stripping resulting in direct contact of lithium metal with the solution, though the inverse reaction, known as “stripping”,
electrolyte. Subsequently, a new SEI layer is continually gener- can recover lithium metal. Uneven deposition and stripping
ated which causes continuous consumption of the electrolyte of lithium results in the formation and growth of cavities, with
and lithium metal. What's more, the SEI can alter the distribu- reports showing that these regions stem from unevenly formed
tion of lithium ions from the bulk electrolyte to the anode.[24] areas of the SEI; these cavities are electrochemically more active
This occurs whereby the lithium ion is desolvated, diffusing than flat surfaces, due to increased surface area: volume (SA: V)
through the bulk SEI with access to the Schottky vacancies per- values.[180–182] Plated metallic lithium undergoes rapid reactions
vading the layer. Eventually, the ion reaches the anode surface with the electrolyte to form the SEI, which can then electrically
where it accepts an electron from the current collector before its isolate the remaining Li to form “dead lithium,” which cannot
deposition as Li metal. be recovered. Dead lithium manifests reduced conductivity and
In synthetic and laboratory settings, commercial lithium loss of lithium inventory with dendrites that can puncture the
metal foil is usually utilized as the lithium metal. Due to the high separator causing an internal short circuit. The Li morphology
surface reactivity with O2, N2, and H2O when exposed to ambient displays that dendrites possess a diameter of a few hundred
air,[176] lithium metal foil is always covered by a layer of thin film nanometers, with dendrite growth shown to be dependent on
comprising Li2O, Li2CO3, and LiOH, which is naturally retained the current distribution.[29,183,184] A key strategy to minimize the
when used in LMBs. Though this layer on the lithium metal sur- degradation of the lithium metal anode relies upon a uniform
face is stable, when put into contact with the electrolyte solution distribution of current density across the entire anode surface
it spontaneously reacts with the solvent and anions within mil- to promote dendrite-free deposition of lithium.
liseconds or microseconds; postulated to even be as quickly as
femtoseconds.[47] In LMBs an external voltage is applied to create
an electric field between the cathode and the anode in order to 4. State-of-the-Art Approaches
activate the electrochemical plating and stripping of lithium ions.
Subsequently, this results in the breakdown of the passivation Knowledge about the passivated interface between electrodes
layer on the lithium metal anode triggering additional reaction and electrolyte is crucial as this interface affects the capacity,
of exposed lithium metal with the electrolyte solution. With the cycling stability, properties, and safety of electrochemical energy
use of lithium metal as the anode in LMBs, more lithium metal storage devices. Nonetheless, there still lacks a comprehensive
atoms are accessible for electrochemical reactions with the elec- understanding encompassing morphology, phase, and chemical
trolyte solution therefore a greater supply of lithium leads to the composition, especially on the nanoscale. The characterization
formation of a “fresh” SEI during each cycle. The surface film of the SEI is difficult because it is a very thin layer with barely
formation on lithium metal anodes was examined by Aurbach distinguishable boundaries with the electrolyte.[37,40] As a result,
et al. (Figure 8) in alkyl carbonates and 1-3-dioxolane solutions; experimental analyses are challenging as it is difficult to ascer-
supported by the associated and widely accepted schematic illus- tain the thickness of the layer on the carbon surface, making
tration of the process.[161,177] precise peeling off near impossible. As the chemical species
On lithium metal anodes, the general SEI layer structure of the solvent and SEI are similar, it is hard to discern which
and composition as well as the electrolyte stability are similar to component belongs to the SEI and which to the electrolyte. This

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Figure 8. Schematic illustration of the surface film formation on lithium electrodes in alkyl carbonates and in 1-3 dioxolane solutions. This figure is
inspired by Aurbach.[177]

is complicated by the sample preparation (separation, washing, With the limitations of current experimental techniques
and isolation) thus it is unlikely that the SEI maintains its orig- to describe the SEI beyond its chemical composition,
inal composition, with its components likely to undergo modi- computational modeling has emerged as a feasible approach to
fication as well as degradation. Further, the components of the making the structure of SEIs intelligible on length scales span-
SEI are highly sensitive to air contamination and humidity, for ning the atomic and nanoscopic through mesoscopic, to the
example, ROLi and ROCO2Li can react with ambient CO2 to full battery systems.[99,209–214] The proposed mechanisms, such
form Li2CO3. It is also worth mentioning that SEI formation is as the initial formation of the SEI layer through the reduction
affected by other factors including additives, concentration, cur- of the electrolyte on the anode surface via one- or two-electron
rent rate, state of charge, temperature, and voltage. reductions, needs to be verified with advanced techniques that
To characterize the SEI, specific experimental techniques can depict the reactions at the electrode/electrolyte interface at
ranging from microscopy to spectroscopy have been applied. extremely small timescales (e.g., pico- or even femtoseconds).
To examine the surface of the layer, surface analysis techniques To explicate which electrolyte species are most susceptible
including AFM, scanning tunneling microscopy (STM), sec- to reduction, QC and molecular dynamics (MD) simulations
ondary ion mass spectroscopy (SIMS), and X-ray photoelectron have been employed, with a range of studies completed to
spectroscopy (XPS) are used.[35,50,86,119,121,150,185–191] Whereas for calculate the redox potential of electrolyte species, in par-
imaging the surface film, SEM and transmission electron micro­ ticular organic (carbonate) solvents and the conventional salt
scopy (TEM) are the preferred techniques, albeit retrospective to LiPF6.[68,96,153,215–220] Other works characterized the decompo-
their destructive natures.[49,102,192–196] In addition, vibrational spec- sition mechanisms and reaction pathways of organic solvents
troscopies are employed to correlate surface information with (Figure 9), with particular foci on one of the most important
functionality, including Fourier transform infrared (FTIR) and components, EC.[155,221–223] Also, the oxidative decomposition
Raman spectroscopies.[76,164,197–203] The most commonly employed pathways of carbonates and solvents were studied using QC
diffraction techniques include X-ray diffraction (XRD) and tech- calculations.[144,156,218,224] Note that such reduction mechanisms
niques that provide bulk information of the SEI components such are involved in the initial SEI formation process, nonetheless,
as nuclear magnetic resonance (NMR).[77,109,171,186,204–208] as these products accumulate on the electrode surface, they

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1 m LiPF6 in EC or DMC as well as specific properties including

cohesive energy, density, and solubility in the solvent.[230–233]
However, these force fields failed to describe the dynamic
breaking of covalent bonds. The ReaxFF reactive force field was
subsequently developed for LiCHO systems that use a
bond-order term along with a variable charge based on the elec-
tronegativity-equalization method (EEM) to describe covalent/
ionic bond formation/breaking.[223,234,235] In the ReaxFF model,
the electrons are treated implicitly prohibiting true simulation
of redox processes (e.g., reduction reactions of EC) thus the eRe-
axFF method was developed which treats electrons explicitly cir-
cumventing this limitation.[236,237] Nonetheless, the parameteri-
zation of the reactive force field models necessitates continual
advancements to accurately describe such complex systems.[238]
Recently, advancements in the study of the battery inter-
phase were achieved using state-of-the-art computational and
experimental approaches. To elucidate the nanoscale heteroge-
neity of the SEI, Raman signal enhancement techniques have
been employed which use the plasmon resonance properties
of metal nanostructures.[239] Such methods can deduce the
composition of surface films on different electrode materials
upon direct contact with organic (i.e., carbonate) electrolytes.
This is exemplified by surface-enhanced Raman spectroscopy
and tip-enhanced Raman spectroscopy (TERS), the latter uti-
lized to study the amorphous silicon thin film anodes toward
understanding SEI topography and chemical mapping.[201]
TERS showed good correlation between the SEI structure and
the distribution of LEDC and poly (ethylene oxide) (PEO) type-
oligomer species. This technique is also applicable to the inter-
phase in alternative battery chemistry such as Na-ion and mul-
tivalent redox systems. Furthermore, shell-isolated nanopar-
ticle-enhanced Raman spectroscopy was used for the operando
study of interfacial composition changes on tin (Sn) anodes
upon cycling in LIB electrolyte.[202]
Figure 9. An exemplary computational study on the redox decomposition A concerted approach combining electrochemical quartz
pathways of electrolytes. The calculated profile of free energy (∆G) of EC
(top), PC (middle), and FEC (bottom) decomposition assisted by lithium
crystal microbalance (EQCM) and AFM[240] was applied to quan-
ions (the hydration energy of the solvated electron in water was −1.63 eV; titatively monitor the interphasial species as they evolve on the
the shaded areas denote the radical carbon and oxygen). Reproduced with electrode surface at various potentials in situ. EQCM is a highly
permission.[156] Copyright 2021, The Royal Society of Chemistry. sensitive mass monitoring technique that permits the weighing
of species depositing on or that are lost from the graphite anode
undergo additional reactions as the surface becomes increas- as a function of the applied potential. AFM images display how
ingly electronically insulating. HOPG interacts with the solvated lithium ions during charge
Toward the study of larger ensembles, ab initio MD (AIMD) and discharge processes. LiF and lithium alkyl carbonates were
has been performed to study the initial SEI formation pro- identified by weighing the graphite anode with an EQCM,
cess including the decomposition of EC on graphite sur- although the exact alkyl carbonate which was predominantly
faces.[222,225–227] AIMD has the advantage of computing the formed could not be resolved. Differential electrochemical mass
exact nuclear forces from the electronic structure without the spectroscopy further proved the preferential reduction of cyclic
use of a fixed chemical topology nor the approximations that carbonates (over acyclic carbonate species); the primary compo-
typify classical force field based methods. This is aided by the nents detected in the SEI. Relevantly, the probability for the SEI
use of periodic boundary conditions which provides the ben- to be re-oxidized is dependent on its age, with the SEI on well
efit of solvation effects in the bulk electrolyte or surface effects cycled electrodes more difficult to re-oxidize.
stemming from the electrode that can be fully captured, despite The use of microscopy and spectroscopic techniques have been
the limitation of unrealistic periodicity.[94,225,227–229] To enable instrumental in resolving the composition and the thickness of
simulations of larger system size and extended timescales, clas- the SEI.[102,195,196] The surface reactions of electrolytes were inves-
sical force fields such as condensed-phase optimized molecular tigated by Nie et al. using binder-free graphite anodes allowing
potentials for atomistic simulation studies and the atomistic assessment of the SEI.[49] A combination of TEM with energy
polarizable potential for liquids, electrolytes and polymers were dispersive XPS along with solution NMR and FT-IR spectroscopy
developed.[230,231] Such classical force fields capture solution enabled the direct analysis of the graphite SEI of LIBs to establish
structures and transport properties of electrolyte, for example, that for EC/LiPF6 electrolytes, the graphite SEI has a thickness of

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≈50 nm after the first full lithiation cycle.[49] The layer was com- structure of the EDL (which becomes anion depleted, because
prised of predominantly LEDC and LiF whereas upon alteration the anions are expelled from the inner-Helmholtz layer struc-
of the electrolyte composition, using EMC/LiPF6, the graphite SEI ture once the electrode is negatively charged) predicting the
is nonuniform and thinner (≈10–20 nm), containing lithium ethyl eventual interphase chemistry. Simulation snapshots along
carbonate (LEC), lithium methyl carbonate (LMC) and LiF. with line plots of the ion distribution close to the Cu electrode
Wang and co-workers’ study provided new insights into the and 1.0 m LiFSI in DME electrolyte with increasing voltage
composition of the SEI in LIBs which contradicts the current showed increasing Li+ enrichment (Figure 10). The liquid SIMS
consensus that LEDC is the primary organic component.[171] chemical profiles reveal a structured SEI with a dense inorganic
Structural and spectroscopic characterizations suggest LEMC is (predominantly Li2O) inner layer (thickness ≈15–20 nm) that is
the major product with complex interconversions and equilibria LiF depleted while the outer layer is rich in organic species.
at play. The authors hypothesize that LEDC does not exist in the The effect of the electrode surface on SEI evolution was
typical LIB environment due to the following reasons: (1) past explored by Zhu et al. focusing on the differences in interphase
studies have linked the organic SEI components to the LEDC formation on HOPG and disordered graphite electrodes.[242]
standard which was actually LEMC; (2) LEDC is highly reactive The preferential formation of the SEI at graphite with defects
to protio-impurities which are abundant in all cell assemblies, over the HOPG was confirmed, supported by DFT calculations
from trace moisture in bulk electrolytes to the graphite anode where the adsorption energy barrier of EC bound to Li is lower
surface.[171] Therefore, LEDC cannot endure in this environ- on the disordered graphite surface. The presence of defects led
ment and even if it is formed via the one-electron reduction to the formation of a thinner, denser, and more uniform SEI
reaction, it is most likely to be converted to LEMC and LMC on the electrode surface with stronger passivating capability
through reactions with protons and DMC. In addition, it was as well as good stability upon cycling.[242] It was also reported
determined that LEMC possesses relatively high Li+ conduc- that the defected graphite surface induced an SEI rich in LiF
tivity which benefits the function of the interphase. Although which aids the passivating component in the layer. This opens
the exact formation mechanism of LEMC remains to be estab- new vistas for the application of graphite with the defects as it
lished, such insights offer a clearer explanation of interphases can be coated onto conventional graphite electrodes along with
and their specific properties relating to LIB performance. other high-capacity electrodes (Li, Si, and Sn).
A dynamic explanation of SEI formation in LIBs using oper- First-principles simulations of the thermodynamic, kinetic,
ando liquid SIMS in combination with MD simulations[241] and electronic properties of the interface between LiF and
established that prior to any interphase chemistry occurring, Li2CO3 showed a significant reduction in the activation barrier
an EDL forms at the electrode/electrolyte interface due to the for Li transport, due to the interface possessing the highest Li
self-assembly of solvent molecules. The formation of the EDL ion diffusion coefficient.[234] As we note, this study was con-
is guided by Li+ and the electrode surface potential with the ducted on a crystalline SEI structure and thus we highlight that

Figure 10. Simulation snapshots and line plots of the ion distribution near a Cu electrode and a 1.0 m lithium bis(fluorosulfonyl)imide (LiFSI) in
1,2-dimethoxyethane (DME) electrolyte interface with increasing voltage. Snapshots (top) from the simulation at a) 0 V, b) 1.0 V and c) 2.8 V with Cu
electrode on the left and the ion distributions near the anode. The corresponding line plots of the ion distribution are shown in (d), (e), and (f). When
no potential was applied no Li+ enrichment at the interface was detected, as shown in (d). (e) and (f) suggest the thickness of the EDL is less than
1 nm. As a higher potential is applied the Li+ enrichment at the electrode/electrolyte interface becomes more significant, comparing (e) and (f). (The
dashed lines indicate an even distribution). Reproduced with permission.[241] Copyright 2020, Springer Nature.

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one must consider the different compositions of the interfaces restricted by typical operating temperatures/pressures far from
with the possibility of amorphous regions being generated in the the battery ambient range (the latter also by selection rules); the
multiphase SEI which will alter the Li-ion diffusion pathways, acquired results and conclusions are likely qualitative at best.[245]
in-turn impacting the ionic conductivity of the phase. As the SEI The remaining issues for the characterization of the SEI
is heterogeneous, this may manifest as a myriad of differing cur- stem from the conflicting reports on the exact composition
rent densities across the electrode/electrolyte interface, hence and properties. This is exemplified by the controversy over the
a combination of computational and experimental approaches existence and role of LiF in the SEI with some studies stating
is required to understand the disordered interfacial behavior, it is not present in the dense inner SEI layer, nor does it have
toward informing on the design of next-generation batteries. a protective function for limiting the electrolyte decomposi-
tion.[32,196,204,240,241,246] To avoid such contradictions necessitates a
shift to in situ operando techniques to characterize the battery
5. Standing Problems and Outlook during operation. Batteries function in a closed environment and
only when the device is opened can researchers analyze the state
5.1. Standing Problems of the electrolyte and electrode materials, hence necessarily retro-
spective with the system possibly altered by change of conditions
The development of battery electrolytes has thus far been pri- from operating ones. Collaborations across disciplines with col-
marily led by empirical observations culminating in the dis- lective advances in theoretical methods, experimental capability,
covery of EC as a viable electrolyte that can actively passivate and advanced characterization techniques can overcome these
graphite. The absence of a structure-property relationship limitations in the study of battery interphases.[247,248]
between electrode and electrolyte materials hinders the rational Lastly, toward the development of high energy density batteries
optimization of LIBs, as well as next-generation battery chem- using modern electrolytes requires the use of different additives,
istry. Current modeling efforts rely on the proposed SEI struc- typically up to 5% per volume or weight. The introduction of addi-
tures and mechanisms, as the continual evolution of the SEI tives further increases the complexity of the reactions which occur
represents a theoretical challenge due to changes in the inter- at the electrode/electrolyte interphase. Additives such as vinylene
phase microstructure spanning different lengths and time carbonate (VC) or fluoroethylene carbonate (FEC) have been
scales. The computational approaches that have been employed studied extensively and are reported to be preferentially reduced
thus far are performed only on idealized ordered and often on the anode to produce an enhanced SEI, ameliorating the cycle
periodic systems. Due to the multi-component polydispersive life of LIBs. The use of electrolyte additives generates SEI compo-
nature of the SEI, an encompassing model which captures the nents with improved stability that impede decomposition, evolu-
various phenomena and effects has yet to be established; one tion, and thickening of the SEI layer. However, the mechanisms
that includes heterogeneities and functional disorder. of such additives, their functionality, or how the SEI is modified
Computational models of the SEI are limited by a compro- remains ambiguous. As a result, the understanding of the next
mise in accuracy between the inverse capability for ensemble generation lithium and post-lithium batteries requires compre-
size (number of atoms/particles) and energetic-temporal reso- hensive advancement to ascertain how electrolyte additives affect
lution. Weakly-polar interactions, dispersion forces, and accu- the SEI composition, morphology, and eventual properties.
rate descriptions of vibrational dynamics being essential to
accurate characterization of electrostatic behavior, yet compu-
tationally costly and thus limiting system size. Existing state- 5.2. Outlook
of-the-art atomic and continuum scale simulation methods
cannot fully characterize the interphase thus simplification of A key facet for the future design of the SEI layer lies in estab-
the system description, governing (physics) equations, and par- lishing the structure-property relationship of the interphase.
ametric scale bridging must be applied. Albeit challenging, the main properties that the SEI must pos-
The study of the SEI is also hampered by the lack of experi- sess have been defined. Firstly, the SEI must be ionically con-
mental techniques which afford the nanoscale or resolution for ductive yet electronically insulating, it must not impede Li-ion
elucidating the SEI structure and the pico- or even femtosecond transport from the electrolyte to the electrode, the layer must be
temporal resolution in relation to the electrode potential and chemically stable not reacting or dissolving into the electrolyte
electrochemical reactions. To avoid exposure to ambient condi- and the SEI must be mechanically stable; it should not crack or
tions that can alter the integrity of the layer, non-destructive and undergo volume expansion during charge-discharge cycles. The
in situ techniques must be effectuated. The widely used in situ large volume change is one of the primary concerns for alloy
microscopies (AFM, TEM) provide minimal molecular informa- anode (e.g., Si, Sn, aluminum, magnesium) design and devel-
tion, while XPS and XRD also lack the spatial resolution neces- opment, though progress has been made incorporating carbon
sary to correlate the chemical insights with the electrochemical additives or a carbon coating, as exemplified by silicon com-
interface. XRD monitors the entire electrode thus it cannot dis- posite anodes.[55,249–251] However, the criteria outlined herein
tinguish specific interactions on the electrode surface between will not be met by a single component of the SEI due to the
particles and electrolytes. Even the most advanced analytical tech- polydispersive nature of the layer, hence it is paramount that
niques such as cryogenic TEM resolve SEI structural and chem- a structure-property relationship is developed in relation to the
ical information, yet, it cannot provide details of the dynamic SEI species and one that accounts for dynamics and structure,
growth features in the layer under actual operating condi- as well as the ensuing disorder in the evolving SEI architecture.
tions.[243,244] While microscopic and spectroscopic techniques are Another key factor is the appropriate thickness of the SEI for

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optimal battery performance; reported to be in the range of a Ultimately, continuum models are efficient computational
few up to ≈20 nm.[41,168,252] methods to simulate the bulk electrochemical performance
The rational development of an artificial SEI offers a viable of batteries and are usually coupled with physical degradation
option toward the rational optimization and tailoring of the models, for example, SEI formation and growth during the
ideal chemistry and features of the multi-layer interphase. The charge/discharge process. The main continuum models that
artificial SEI can be advanced through predictive computational can be employed include the following: single particle (SP)
modeling, particularly when combined with knowledge and model, pseudo-2D (P2D) model, pseudo-3D (P3D) multiscale
precise characterization of relevant electrode surface-coating model, phase-field model, and 4D-resolved model.[213,268,269]
technologies. Methods such as atomic layer deposition (ALD)
and molecular layer deposition (MLD) can deposit a conformal
thin insulating coatings of uniform distribution and thickness 5.2.2. Machine Learning Models
at the atomic scale on electrode surfaces.[253–258] Regardless, the
rational engineering of a stable SEI will involve a transition ML is a type of artificial intelligence that can extract information
to employing complementary techniques across three main from large datasets, with algorithms that build a model based
areas: computational modeling, machine learning models, and on sample data, leveraging the data for predictive outcomes.
advanced operando experiments. ML potentials are a mathematical representation of the 3-N
dimensional potential-energy surface, which is the total energy
and interatomic forces for a given set of N atomic centers.[270]
5.2.1. Computational Modeling Such models “learn” the correlation between structure and
energy/forces from data acquired through simulations. These
To develop a framework for the comprehensive characterization models are only limited by the quantity and quality of the ref-
of the SEI structure, order-disorder transitions, dynamics, and erence data used to train them, with the computational cost
functional properties, it is essential to consider all the factors that of ML-based force fields only dependent on the choice of the
influence its formation. Specifically, the electrolyte along with the model but not the complexity of the interactions.
solvation structure of lithium ions and the EDL behavior at the Three state-of-the-art ML models exist that can be combined
interface determines the preferential reduction reactions during with atomic and electronic simulations.[44] Neural network
SEI formation.[259] Computational methods that take into account potentials use predetermined structure fingerprints of the local
the full electronic structure at the atomic scale are requisite to environment, these models can handle complex systems and
quantitatively characterize the SEI formation and evolution with large data sets. Gaussian process regression utilizes structural
descriptors and interpretation complementary to ML and oper- fingerprints such as Smooth Overlap of Atomic Positions
ando experiments.[260] A reductionist approach can be employed (SOAP) which are data efficient. Graph neural networks learn
in the construction of electrolyte complexes which can then be the fingerprints and map them to the energy and forces. Such
evolved to larger clusters, whilst retaining the specificity arising models are applicable to study the SEI using the automated
from differing 3D structures and oscillations between poses and learning of the most efficient fingerprints and the graph data
forms. DFT calculations can compute the specific inter- and structure which is related to the atomic structure. ML models
intramolecular interactions in electrolyte systems (including Van have been incorporated with atomic and electronic simulation
der Waals, dispersion, etc.) providing information on structural methods therefore the foundation is present to expand upon
configurations, conformations, and dynamics as well as reaction existing ML potentials extending their capabilities for complex
mechanisms that underpin electrolyte behavior. These details systems.[271–278] To build effective ML potentials to model the
can be incorporated into large scale models or used to better- SEI, they must consider electrostatic interactions and determine
parameterize these, toward providing an ever evolving meso- and accurate structures in reaction pathways that deviate from equi-
macroscopic understanding of the SEI. librium. In addition, to enhance the accuracy of the ML models,
AIMD is suitable for the large scale simulation of electrolyte advancements in the description of inter/intramolecular forces
systems to acquire time-resolved information of the SEI forma- and short/long-range interactions need to be implemented.
tion and functional mechanisms. This permits the scale-up of Ab initio methods are computationally demanding approaches
base-descriptors from DFT calculations from atomistic to nano- while force field methods can model larger systems yet com-
scopic-mesoscopic insights and beyond. The ReaxFF and eReaxFF promise accuracy. ML models can bridge this gap for the study
reactive force fields can also be utilized to simulate electrolyte of progressively larger chemical systems such as the SEI, at ab
solvent decomposition reactions as bond breaking/formation initio accuracy with force field efficiency.[271] It is important to
are sufficiently well described by empirical potentials to generate note that, despite their wide applications, ab initio methods are
semi-quantitative information. Modeling of larger systems is not as accurate as required; ML has been employed to improve
essential to elucidate the dynamic interfacial structures and inter- the DFT's accuracy.[273,279,280] The ML-assisted ab initio methods
actions as well as the long-range order structure, especially with can be used to ensure the reliability of the simulation results.
increasing evidence of EDL impacting the resultant SEI forma-
tion.[259,261–263] First-principles methods for open quantum sys-
tems can be employed to investigate the electronic structures at 5.2.3. Advanced Operando Experiments
the SEI-anode and SEI-electrolyte interfaces.[264] Time-dependent
DFT open system method[264–267] can be used to simulate in real- As batteries function in a closed environment and the SEI for-
time the electron injection, reduction reaction, and SEI formation. mation, composition and evolution are interfacial dynamical

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processes, in situ and ultimately operando characterization measurements due to the lack of compact, high-power, and
techniques present unique advantages. Among the techniques low-consumption solid state coherent sources and efficient
under development, those that utilize non-destructive and non- detectors. Opportunely, the rapid development of relevant tech-
ionizing probes with high material penetration depth, offering nology for the generation and detection of coherent THz radia-
lithium battery-relevant energy/frequency range and spatio- tion has made this frequency region more accessible and with
temporal resolution have the most potential for breakthrough. high-resolution. The general description of THz spectroscopy
In this sense, neutron and terahertz (THz) probes have intrinsic refers to techniques that employ coherent (heterodyne) trans-
advantages over X-ray, electron, and optical techniques. ceivers as opposed to the incoherent (noise) sources, as histori-
In situ neutron scattering at pulsed sources offers time- cally used in far-IR spectroscopies. Furthermore, THz radiation
resolved information on a sample's atomic/nano- through suffers less from scattering compared to IR due to the larger
meso-, to macro-scale structuring for crystalline, amorphous, wavelength, while remaining non-ionizing (non-destructive),
liquid, and even gaseous components of systems under study. while allowing it to penetrate deeper into materials whilst not
Further, quasi-elastic neutron scattering (QENS) techniques contributing to changes in the sample, especially important for
can provide information on ionic, atomic, and molecular diffu- time-dependent measurements. THz-TDS most often operates
sions and rotations, whilst inelastic neutron scattering (INS) in the ≈0.1–10 THz frequency range (1011 – 1013 Hz ≈ 0.41–41 meV)
measurements can resolve collective, cooperative whole system and provides contact-free, non-destructive characterization
vibrations (i.e., phonon modes) through to higher-energy local- through measurable frequency-resolved attenuation of the
ized vibrational dynamics. Neutron Compton scattering (NCS), reflected/transmitted THz field following its interaction with
also termed “deep-INS” (DINS), albeit particularly rare, pro- a sample.[295] The measured time-resolved THz signals can be
vides a unique opportunity to resolve and track element-specific converted to battery-related parameters depending on the exper-
kinetic energies, which are related to atomic cohesions and thus imental setup. For example, THz-TDS can help resolve aspects
bonding strengths on the nano-scale, whilst also being relevant of the ionic conduction mechanism[247] as well as SEI formation
to bulk and physical properties;[281] thus able to provide a glimpse and evolution[248] in response to external stimuli, such as the
into the evolving properties of the SEI and in real-time, as with applied voltage or current and their time duration in LIBs.
other disordered and amorphous systems. QENS, INS, and NCS As neutron and THz probes interact with all the atoms in the
operate via determination of energy change of the incident and beam path of a bulk sample, the design and placement of the
subsequently scattered neutrons after they interact with atoms in situ multi-component electrochemical cells for interaction
in the sample system, to determine the quantized momentum with the components of interest, as well as material selection,
transfers to the sample (similar to absorption-specific energetics are all crucial for achieving high signal/background ratio and
in optical techniques).[282] Being charge-free, neutrons are non- minimal multi-scattering. Traditional experimental techniques
ionizing, non-destructive, and do not interact with electrons, (e.g., impedance analyses) should be used in conjunction to
instead directly interacting with the nuclei. Neutrons easily assist data interpretation. Indeed, as with all empirical determi-
penetrate ≈1–2 cm of most materials and thus have the ability nations the trends emerging from neutron and THz measure-
to probe the relationship between structure and electrochem- ments become even more intelligible when a synergy is formed
ical performance in battery materials under operation, as being with related computational simulations of the phenomena
employed in other energy and climate related systems (eg. CO2- being probed.
mineralisation and carbonation). The high sensitivity of neutrons However, neutron and THz techniques are not without their
to Li[283] can precisely quantify Li content and its manifold den- own shortcomings and challenges, including first and fore-
sity at the anode surface, including its adsorption or insertion most access, where both techniques are rare at best and neu-
into the porous framework[283] and subsequent Li-containing tron scattering only available at large-scale facilities. Further,
component deposition/decomposition in the SEI layer.[284–288] the amount and size of sample required are relatively large in
Neutron reflectometry, in particular in situ neutron reflec- terms of size, volume, or weight often at the limit or beyond of
tometry (NR) offers advantages over ex situ techniques, such as prototype systems or materials employed in laboratory determi-
XPS,[289] time-of-flight SIMS and FTIR. These ex situ techniques nations; potentially limiting their study due to availability and/
are necessarily retrospective due to technical and experimental or cost. Even with sufficient sample, neutron scattering also
limitations and thus are not resolving phenomena neither at an presents challenges of analyses and interpretation due to the
active electrode, nor one in contact with the electrolyte.[289] In relative novelty of the techniques in the context of complex or
NR measurements, neutrons are reflected from most materials applied systems, with a much smaller experiential literature to
at grazing angles and the absorption is neglected[290] so the total draw upon.
number of neutrons remains constant via the sum rule, from Further, the scattering cross section of each element widely
which SEI thickness, density, chemical nature, and structural differs with some presenting a significant challenge to resolve,
evolution can be elucidated.[291–294] especially in the presence of “good scattering” ones; H-atoms
With respect to the resonance frequencies of the electrons being the best scatterers, yet only in forward scattering due
and vacancy-defects in a doped semiconductor, these appear in the to the matching proton-neutron mass, back-scattering is not
low-energy or “THz regime” and together with the electronic possible off of H-atoms. Organic solvents and systems con-
conductivity also having a dynamic component in the THz fre- taining C, O, N, S can also be transparent to neutrons, espe-
quency range, where THz time-domain spectroscopy (THz-TDS) cially in the presence of high-H content samples due to their
can be employed. This low-energy far-IR range, also termed smaller coherent absorption cross sections (relative to H). 1H
the fingerprint region, presents challenges for performing also has a large incoherent cross section; hence in diffraction

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experiments will contribute background, which if troublesome, measurements. The lack of structural or dynamic informa-
can be eliminated by using deuterated solvents. Otherwise, tion can also be accessed with cryogenic TEM and ultra-high
this incoherence “clouding” measurements can be addressed resolution SEM and TERS to probe and to help resolve the mor-
by carrying out comparative measurements tracking changes phology, nanostructure, and nanoparticle grain boundaries in
over time, in differing environments (i.e., temperature, sol- lithium-ion transport through the SEI.[296,297]
vent) else diverse concentrations toward generating relative To summarize, a unified cross-discipline approach merging
trends. Analyses can be limited to the back-scattering or on the modeling, artificial intelligence, and large-scale facility experi-
differences between front and back-scatter, yet the loss-of data ments within a centralized framework will transition battery
from eliminating front-scattering can significantly limit some research toward innovative discoveries (Figure 11). Cultivating

Figure 11. Summary outlook detailing the innovative cross-discipline characterization techniques which can provide a means to resolve the SEI
complexities.

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Henry Adenusi completed his Ph.D. at Sapienza University of Rome; he was awarded the “Vito
Volterra” International Fellowship. Currently, he is a postdoctoral fellow at the Hong Kong
Quantum AI Lab, joint center of The University of Hong (HKU) and the California Institute of
Technology (Caltech) working on the AI and quantum mechanical simulation platform for next
generation materials discovery. Research focus is on merging computational simulations with
electrochemistry experiments and AI technologies (machine learning) for battery materials.

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Gregory A. Chass is a reader in Computational Chemistry at the Queen Mary University of

London, with adjunct professorship at McMaster University and the University of Hong Kong.
His research focus and expertise lie in the computational design of experimental (neutron scat-
tering, muon-spin resonance) characterization and optimization of novel homogeneous catalysts,
cement composites, and bioactive compounds. Additional focus involves tracking of radical-
scavenging proficiency in natural anti-oxidants. Fundamental methodology development involves
entropy partitioning to accurately quantify free-energy of solvation and translational entropy in the
condensed phase, in addition to evolving molecular-cluster approaches to computing amorphous
materials and chemical transformations in solution.

Stefano Passerini is a professor at the Chemistry Department of Sapienza University of Rome.

Formerly a professor at the Karlsruhe Institute of Technology, Helmholtz Institute Ulm (Germany)
and the University of Muenster (Germany), he co-founded the MEET battery research center. His
research focuses on the basic understanding and development of materials for high-energy bat-
teries and supercapacitors, with the goal to create sustainable energy storage systems from envi-
ronmentally friendly and available materials and processes. He is an internationally recognized
pioneer in the field of ionic liquids and the development of alkali-ion batteries.

Kun V. Tian (田坤) is a senior researcher at Sapienza University of Rome, associated with
McMaster University and the University of British Columbia. She applies neutron and THz
spectroscopy, complemented by conventional spectroscopy, computer simulations, and bulk
mechanical tests to the understanding of micro-, meso-, and macro-scale properties of mate-
rials, systems, and processes, including but not limited to functional biomaterials, cement and
concrete, energy storage systems, CO2 capture and utilization, mineralization, and agro-industrial
waste utilization. Her research activities encompass basic and applied research as well as experi-
mental development of relevant industrial processes.

Guanhua Chen is a professor of Chemistry at the University of Hong Kong. He received his Ph.D.
degree in Physics in 1992 under the supervision of Prof. William Goddard III at the California
Institute of Technology. He joined the University of Hong Kong in 1996 and was the head of the
department of Chemistry from 2010 to 2016. He is a Fellow of the American Physical Society and
a Fellow of the Royal Society of Chemistry, and the recipient of the Croucher Senior Researcher
Award in 2016 and the National Natural Science Award in 2008.

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