Graphite in Lithium-Ion Batteries: Review
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Sofía Oliva GarcíaVolume 4
Number 11
November 2020
Pages 5363–5870
Sustainable
Energy & Fuels
Interdisciplinary research for the development of sustainable energy technologies
rsc.li/sustainable-energy
ISSN 2398-4902
REVIEW ARTICLE
Zhen Chen, Dominic Bresser et al.
The success story of graphite as a lithium-ion anode
material – fundamentals, remaining challenges, and
recent developments including silicon (oxide) composites
Sustainable
Energy & Fuels
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The success story of graphite as a lithium-ion
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Cite this: Sustainable Energy Fuels,
anode material – fundamentals, remaining
challenges, and recent developments including
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2020, 4, 5387
silicon (oxide) composites
Jakob Asenbauer,†ab Tobias Eisenmann,†ab Matthias Kuenzel, †ab Arefeh Kazzazi,ab
Zhen Chen *ab and Dominic Bresser *ab
Lithium-ion batteries are nowadays playing a pivotal role in our everyday life thanks to their excellent
rechargeability, suitable power density, and outstanding energy density. A key component that has paved
the way for this success story in the past almost 30 years is graphite, which has served as a lithium-ion
host structure for the negative electrode. And despite extensive research efforts to find suitable
alternatives with enhanced power and/or energy density, while maintaining the excellent cycling stability,
graphite is still used in the great majority of presently available commercial lithium-ion batteries. A
comprehensive review article focusing on graphite as lithium-ion intercalation host, however, appeared
to be missing so far. Thus, herein, we provide an overview on the relevant fundamental aspects for the
de-/lithiation mechanism, the already overcome and remaining challenges (including, for instance, the
potential fast charging and the recycling), as well as recent progress in the field such as the trade-off
Received 2nd February 2020
Accepted 29th April 2020
between relatively cheaper natural graphite and comparably purer synthetic graphite and the
introduction of relevant amounts of silicon (oxide) to boost the energy and power density. The latter, in
DOI: 10.1039/d0se00175a
fact, comes with its own challenges and the different approaches to overcome these in graphite/silicon
rsc.li/sustainable-energy (oxide) composites are discussed herein as well.
lithium into graphite electrochemically, however, failed due to
1. Introduction and outline the continuous co-intercalation and decomposition of the
Lithium-ion batteries (LIBs) have been on the market for almost commonly used liquid organic electrolytes based on, e.g.,
thirty years now and have rapidly evolved from being the pow- propylene carbonate (PC) and the resulting graphite exfolia-
ering device of choice for relatively small applications like tion.12,13 The rst successful attempt was reported in 1983 by
portable electronics to large-scale applications such as (hybrid) Yazami and Touzain,14 employing a solid polymer electrolyte. In
electric vehicles ((H)EVs) and even stationary energy storage 1990, Dahn and co-workers15 eventually found that the revers-
systems.1–7 One key step during these years has been the ible electrochemical lithium intercalation is possible also for
development of graphite-based anodes, replacing the initially liquid electrolyte when using ethylene carbonate (EC) as elec-
used so and hard carbons, allowing for greatly enhanced full- trolyte co-solvent thanks to the formation of a stable solid
cell energy densities due to its low de-/lithiation potential and electrolyte interphase (SEI) – a term that had earlier been
high (theoretical) gravimetric capacity of 372 mA h g1.1,8 proposed by Peled16 – on the graphite surface. Shortly aer this,
This development has been made possible by several the rst lithium-ion battery was commercialized by Sony in
important milestones, which are – together with more recent 1991; at that time, though, still incorporating PC as electrolyte
developments – summarized illustratively in Fig. 1. The possi- solvent and a coke anode.1 The subsequent quest for suitable
bility to form lithium intercalation compounds with graphite up electrolyte compositions based on EC, which were compatible
to a maximum lithium content of LiC6 using molten lithium or also with 4 V-cathodes, while providing suitable ionic conduc-
compressed lithium powder has been known, in fact, since tivity and electrode wettability, led to the development of
1975.9–11 Initial attempts in the 1970s to reversibly intercalate mixtures comprising EC and dimethyl carbonate (DMC), as re-
ported by Guyomard and Tarascon in 1993.17 As a result, start-
ing from 1994, almost all commercial LIBs were (and still are)
a
Helmholtz Institute Ulm (HIU), Helmholtzstrasse 11, 89081 Ulm, Germany. E-mail: based on graphite as active material for the negative electrode.18
[email protected]; [email protected] Since then, the performance of graphite anodes – especially the
rst cycle coulombic efficiency, but also the reversible capacity
b
Karlsruhe Institute of Technology (KIT), P.O. Box 3640, 76021 Karlsruhe, Germany
† These authors have contributed equally to this manuscript.
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Fig. 1 Illustrative summary of major milestones towards and upon the development of graphite negative electrodes for lithium-ion batteries.
and cycling stability – was continuously improved, for instance, rather fundamental issues, we discuss also very applied
via the identication of suitable lm-forming electrolyte addi- considerations, including the potential recycling and the
tives and coatings, as also discussed herein in the following. benets and drawbacks of using either synthetic or natural
Further progress in the early 2000s included the development of graphite – both aspects being highly relevant with respect to
aqueous and sustainable electrode processing technologies, the potential criticality of natural graphite32 and the rapid
replacing the toxic and harmful polyvinylidene uoride (PVdF) increase in (H)EV sales.7 Finally, we review the most recent
and N-methyl-2-pyrrolidone (NMP) as binder and solvent, development for commercial LIB anodes, the incorporation
respectively. Latest research and development efforts focused of silicon oxide, silicon–metal alloys, or elemental silicon,
especially on the increase in energy and power density by with a particular focus on those systems, which are or will
incorporating silicon (oxide) as secondary active material. presumably be of practical relevance within the near- to mid-
Remarkably, despite extensive research efforts on alternative term future and various cost-efficient approaches to over-
anode materials,19–25 graphite is still the dominant anode come the associated challenges. Covering all these aspects,
material in commercial LIBs. Even more remarkably in this we may anticipate that this review article will serve as intro-
regard maybe is the fact that there have been several review ductory starting point for researchers newly entering the eld
articles published in recent years on these alternatives, of LIB research and development, while potentially providing
including alloying-, conversion-, and conversion/alloying-type some insightful information and serving as reference work
anodes,19–27 but – to the best of our knowledge – no compa- also for experienced scientists and engineers.
rable review on graphite anodes, apart from a few book chapters
dealing with this subject.8,28–31
With this review article we are attempting to ll this gap
2. Fundamentals – the lithium
and provide a comprehensive overview on the recent devel- storage mechanism
opment and anticipated progress, starting from some rather 2.1 General suitability as host material
fundamental considerations concerning the de-/lithiation
Solid carbon materials essentially exist in two hybridization
mechanism. Subsequently, we briey summarize the impor-
states, i.e., sp3 (diamond) or sp2 (e.g., graphite). In case of
tance of the formation of a suitable SEI and its impact on the
graphite, the sp2 hybridized graphene layers are linked by rather
reversible lithium de-/intercalation – as far as it is important
weak van der Waals forces and p–p interactions of the delo-
for the further reading – and highlight the great advantages
calized electron orbitals.33 These layers can be stacked either in
of graphite as lithium-ion host structure, while pointing out
the thermodynamically more stable ABAB sequence with
also the remaining challenges – especially when it comes to
hexagonal symmetry or in the less stable ABCABC sequence
the rst cycle irreversibility and rate capability. Aer these
with rhombohedral symmetry.34–36 Bulk graphite commonly
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comprises both phases (Fig. 2a), although the rhombohedral the intercalation (i.e., insertion into 2D layered structures) of
phase accounts usually for less than 30% as a result of its ionic and molecular species across the prismatic surfaces, as
inferior thermodynamic stability.37 As a consequence of this they allow for an expansion of the interlayer distance, even-
layered structure, graphite particles are usually characterized tually accompanied by a re-stacking of the graphene layers.41
by a ake-like particle morphology with two different kinds of The general concept of such graphite intercalation
surfaces – basal planes and edge planes, the latter also compounds (GICs) has been established as early as 1840.42 In
referred to as prismatic planes, as schematically illustrated in principle, there are two different kinds of GICs, namely
Fig. 2b and indicated for an SEM (scanning electron micros- covalent GICs (e.g., graphite oxide43 and graphite uoride44)
copy) micrograph in Fig. 2c. The prismatic planes can be and ionic GICs such as alkali-metal GICs.
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further divided into the so-called zig-zag surfaces and arm-
chair surfaces (Fig. 2d), depending on the corresponding 2.2 The structural changes upon intercalation via ‘staging’
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stacking sequence. Generally, the prismatic planes show
a higher surface reactivity than the basal planes due to their The intercalation of secondary species like ions or molecules
higher surface energy.38 As a matter of fact, the 2D layered (generally referred to as intercalants) into the graphite host
structure does not only lead to an anisotropy concerning structure reveals a characteristic concentration-dependent
surface energy, but moreover has a dramatic effect on its feature, the so-called staging mechanism, as developed for the
electronic, physicochemical, and mechanical properties in rst time by Rüdorff and Hofmann in 1938.45,46 According to
general. For instance, the electronic and thermal conductivity this mechanism each ‘nth stage compound’ is characterized by
are very high (about 2.26 104 U1 cm1 (ref. 39) and 140 to a periodic sequence of intercalant layers, i.e., a sequence of
500 W mK1 (ref. 40), respectively) along the basal planes (due layers incorporating the intercalated species, separated by
to the metallic character of the in-plane bonding), but rather layers not incorporating any intercalated species, for which ‘n’
poor perpendicular to them (i.e., 5.9 U1 cm1 (ref. 39) and 3 denes the number of graphene layers separating two interca-
to 10 W mK1 (ref. 40), respectively).33 The rather weak van der late layers (Fig. 3, upper path). Consequently, as the concen-
Waals forces between the graphene layers, however, enable tration of the intercalant in the graphite host structure
increases, the number of empty layers (i.e., ‘n-1’) decreases.
Fig. 2 (a) Representative XRD (X-ray diffraction) pattern for natural graphite, indicating the presence of hexagonal and rhombohedral graphite
structures, with a relatively lower fraction of the latter. (b) Schematic illustration of the layered structure and the resulting presence of basal and
edge planes. (c) Exemplary SEM micrograph, indicating the basal and edge planes for a graphite particle. (d) Schematic illustration of the layered
graphite structure in bird's eye view (i.e., along the c axis), indicating the difference between zig-zag and arm chair surfaces.
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Fig. 3 Schematic illustration of the intercalation mechanism of secondary species (i.e., the intercalant; purple spheres) into the layered graphite
structure (illustrated by the black lines) according to the model of Rüdorff and Hofmann (upper path) and Daumas and Herold (lower path; figure
partially redrawn from ref. 69).
Thermodynamically, this staging phenomenon is related to optical microscopy, scanning transmission electron micros-
the interplay of (i) the energy required to expand the gap copy (STEM), and voltammetry indicated that the de-/
between two graphene layers and (ii) the repulsive interaction intercalation transport is substantially affected by defects in
between intercalant layers.47 A substantial limitation of this the crystal structure, while the expectations of both models
model, however, remains to be the missing ability to explain may be valid only in average for the bulk sample.54
the transition from Stage 3 to Stage 2, for instance, when
assuming that the layers span the entire graphite crystal, as
also discussed by Rüdorff and Hofmann in their seminal 2.3 The intercalation of Li+ for secondary lithium-ion battery
work.45,46 In fact, such a transition would require the dein- anodes
tercalation of a complete layer and the re-intercalation of the While the previous considerations are applicable to any
intercalants into a neighboring layer, as the diffusion across potential intercalant, the greatest commercial attention has
the basal planes has been discarded. In an attempt to over- certainly been on the application of graphite as host structure for
come this limitation, Daumas and Herold postulated the reversible intercalation of lithium cations, i.e., its employment
a modied model,48 for which for all stages with n > 1 the as active material for the negative electrode of lithium-ion
graphene layers are exible and deforming around domains batteries (LIBs), as introduced by Yazami and Touzain in 1983.14
(or as initially referred to ‘islands’) of the intercalated species The de-/intercalation process, however, essentially follows the
(Fig. 3, lower path). These domains are rather small general mechanism discussed above with Stage 1 as the nal
compared to the crystallite size and stacked according to the stage for the lithium ion intercalation, i.e., an overall stoichiom-
initial model by Rüdorff and Hofmann. Thus, the ordering etry of LiC6 as the highest possible Li content at ambient condi-
according to the earlier mentioned staging is maintained tions, accounting for a theoretical specic and volumetric
locally, but not in such rigid fashion. For the transition capacity of 372 mA h g1 and 850 mA h cm3, respectively.8 To
between, e.g., Stage 3 and Stage 2, the intercalated species accommodate such a high lithium content, the single graphene
would simply need to diffuse within the same layer (or via the layers slightly slide with respect to each other, resulting in
“sliding motion” of the intercalant islands49), forming the a symmetry change from an ABABA stacking in pristine graphite
next lower or higher stage upon intercalation or dein- to an AIAIA stacking in the fully lithiated state (LiC6; with I being
tercalation, respectively. While several studies provided the intercalant layer).55 Simultaneously, the interlayer distance
experimental evidence for such a “domain-dominated” between the graphene layers is moderately increasing by around
structure for GICs according to the model of Daumas and 10.4%, i.e., from 3.35 Å for lithium-free graphite to 3.70 Å for
Herold – based on, e.g., simulations,50 high-resolution elec- LiC6.56 The detailed de-/lithiation steps, however, slightly vary
tron microscopy,51 scanning ion microprobe,52 or a combina- with respect to the general staging mechanism (Fig. 4). In fact, for
tion of optical microscopy and Raman spectroscopy53 – the increasing lithium contents, the consecutive occurrence of the
staging mechanism, i.e., the transition from one stage to Stages n ¼ 1L, 4, 3, 2L, and 2 (before eventually reaching Stage 1)
another remains to be fully elucidated and more complex has been observed, for which the additional letter ‘L’ indicates
than initially proposed.53 A very recent study, combining that the lithium ions are not perfectly ordered within the layers,
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Fig. 4 Illustration of the staging mechanism for the electrochemical de-/intercalation of lithium cations (purple spheres) into graphite. The given
representative potential profile refers to the 2nd dis-/charge cycle in half-cell configuration, i.e., vs. metallic lithium as counter electrode.
but organized in a rather liquid-like manner.57 The rst stage, 2.4 The solid electrolyte interphase (SEI) as key for the
Stage 1L, represents a random, solid-solution-type lithium inter- reversible Li+ de-/intercalation
calation throughout the graphite particle, i.e., in every interslab of
The key for the present and ongoing success of graphite as state-
the graphite lattice. Subsequently, a rst-order phase transition
of-the-art lithium-ion anode, beside the potential to reversibly
occurs from Stage 1L to Stage 4, followed by the transition to Stage
host a large amount of lithium cations, in fact, has been the
3 along a sloped decrease in potential. Despite this indication for
identication of a suitable electrolyte composition in order to
the absence of a rst-order transition, the detailed mechanism is
overcome an intrinsic challenge associated with the use of
still not fully claried and might, indeed, be rather complex.57,58
graphite as active material in a LIB: the continuous exfoliation
Similarly, the following transition from Stage 3 to Stage 2L, which of graphene layers as a result of the solvent co-intercalation and
appearance is temperature-dependent57 and for which the de- the reductive electrolyte decomposition at the electrode/
nite structure is still discussed,57,59–61 remains to be completely
electrolyte interface, as common organic liquid electrolytes
understood. The next transition from Stage 2L to Stage 2 includes
are not sufficiently stable towards such low potentials.18,26,73,74
an increasing lithium content within the same intercalant layers
We may elaborate on this in more detail in the following. The
(i.e., every second in the graphite lattice), accompanied by an
electrochemical stability window (ESW) of an electrolyte is
enhanced in-plane ordering.57,59,60 The nal (rst-order) transition
related to its LUMO (lowest unoccupied molecular orbital) and
to Stage 1, leading to the formation of LiC6 and providing the
HOMO (highest occupied molecular orbital) energy. Hence, if
largest capacity fraction, is probably the best understood one.62 the electrochemical potential m of the relevant active material
Generally – as also depicted in Fig. 4 – the occurrence of these for the anode (ma) and cathode (mc) is lower than the LUMO or
phase transitions can be well monitored electrochemically by the
higher than the HOMO energy of the electrolyte, respectively,
appearance of a sequence of galvanostatic potential plateaus57 or
the electrolyte is theoretically stable for the operation of such
redox peak couples when performing cyclic voltammetry,63 while
a cell (from a thermodynamic point of view).74 The intercalation
a series of complementary techniques, including in situ
of lithium cations into graphite, however, occurs between 0.25
XRD,57,64–66 in situ neutron diffraction,58,67,68 or in situ Raman
and 0.01 V vs. Li/Li+, which is well below the electrochemical
spectroscopy,69 has been used to provide additional insights.
stability of, e.g., organic carbonate-based electrolytes, as these
Nonetheless, the detailed de-/lithiation mechanism and, partic- commonly decompose at about 0.8 V vs. Li/Li+.18,26,73,74 While
ularly, the transition between the elevated stages remains to be such a low operational potential is highly advantageous with
fully elucidated and is, thus, still under debate.58,70–72
regard to the energy density of the full-cell – as will be discussed
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in the subsequent chapter – the consequence is that the elec- density, and the initial charge loss, i.e., the energy density, there
trolyte is continuously decomposed at the (lithiated) graphite have been tremendous efforts undertaken to unveil its chem-
surface. In 1990, however, Dahn and co-workers15 showed that istry, functionality, and formation mechanism. These studies
Li+ can be reversibly intercalated into graphite in liquid elec- have been comprehensively reviewed in several articles18,76,80–83
trolytes comprising EC as (co-)solvent rather than the earlier and we will, hence, just provide a brief overview herein for the
used propylene carbonate (PC),75 for which massive graphite sake of completeness. It has been proposed that the SEI has
exfoliation had been observed as a result of the co-intercalation a mosaic-like structure, consisting of multiple inorganic and
of the Li+ cation along with its solvation shell.76 Differently, organic grains and layers.84 Close to the graphite particle,
when using a sufficient amount of EC as (co-)solvent, the elec- a dense layer of inorganic compounds like Li2O, Li2CO3, and LiF
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trolyte decomposition occurring during the initial charge (i.e., is formed, i.e., compounds which are thermodynamically stable
lithium intercalation) – commonly continuing for a few cycles – against lithium. This inorganic “layer” is covered by (rather)
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leads to the formation of a solid layer of the corresponding organic decomposition products such as semicarbonates and
organic and inorganic decomposition products on the graphite polyolens.84–86 Such general composition of the SEI has been
particle surface, accompanied by an irreversible capacity loss, as conrmed by a great variety of complementary experimental
illustrated by the comparison of the 1st and 5th dis-/charge cycle techniques, including spectroscopic85,87–90 and microscopic91–95
in Fig. 5. This layer prevents the direct (electronic) contact of the studies as well as theoretical investigations.96–99 In fact, the
graphite particles with the electrolyte and, thus, kinetically formation of a thin, but dense internal layer of inorganic
suppresses the continuous electrolyte decomposition kineti- compounds like Li2CO3 and LiF rather than organic metastable
cally16,77 and inhibits the solvent co-intercalation,78 while compounds like ROLi and ROCO2Li (with R being a low-
allowing for lithium cation conduction. Accordingly, it has been molecular alkyl group) is considered to limit the initial charge
termed solid electrolyte interphase (SEI),16,79 as it is an addi- loss by rapidly suppressing electrolyte decomposition.77,81,100
tional (in situ formed) phase that is acting essentially like a solid The ion conduction mechanism in these two different phases,
electrolyte at the interface between the graphite active material however, appears to be different, as proposed by Shi et al.101
and the liquid electrolyte. As this layer is essential for the employing DFT calculations for their studies of the Li+ transport
reversible operation of a lithium-ion cell and greatly determines in the SEI. According to their work, the Li+ diffusion is fast in
its properties, including the rate capability, i.e., the power the outer organic layer and following a relatively slower repeti-
tive “knock-of” mechanism in the dense inner inorganic layer,
largely consisting of (nanocrystalline) Li2CO3. Using highly
oriented pyrolytic graphite (HOPG) as a model, it was shown
that the composition and the thickness of the SEI, however, at
the edge planes and at the basal planes differ signi-
cantly.89,90,102 On the basal planes, the fraction of organic species
is higher, while it mainly comprises inorganic compounds,
resulting from the lithium salt decomposition, on the edge
planes. Moreover, TOF-SIMS (time-of-ight secondary ion mass
spectrometry) studies revealed that the basal SEI with
a common thickness of about 7 nm is around three to ve times
thinner than the SEI on the edge plane with around 35 nm.103 In
situ AFM (atomic force microscopy) studies indicated, slightly
differently, a smaller difference in the thickness of the basal and
edge SEI. Nonetheless, it was also shown that the thickness of
the SEI on the basal plane continues to grow upon cycling,
whereas the thickness of the SEI at the edge plane does not
change signicantly aer the rst cycle.91,104 Some studies sug-
gested that these differences are related to the fact that the Li+
ions are desolvated at the edge planes before being intercalated
in-between the graphene layers. Accordingly, the anions of the
Li-salt decompose at the edges into inorganic species, while
there is essentially no lithium intercalation across the basal
planes in absence of defects.86,105 In addition and/or alterna-
tively, the different electrochemical reaction and charge trans-
fer kinetics at the edge planes and the basal planes may play
a role for the different behavior towards the reductive electrolyte
decomposition.86,106,107 In fact, these differences in SEI compo-
sition and morphology somehow also reect the different
Fig. 5 Comparison of the potential profile of graphite half-cells for the functionality, as the SEI on the basal planes does not have to
1st (upper panel) and 5th (lower panel) dis-/charge cycle. serve as Li+ conductor, if there is no Li+ intercalation across
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these planes. Strictly speaking, it is thus not an SEI, though it volume changes upon de-/lithiation – even if only considering
still prevents the continuous electrolyte decomposition at these the energy density on the basis of the comprised active mate-
surfaces.76 While the precise composition and formation rials and, thus, ignoring the impact of the inactive cell
mechanism as well as the lithium transport through the SEI and components, i.e., the binder, conductive additives, the current
across the interfaces with the electrolyte and the graphite collector, the packaging, or the amount of electrolyte. In
particles still remains to be fully elucidated, also the important a recent study, Andre et al.6 compared different anode materials
difference between EC and PC is not completely understood, and their effect on the practical full-cell energy densities in full-
yet. Chemically speaking, the two molecules differ only by an cells. According to this study, most alternative anode materials
additional methyl group in PC, but only the presence of EC would provide lower energy densities than graphite, which
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allows for the formation of a stable SEI that suppresses solvent explains why it is still used in most commercial lithium-ion
co-intercalation and graphite exfoliation, as mentioned earlier. batteries. Another reason is the frequently neglected energy
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Based on the consideration that the Li(solvent)x complexes are efficiency, i.e., the ratio of energy that is stored relative to the
initially intercalated at the edge planes, followed the subse- amount of energy that is released upon discharge, which is
quent decomposition of the ternary Li(solvent)x-GICs,78 Shkrob directly linked to the difference between the charge and
et al.108,109 investigated the radical intermediates formed during discharge potential (if considering a constant coulombic effi-
the reduction of organic carbonate-based electrolytes. They ciency). For graphite, this difference, also referred to as voltage
found that the one-electron reduction of EC generates hysteresis, is relatively small, rendering it additionally favorable
secondary radical intermediates, which are forming a branched compared to most alternatives investigated so far,111 although
3D polymer network. In contrast, the formation of ternary some progress has been reported very recently for (pre-lithiated)
radicals in PC leads either to the formation of substituted conversion/alloying-type materials when limiting the de-/
olens via disproportionation or to linear polymer chains via lithiation to a rather narrow potential range.112
anionic polymerization. These different decomposition prod-
ucts were considered the reason for the successful graphite 3. Remaining (intrinsic) challenges
passivation in case of EC and the continuous electrolyte
decomposition and graphite exfoliation in case of PC. 3.1 Rate capability
Xing et al.110 proposed recently a different explanation based One of the major challenges for graphite anodes in LIBs is the
on the different solvation energy of the two solvents. For EC, the limited rate capability, especially for the lithiation process, i.e.,
solvation energy is signicantly smaller compared to PF6, the charging of the full-cell, and the associated risk of lithium
which leads to the co-intercalation of Li+ along with a large metal plating on the electrode surface, potentially resulting in
fraction of PF6 and the latter substantially contributes to the a short-circuiting of the cell or at least rapid ageing and accel-
SEI. In contrast, the solvation energy of PC is only slightly erated cell fading.113,114 While it has been reported that the rate
smaller than for PF6. Hence, the fraction of co-intercalated performance is directly related to the ambient temperature,115
PF6 is smaller and more solvent molecules are co- the particle size and morphology116,117 as well as the electrode
intercalated, resulting in a rather organic decomposition layer engineering,118 other studies revealed that the Li+ diffusion in-
that does not effectively suppress further degradation reactions between the graphene sheets is, in principle, extremely fast.
at the electrode/electrolyte interface. Kühne et al.,119 for instance, investigated the Li+ diffusion in
bilayer graphene via in situ time-dependent Hall voltage
measurements and found a diffusion coefficient as high as
2.5 The low de-/lithiation potential and its advantages 7 105 cm2 s1. Similarly, Persson et al.120 measured the
The theoretical specic capacity of graphite is 372 mA h g1, diffusion of lithium ions in HOPG and found a high lithium-ion
higher than the capacity of most common cathode materials, diffusivity of 107 to 106 cm2 s1 parallel to the graphene
but lower than the capacity of conversion- or alloying-type planes and a sluggish ion transport (1011 cm2 s1) perpen-
anodes as the most promising alternatives.22 Nevertheless, an dicular to them. Based on these ndings it would be possible to
aspect that is frequently overlooked is the nal energy density at de-/lithiate graphite with a typical crystalline domain size of
the full-cell level, which depends not only on the capacity, but 45 nm in less than 0.2 ms. Nevertheless, this is in contrast to the
also on the cell voltage. In this regard, graphite has a clear experimental observation that for standard electrodes the lith-
advantage compared to these alternatives, since it benets from iation process is limited to charge rates of maximum 1C, while it
the lowest average de-/lithiation potential (i.e., 0.2 V vs. Li/Li+) is possible to delithiate such electrodes at discharge rates as high
except metallic lithium. Nonetheless, the simplicity of deter- as 10C.118 According to the study by Persson et al.,120 the lithium-
mining the specic capacity compared to the rather complex ion diffusion coefficient was calculated to be 107 cm2 s1 for
determination of the energy density – especially if determined the Stages 1 and 2 in presence of many vacancies, but decreased
experimentally in suitable full-cells – render this common to 5 109 cm2 s1 for both stages in the fully lithiated state. A
procedure more favorable. In fact, the evaluation of the gravi- similar trend was also observed by Levi et al.,121 who determined
metric and volumetric energy density in full-cells is rather the Li+ diffusion coefficient of graphite at elevated temperatures
challenging, since one has to consider the balancing between by the potentiostatic intermittent titration technique (PITT).
the anode and the cathode, the dis-/charge rate and its impact Additionally, they found an increased lithium-ion diffusion
on the achievable capacity of both electrodes, as well as the coefficient (by a factor of 10) for the liquid-like stages compared
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to fully lithiated planes. Recently, Guo et al.122 reported an all- shrinking annuli mechanism thereby can explain the asymmetry
optical investigation of the lithium intercalation in a single- of the rate capability for the charge and discharge process.
crystal graphite disc-electrode. They found that the liquid-like Recently, the shrinking annuli mechanism was conrmed by
stages are homogeneously formed across the disc. This indi- Bauer et al.,123 who found that the dilatation behavior of graphite
cates that the Li+ diffusion from the edge to the center of the varies with the dis-/charge rate applied and that this deviation is
particle is fast compared to the Li+ “injection” at the edge. due to the formation of over-next GICs, especially at elevated
However, the Stage 2 phase nucleates at the boundaries of the states of charge (SOCs). Moreover, the relaxation behavior differs
disc electrode, followed by the nucleation of Stage 1 almost for the charge and discharge step.
immediately aer Stage 2 forms. This indicates a slower Li+ While these studies essentially focused on the Li+ transport
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transport through Stage 2 and Stage 1 compared to the diffusion within the graphite particle, another limiting factor, in fact, is
in Stage 1L. Furthermore, the system must be out of equilibrium considered to be the initial Li+ intercalation step. Electro-
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when three phases are observed, since in equilibrium maximum chemical impedance spectroscopy (EIS) measurements of
two phases exist simultaneously in the phase diagram for the lithium-ion cells at low temperatures showed that the cell
lithiation of graphite.57 Heß and Novák62 studied the kinetic impedance is mostly dominated by the charge transfer resis-
performance of highly crystalline graphite particles in thin layer tance.124 This nding is in line with the study by Wang et al.125
electrodes of ca. 1 mm thickness. They found that the Li+ diffusion who investigated the low-temperature performance of graphite
coefficient in the liquid-like stages substantially differs from the and mesocarbon microbeads (MCMBs) by microperturbation
densely lithiated stages. During lithiation, the transition from and found that at room temperature the phase transitions are
Stage 2L to Stage 2 cannot deliver its full capacity at high current the rate limiting step, whereas at 30 C the resistance of the
rates. Consequently, the overpotential increases due to diffusion SEI becomes limiting. In fact, the charge transfer can be sepa-
limitations until the next stage, i.e., Stage 1 nucleates at the edge rated in different processes: rst, the solvated Li+ ions, present
planes of the graphite particle (Fig. 6). Since the different stages in the liquid electrolyte, are desolvated, before, second, entering
propagate into the particle like the annuli of a tree, they named into the SEI layer and further into the graphite particle.
this phenomenon the “shrinking annuli model”. Upon delithia- Simultaneously, an e is injected at the electrode/SEI interface,
tion, the diffusion-limited transition from Stage 1 to Stage 2 takes as described in the following equations:126
place rst. Once the overpotential is high enough, Stage 2L
nucleates at the edge of the particle. Due to the higher diffusion Li+(Solvent)n / Li+ + nSolvent
coefficient for this stage, the phase boundary between Stage 2 and
Stage 2L propagates rapidly into the particle. As a result, Li+ / Li+SEI
according to this model, the liquid stages with a high diffusion
xLi+ + xe + C6 / LixC6
coefficient can balance the slow lithium-ion diffusion of the
densely lithiated stages only during the delithiation of graphite.
Beside the limited maximum overpotential for the lithiation To further elucidate the impact of the different contribu-
process (due to the generally low lithiation potential), the tions, Abe et al.127 investigated the Li+ charge transfer process at
the interphase between a HOPG-based electrode and the elec-
trolyte by alternating current (AC) EIS. When a 1 M solution of
LiCF3SO3 in 1,2-dimethoxyethane (DME) was used, the solvated
Li+ ions can be rather directly intercalated into HOPG, as there
is no substantial SEI formation. For this process, they found an
activation energy of only 25 kJ mol1. Differently, the activation
energy increases to 53–59 kJ mol1 when a 1 M solution of
LiClO4 in a mixture of EC and diethyl carbonate (DEC) was used,
since such electrolyte composition leads to the formation of
a relevant SEI and Li+ needs to desolvate rst before diffusing
through the SEI. Therefore, the authors concluded that the
desolvation of Li+ at the SEI surface prior to the intercalation
into the graphite particle is the rate limiting step. This
conclusion was supported by the nding that the lithium-ion
transfer resistance at a model interface, consisting of
a lithium-ion conductive ceramic and a liquid electrolyte,
correlates with the interaction between the lithium ions and the
nature of the solvent in the liquid electrolyte.128 Nevertheless,
Fig. 6 Schematic illustration of the “shrinking annuli model” for
since the desolvation of Li+ ions occurs at both the anode and
a single graphite particle. The golden, red, and purple color indicate the cathode, one would expect similar activation energies for
the formation of Stage 1, Stage 2, and Stage 2L, respectively. The figure both electrodes.126 Accordingly, Jow et al.129 investigated two
has been reproduced from Heß and Novák62 with permission from different full-cell chemistries by EIS, i.e., graphite//LiFePO4
Elsevier.
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(LFP) and graphite//LiNi0.80Co0.15Al0.05O2 (NCA), with an elec- a subsequent treatment with a hot LiOH solution. In both cases,
trolyte consisting of 1 M LiPF6 in a mixture of EC, dimethyl the “SEI-like lms” formed on the graphite surface reduced the
carbonate (DMC), and methyl butyrate (MB) as well as vinylene extent of initial electrolyte decomposition and, thus, enhanced
carbonate (VC) as additive. The activation energies for the the ICE and the reversible capacity.
graphite/electrolyte, NCA/electrolyte and LFP/electrolyte inter- Apart from these pioneering works, the surface modica-
facial charge transfer were calculated to be 67 kJ mol1, tions investigated can be mainly categorized into inorganic,
50 kJ mol1, and 33 kJ mol1, respectively. The authors organic, and carbonaceous coatings. Yu et al.,134,135 for instance,
concluded that the large differences in activation energy cannot reported an improved electrochemical performance in PC-
be explained by the desolvation as the predominant step for based electrolytes when nano-sized Ni-composite particles
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limiting the kinetics only. Instead the results suggest, that the were deposited on the graphite surface. The thus limited direct
different nature of the corresponding electrode/electrolyte contact with the electrolyte reduced the solvent co-intercalation,
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interfaces is inuencing the Li+ charge transfer kinetics. This mitigated PC reduction, and decreased the charge transfer
was supported by the nding that the activation energy is resistance. For the optimum ratio of such coating (ca. 10 wt%),
greatly inuenced by incorporating different additives into the the ICE and reversible discharge capacity were improved from
electrolyte,130 which would theoretically not have a signicant 59% to 84% and by about 30–40 mA h g1, respectively. Besides
effect on the solvation energy of the electrolyte. Moreover, the Ni, the incorporation of a series of other metals such as Ag, Au,
pre-formation of the SEI on graphite leads to a great variation of Al, In, Bi, Pd, Pb, Sn, Zn, and Cu has been studied as either by
the activation energy for the Li+ transfer, which further supports forming composites or applying them as coating materials for
the conclusion that the Li+ ion transfer kinetics are substan- graphite.136–138 In general, the application of such metal lms
tially inuenced by the SEI composition.131 facilitates the SEI formation and leads to higher reaction
In sum, the rate capability of graphite, even though not fully kinetics for the lithium de-/intercalation due to an enhanced
understood yet, appears to be the complex interplay of all charge transfer and reduced SEI resistance, originating from
potential contributions, i.e., the particle size and morphology, the reduced activation energy for the Li+ desolvation and
the electrode architecture, the phase transitions occurring, the subsequent migration through the SEI towards the intercalation
chemistry and composition of the SEI (and, accordingly, the sites.139 This improvement is particularly pronounced at low
electrolyte composition), the desolvation prior to entering the temperatures, at which a drastic polarization is observed
SEI layer, and the ambient temperature. otherwise. When the metal itself is electrochemically active, i.e.,
able to alloy with lithium, just like for Sn, it was found that the
impact on the electrochemical performance is highly depen-
3.2 First cycle irreversible capacity dent on the metal concentration. For instance, in case of rather
Apart from the rather poor rate capability, another drawback of small amounts of Sn (up to 20 wt%), its incorporation strongly
graphite anodes in LIBs is the rst cycle irreversible capacity favors the reaction kinetics, hence, contributing to signicantly
(Cirr) due to the reductive electrolyte decomposition and, thus, enhanced specic capacities.140 For larger amounts, however,
the consumption of Li+ as the charge carrier. One strategy to the presence of the alloying metal increases the volume
reduce the Cirr, that has been pursued since the commerciali- expansion upon lithiation and, as a consequence, reduces the
zation of graphite-based LIBs, is the modication of the ICE compared to pristine graphite.141 In case the metal does not
graphite particles' surface (Fig. 7a). Such surface modication alloy electrochemically with lithium (and is ideally character-
can employ the treatment of the graphite particles by either ized by a different crystal structure – such as Ni or Cu), such
using (oxidative) solutions, ceramic materials, or gases, coatings may, moreover, address the issue of lithium metal
commonly followed by a heat treatment. As a result, both basal plating at elevated current densities (and low temperatures – see
and edge planes are chemically altered to enhance the electro- Section 3.3), thanks to an increase of the lithium metal depo-
chemical performance. Another approach relies on the intro- sition overpotential.142
duction of electrolyte additives that kinetically favor the SEI In addition to the potential introduction of metals, also
formation in a more efficient way and, thus, allow for increasing metal uorides and oxides have been investigated in order to
the initial coulombic efficiency (ICE). These two different reduce the initial irreversible capacity loss. For example, the
approaches will be discussed in more detail in the following two application of a thin AlF3 layer on graphite demonstrated
paragraphs. improved cycling stability and capacity retention; nonetheless,
3.2.1 Improving the ICE via ex situ surface modication. In with a slightly negative effect on the ICE.143 Differently, Al2O3,
1996, Peled et al.132 demonstrated the modication of graphite characterized by a suitable bandgap, serves as SEI formation
edge planes via a mild oxidation at 550 C for 1 h (Fig. 7b), inhibitor and, thus, enables an increased ICE by up to 5%.144
leading to a more efficient SEI formation. In such case, the SEI The application of an Al2O3 coating on the readily made elec-
is chemically bonded on a monolayer of acidic functional trode rather than on the graphite powder by atomic layer
groups formed on both zigzag and armchair edge faces, deposition (ALD), thus avoiding the extensive introduction of
resulting in an improved ICE of only 10% in best case. A electronically insulating surfaces and interfaces (Fig. 7c), has an
different approach was reported by Ein-Eli and Koch133 in 1997 even higher impact on the electrochemical performance
who dispersed graphite particles either in nitric acid or in (Fig. 7d).145 The authors did not only record a higher ICE and
a saturated solution of (NH4)2S2O8 in sulfuric acid, followed by
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Fig. 7 Different approaches to optimize the electrochemical performance of graphite by surface modification: (a) the general target of achieving
a more efficient SEI layer formation and the consequent realization of thinner SEI films. (b) Schematic illustration of the mild oxidation proposed
by Peled et al.,132 resulting in a “smoothening and cleaning” of the particle surface, in contrast to the application of a strong oxidation, leading to
particle degradation (figure redrawn from ref. 360). (c) Illustration of the difference between powder coating (upper panel) and electrode coating
(lower panel) approaches; the latter one resulting in the formation of less electronically insulating surfaces and interfaces in case of, e.g., Al2O3
coatings (figure redrawn from ref. 145). (d) Comparison of the galvanostatic cycling of bare graphite electrodes and those coated with Al2O3 at
the powder and electrode level (figure reproduced from Jung et al.145 with permission from Wiley).
enhanced capacity retention, but moreover such coating carbonates. They found that in their case a carbon coating
allowed for the use of PC as electrolyte solvent. content of 17.6 wt% marked the optimum concerning the ICE,
Similarly to inorganic coatings, also the utilization of poly- resulting in an improvement from 87.2% to 94.5% and from
mer coatings, including inter alia polyaniline,146,147 (poly)acry- 76.6% to 92.4% for an electrolyte composition of EC : DMC
lonitrile,148 polypyrrole,149 polymerized thiophene,150 or (1 : 2) and PC : DMC (1 : 4), respectively. An important draw-
nitrophenyl,151 has been reported as an effective strategy to back of such (rather large amount of) carbonaceous coating,
improve the ICE. Compared with the use of inorganic however, is its commonly lower density than graphite, accom-
compounds, the implementation of polymers as the coating panied by signicantly inferior contribution to the overall
material exhibits two salient advantages which are high chem- capacity, which leads to signicantly reduced gravimetric and
ical diversity and mechanical exibility. For example, Li et al.152 volumetric energy densities at the full-cell level. This issue could
demonstrated that the application of a polyether-based coating be overcome by employing spherical graphite particles and the
drastically increased the ICE and enhanced the rate capability if consequent reduction of the required carbon coating content to
the ether has a phenyl-based terminal group, as this enables only 3 wt% while still offering superior electrochemical
a good adhesion to the graphite surface due to the p–p inter- performance161 and even enhanced thermal stability.162 It
action. Furthermore, they were able to strengthen the should be noted, though, that the application of carbonaceous
mechanical stability of the electrode by crosslinking the ether coatings might also have a negative impact on the irreversible
molecules via the additional introduction of an allyl-amine electrolyte decomposition if it leads to an increased surface area
polymer. of the active material.163 Hence, particular attention has to be
The mostly investigated and presently most cost-efficient paid on the choice of the carbon coating precursor and its
surface coating material, though, is probably carbon – in fact, content, the graphite particle morphology, and the general
not only for graphite, but for essentially every LIB active mate- processing to achieve an enhanced electrochemical perfor-
rial.153–159 In one of the very early studies, Yoshio et al.160 inves- mance regarding the long-term cycling stability, the initial
tigated the impact of different carbon coating amounts, applied charge loss, and the eventual energy density.
via thermal vapor deposition from toluene as precursor, on the 3.2.2 Improving the ICE via electrolyte additives. Beside (or
electrochemical performance of natural graphite using different in addition to) the ex situ modication of the graphite surface
electrolyte compositions based on 1 M LiPF6 in various organic prior to the electrode preparation and cell assembly,
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a comparable effect can be achieved by tailoring the electrolyte relatively low stability towards oxidation strictly limits the
composition, since the rst cycle coulombic efficiency is driven amount that might be added to the electrolyte in lithium-ion
by the extent of electrolyte composition – similarly to the cells.164
introduction of EC as co-solvent, in fact. Commonly, this In combination these different, but complementary
approach is referred to as introduction of lm forming addi- approaches to reduce the rst cycle irreversibility have led to
tives, i.e., the incorporation of small/certain amounts of an coulombic efficiencies as high as 90–96% for commercial
additional in-/organic compound (or several) into the (liquid) graphite anodes, thus providing the benchmark for any alter-
electrolyte. Indeed, the precise composition of electrolytes used native negative electrode active material.
in commercial LIBs is probably the greatest secret of the battery
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cell producers and it is hard to unveil such compositions, as
these additives are usually decomposed during the in-house 3.3 Ageing and the resulting safety concerns
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conducted formation cycles, while the detailed reaction mech- An issue that essentially concerns all battery materials, but is
anisms are as difficult to understand as the formation mecha- particularly important for graphite as a result of the low de-/
nism of the SEI in general.76,77 Since there have been several lithiation potential close to the plating of metallic lithium,
comprehensive review articles published recently on electrolyte is ageing – induced by both usage (cycling) and storage
additives,74,80,164,165 we may focus herein on the impact on the (calendar ageing).181,182 Generally, ageing processes are very
ICE and illustrate the benecial effect of a few selected complicated – not least due to the long time frames that have
examples. to be considered and the fact that a large variety of different
Generally speaking, electrolyte additives that are improving electro-/chemical processes and their interactions have to be
the ICE are either contributing to a more efficient SEI by being considered.182,183 In fact, the ageing mechanisms at the nega-
simply electrochemically reduced (e.g., prior to the base elec- tive and positive electrode signicantly differ from each other
trolyte itself), inducing the reduction of other electrolyte and while we will focus herein on those occurring at the
components in a favorable way, or reductively polymerizing – or graphite anode, also the impact from the cathode has to be
a combination of these mechanisms. Ideally, the thus formed kept in mind.
surface layer inhibits further extensive electrolyte decomposi- The cathode-induced ageing that has been most investigated
tion and, by this, leads to an increased ICE. Classic examples are so far is related to the dissolution of transition metal cations
uoroethylene carbonate (FEC)166,167 and VC.168–171 The latter has from the cathode and their diffusion to and deposition on the
been reported to form a polymeric lm on the graphite anode anode, as comprehensively reviewed recently by Zhan et al.184
following a ring-opening reaction prior to the decomposition of and Li.185 The most prominent example in this regard is the
EC and, thus, stabilizing the electrode/electrolyte interface.169 manganese dissolution from spinel-structured LiMn2O4 (ref.
Moreover, it was reported that the addition of VC allows for 186–192) or LiNi0.5Mn1.5O4 (ref. 112, 193 and 194) due to the
effectively deactivating the oxides at defective sites and at the formation of soluble Mn2+, resulting from the Jahn–Teller
edge planes of (HOP) graphite and that the resulting modied distortion.195,196 As a consequence, the manganese dissolution
SEI would be extremely thin, i.e., only a few nm.168 Remarkably, does not only lead to capacity and power fading at the cathode,
the use of VC as electrolyte additive enables even the utilization but also inuences the SEI composition at the anode.184 In fact,
of PC as electrolyte solvent and successfully suppresses the PC an analysis of aged LiMn2O4/graphite cells via EIS revealed that
co-intercalation and subsequent graphite exfoliation.171,172 the increased impedance at the graphite anode is largely
Additionally, several studies reported a benecial effect of VC contributing to the capacity fading of such lithium-ion cells.187
also for suppressing the irreversible reactions occurring at the It was reasoned that – due to the low de-/lithiation potential of
cathode,173–175 rendering it particularly advantageous. Never- graphite, well below the reduction potential of Mn2+ – metallic
theless, it has been reported as well that the incorporation of VC manganese is deposited either via electrochemical197 or chem-
leads to an increased irreversible capacity at elevated tempera- ical192 reduction at the anode surface, causing an increased
tures,176,177 which has been assigned to its rather poor thermal electrolyte decomposition.198,199 An alternative mechanism was
stability.178 As a potential alternative, vinyl ethylene carbonate reported by Zhan et al.,200 who showed that the oxidation state of
(VEC) was found to be more stable than VC owing to its electron manganese deposited on the surface is 2+ and postulated an ion
rich double bond. According to Hu et al.172 the stable passiv- exchange model in which Mn2+ accumulates in the SEI by an
ation layer formed due to the reductive decomposition of VEC ion-exchange reaction with Li+ and, thus, blocks lithium ion
on the graphite surface contributed to an improved battery diffusion. Apparently, these two mechanisms do not exclude
performance and prevented PC co-intercalation into the each other and further research will be needed to fully under-
graphite anode. stand the ongoing ageing phenomena.
A slightly different mechanism was reported for additives Another cathode-induced ageing mechanism for graphite
such as ethylene sulte179 and propylene sulte,180 as their anodes is related to the decomposition of the electrolyte at
reduced products are adsorbed on the catalytically active sites of elevated potentials (and temperatures) at the cathode surface
graphite, resembling somehow the poisoning of a catalyst and, and the migration of soluble decomposition species to the
by this, suppressing the electrolyte decomposition that would anode, where they can further react – also referred to as “cross-
be preferably occurring at these sites. Nonetheless, their talk” species and reactions.201,202 Sahore et al.201 developed very
recently a two-compartment lithium-ion cell, in which they
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separated the two electrodes by a solid electrolyte interlayer to lithium plating, as depicted in Fig. 8a.211 Waldmann et al.212
retrieve and segregate such species before they can further react demonstrated in a post mortem study that the rate of lithium
at the negative (or positive) electrode. They suggested that these plating increases when the temperature is decreased from 25 C
species are likely uorinated carbons and compounds with to 20 C as a consequence of the slower Li+ diffusion. More-
carbon–carbon double bonds, as proposed also earlier.203–205 over, in a recent study by Lüders et al.,213 it was shown that the
Focusing essentially on the anode, Vetter et al.181 compre- degree of lithium plating correlates with the applied current; by
hensively summarized the potential ageing mechanisms for this limiting the possibility to rapidly charge the lithium-ion
graphite and provided a general classication, differentiating cell (as discussed above in Section 3.1). Interestingly, though,
ageing processes with respect to (i) the (long-term) instability of it appears that the rate of lithium plating is decreasing upon
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the SEI (which also includes the aforementioned cross-talk cycling, which was assigned to the fact that the potential (or
phenomena), (ii) lithium plating, and (iii) the contribution of SOC) at which plating commonly occurs is not reached anymore
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electrochemically inactive electrode components such as the due to the (also plating-induced) capacity fading upon long-
binder, conductive additives, and the current collector. Among term cycling. Hence, it has been stated that lithium plating
these, they considered the former two most relevant – also with “counteracts with its own occurrence”.214 Precisely, it has been
regard to potential safety issues. found that the plated metallic lithium reacts with the electro-
As mentioned above, the formation of the SEI occurs mainly lyte, thus, forming its “own SEI” on top of the graphite electrode
during the rst cycles – but not exclusively. Upon cycling and at elevated SOCs and is partially consumed during this process.
storage, the morphology and composition of the SEI further Upon the subsequent stripping, the metallic lithium is partially
develop. This temperature-related evolution of the SEI induces reoxidized and reinserted into the cathode, while electronically
a continuous loss of lithium, consumption of the electrolyte, insulated lithium continues reacting with the electrolyte,
and, as a result, an increasing resistance. Beside the impact on leading to the formation of so-called “dead” lithium species (see
the performance, however, the occurring changes also affect the also Fig. 8b).214,215 In line with these ndings, Fleischhammer
overall safety of the battery cell. According to Feng et al.206 the et al.216 correlated the ageing history of commercial cells with
destructive interactions between the graphite anode and the their safety behavior by means of accelerating rate calorimetry
electrolyte can be summarized into three characteristic stages: and simultaneous thermal analysis and observed that the self-
the rst stage is the heat-induced SEI decomposition. This heat heating rate and extent of thermal runaway were much more
may evolve from severe abuse conditions such as a deep over- severe for cells that were aged at low temperature (i.e., with
charge, (too) high and/or highly inhomogeneous current lithium plating) due to reaction of the electrolyte with metallic
distribution, or external heat sources. The onset of the SEI lithium, while cells aged under high current conditions did not
decomposition has been reported to occur at ca. 90 C, but show signicant differences regarding their safety compared to
might even be as low as ca. 57 C, depending on individual unaged cells. As a consequence, temperature is a highly decisive
system.207,208 During the second stage (at ca. 120–250 C), the SEI parameter for ensuring long-term stable electrochemical
decomposition and regeneration occur simultaneously, leading performance and, eventually, the evaluation of the cells con-
to a rather thick, but stabilizing SEI. Nevertheless, if the cerning their suitability for second-life applications such as
temperature increases further, i.e., above 250 C, the third stage stationary storage.
occurs – the breakdown of the SEI due to the structural collapse
of graphite206 and/or the decomposition of the electrolyte.209
This series of reactions marks the origin of the thermal runaway 3.4 Recycling
of the battery cell, including the extensive decomposition of the The recycling of spent LIBs has focused so far mostly on the
electrolyte, the melting of the separator, and the degradation of recovery of (heavy) metals, i.e., on the elements comprised in
the cathode active material, potentially causing severe safety the cathode and the current collectors, and little attention has
issues such as inammation and even the explosion of the been paid on the recycling of the graphite anode. The latter
cell.206,210 In fact, to inhibit this series of destructive reactions aspect has been dealt with only by very few studies.217–219 As
and, hence, prevent the cell from thermal runaway, enormous a matter of fact, the recycling rate of graphite in 2010 was 0%
efforts have been devoted towards the development of suitable and even by 2014 the recycling of graphite was still of low
surface modications for the graphite anode and SEI forming (economic) priority.220 Nonetheless, natural graphite has been
additives, as also discussed earlier in the Sections 3.2.1 and classied as a critical resource by the European Union (EU) – not
3.2.2, targeting not only an improved electrochemical perfor- least as there are no natural resources in the EU.221 Thus, the
mance, but also enhanced thermal stability of the SEI and, thus, recovery of graphite might become more important in the
pushing its decomposition towards higher temperatures. future along with an increasing electrication of the transport
Another severe safety issue is the potential plating of metallic sector and the consequently rising number of spent LIBs.
lithium at the graphite electrode surface due to the low lith- Generally, LIB recycling can be categorized into pyro-
iation potential close to the deposition of metallic lithium. metallurgical, hydro-metallurgical, and physical processes.
Accordingly, any increased overpotential for the lithiation However, it has been shown that both pyro-metallurgical
process, resulting from, e.g., a sufficiently low operational processes (due to the high temperature needed) and hydro-
temperature or elevated currents, especially in combination metallurgical processes (due to the aggressive chemicals
with an (ageing-induced) increase in resistance, might cause involved) fail in recycling graphite in a reusable way.219
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Fig. 8 (a) Schematic illustration of lithium plating/stripping on graphite electrodes in competition with the de-/intercalation of lithium cations
into graphite depending on the applied current and temperature (figure redrawn from ref. 211). (b) The behavior of plated lithium metal on top of
a graphite electrode as a function of the ‘state of charge’ (SOC) and ‘state of discharge’ (SOD) upon plating and stripping, respectively (figure
redrawn from ref. 215).
Differently, the physical processing allows for the recycling of the active material agglomerates are broken down to primary
the current collectors, the cathode active material (in form of particles through mechanical impact. However, during the
suitable precursors), and the graphite anode, as schematically separation and de-agglomeration most of the graphite particles
illustrated in Fig. 9. Hanisch et al.222 described the Adhesion get lost. Bertuol et al.223 were able to separate cell components
Neutralization via Incineration and Impact Liberation (ANVIIL) by physically shredding commercial LIBs and separate the
process which can be adapted to the process depicted in Fig. 9 components, i.e., the separator, metals, and active materials, by
aer shredding the cell and electrolyte extraction. This process spouted bed elutriation. The fraction of recovered active mate-
employs moderate heat treatment to decompose the PVdF rials was 42.7 wt% (containing both LiCoO2 and graphite),
binder and, thus, lower the adhesion between the electrode which is certainly remarkable already, but still insufficient with
coating and the current collector. Subsequently, the metal foils respect to the continuously increasing importance of LIBs and
and electrode coatings are separated in an air jet separator and the need for efficient recycling technologies. In 2016, Nowak
Fig. 9 Schematic illustration of the ‘physical recycling’ process for LIBs, enabling the recycling of the metallic current collectors, the cathode
active material (in form of suitable precursors), and the graphite anode (figure redrawn from ref. 217).
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and co-workers217 studied possible routes towards the recycling
of graphite by means of different electrolyte extraction and SEI
removal strategies. Both aged and non-aged commercial cells
were discharged, opened in a glove box, and the jelly rolls were
extracted. Aer several steps to obtain lab-scale electrodes, the
graphite anode was subjected to electrolyte extraction via
subcritical CO2 or static supercritical CO2, followed by a subse-
quent simple heat treatment. The results showed that, by
subcritical CO2-assisted electrolyte extraction, the re-used
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graphite provided superior performance compared to
commercial synthetic graphite. Interestingly, all re-used
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graphite samples from aged cells outperformed the ones ob-
tained from non-aged cells, suggesting that such treatment
appears generally favorable.
As an alternative, aer having shredded the lithium-ion cells,
graphite can also be recovered via wet chemistry, e.g., by Fenton
reagent (Fe2+/H2O2) assisted otation. He et al.218 showed that
treatment of graphite and LiCoO2 with the Fenton agent allows
for removing the organic surface layer (as validated by XPS) on
both the cathode and the anode active material. Subsequently,
the two materials can be simply separated by otation when
taking into account the different hydrophility. Nevertheless,
their study also revealed that the optimum recovery rate is
achieved only with high excess of the Fenton agent, which limits
the commercial applicability of this process for the moment.
4. Recent developments
4.1 Natural vs. synthetic graphite
There are essentially two kinds of graphite used in state-of-the-
art LIBs – natural graphite (NG) and synthetic graphite (SG). In Fig. 10 Comparison of SEM micrographs of sphere-shaped natural
both cases, the particles are polycrystalline and composed of graphite (NG; after several processing steps) and synthetic graphite
numerous single-crystalline domains (depending on the size of (SG).
these domains, one differentiates between micro- and macro-
crystalline graphite).224–226 In NG, though, these domains are
commonly oriented in the same direction, while their orienta- carbon, commonly derived from petroleum, to 2500 C for
tion in SG is more random, as also apparent from Fig. 10. In a certain period up to several days in some cases.36,224 This high-
fact, for obtaining such spherical particle shape (also referred to temperature treatment renders SG relatively expensive
as “potato shape”), the originally ake-like NG particles and the compared to NG (ca. 8 US$ kg1 vs. around 13 US$ kg1,
frequently randomly shaped SG particles have to be subjected to respectively229), but offers the advantages of higher purity, lower
an additional mechanical treatment aer the mining process, thermal expansion, and better thermal stability.230 Additionally,
the spheroidization.227 This process aims at homogenizing the the possibility to synthesize graphite, in ideal case from
particle size (ideally, 8–30 mm) and morphology and, thus, sustainable resources (though this is highly challenging given
improving the packing density in the electrode coating layer for the required reproducibility, quality, and availability of
enhanced volumetric capacities. In case of NG, this modica- precursors with a suitable structure, frequently resulting in
tion of the particle morphology allows moreover for avoiding rather amorphous carbons231), provides the advantage of being
the parallel-to-the-current-collector orientation of the ake-like independent of natural graphite resources and the rather
material, which would hinder rapid lithium cation de-/interca- isotropic orientation of the crystalline domains within each
lation.161 In both cases, this mechanical treatment is frequently particles, accompanied by a relatively larger fraction of edge-
followed by applying a thin carbon coating to reduce the surface planes at the particle surface. This allows for superior de-/
area and, hence, improve the ICE by reducing the reductive lithiation kinetics, although also frequently higher irrevers-
electrolyte decomposition and further suppressing solvent co- ibility in the initial cycles.36,71,225 Simultaneously, the smaller
intercalation.228 domain size and the, thus, relatively larger fraction of domain
While the eventual performance of any specic graphite interfaces leads to lower capacities compared to NG, charac-
material eventually depends on a variety of different parame- terized by larger, rather anisotropically oriented crystalline
ters, there are several general characteristics for the two domains.71
different kinds: SG is basically produced by heating unsaturated
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For such reason, both materials are presently used for
commercial LIBs;32,227,232 SG especially in EV applications (due to
the higher purity and quality, despite the higher cost) and NG
typically for portable electronics, as these applications do not
have the requirement of very long cycle life. Accordingly, it is
expected that the demand for both NG and SG will further
increase with the increasing importance of LIBs, while the fact
that NG is considered a critical raw material is anticipated to
further trigger the development of high-performance SG.32,227,233
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4.2 Aqueous electrode processing
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An aspect about graphite anodes that is nowadays very well
established (also in industry), but has happened, in fact, only Fig. 11 Illustration of the impact of increasing anode capacities on the
about ten years ago, is the use of water-soluble binders for the total capacity of lithium-ion full-cells in combination with different
electrode preparation, providing substantial advantages con- cathodes, i.e., varying cathode capacities, here exemplarily presented
cerning cost and sustainability. Since this has very recently been for state-of-the-art LiCoO2 (140 mA h g1, in black), a next-generation
layered lithium-rich transition metal oxide cathode (LR-MO,
reviewed very comprehensively for LIBs in general,234 we may
250 mA h g1, in red), an oxygen cathode with a limited specific
just provide a brief overview herein, highlighting several nd- capacity of 500 mA h g1 (in yellow), and a capacity-limited sulphur
ings that are particularly relevant for graphite. One of its key cathode (1000 mA h g1, in green). The values represent the ideal
advantages in this regard is its chemical stability towards water, maximum that can theoretically be achieved for a specific combina-
which has triggered extensive efforts for nding alternative tion neglecting full-cell balancing and oversizing effects.
polymeric binders to replace relatively costly PVdF as well as
harmful and teratogen NMP.235–239 Among the rst (and pres-
ently used) are styrene butadiene rubber (SBR) in combination development efforts in the past decades. The impact of further
with sodium carboxymethyl cellulose (CMC), polyacrylic acid increasing the specic capacity of the anode on the total
(PAA), or gelatine.229,240–246 Especially CMC does not only add to lithium-ion cell capacity is illustrated in Fig. 11 for a few
the binding functionality, but moreover enables the realization selected cathode material candidates, ranging from state-of-the-
of stable suspensions of the hydrophobic graphite particles in art LiCoO2 with a specic capacity of 140 mA h g1 (in black),
water thanks to the coordinative interaction between the next-generation layered lithium-rich transition metal oxides
carboxylic groups and, e.g., hydroxyl groups at the graphite (LR-MO) with an anticipated capacity of 250 mA h g1 (in red),
surface.234 The use of CMC only, however, does not allow for an oxygen cathode with a limited specic capacity of
mechanically stable high mass loading electrodes due to its 500 mA h g1 (in yellow), and a sulfur cathode with a limited
rather brittle nature. Hence, SBR is added as well, providing capacity of 1000 mA h g1 (in green). While an increase in
a highly suitable combination of properties. Remarkably, the capacity for the anode has a benecial effect in combination
utilization of such water-soluble binding agents does not only with all these cathodes, this effect is particularly pronounced
reduce the cost for the electrode processing and adds to the for increasing cathode capacities well beyond the state of the
environmental friendliness of LIBs,234 but also presents bene- art. Nevertheless, it is also apparent from Fig. 11 that for a given
cial electrochemical characteristics such as a decreased initial cathode capacity the total full-cell capacity reaches a plateau at
capacity loss and a stabilized SEI.240,247 Furthermore, the a certain anode capacity, suggesting that especially for the state-
replacement of PVdF by CMC and PAA, for instance, enhances of-the-art and next-generation cathodes an anode capacity of
the thermal stability of the resulting electrodes and suppresses about 1000–1500 mA h g1 will be sufficient – at least from the
the thermal runaway246 thanks to a lower reactivity with lithiated total gravimetric capacity point of view.255 Accordingly, the
graphite.248–251 In some cases, the water-soluble alternatives incorporation of reasonable amounts of high-capacity anode
even provide enhanced charge transfer kinetics for the lithium materials like abundant and environmentally friendly silicon
de-/intercalation,249 rendering this development advantageous with a theoretical capacity of 3578 mA h g1, in fact the alloying
from essentially every perspective and without any apparent element with the highest capacity known (Fig. 12), and an
performance loss or other signicant disadvantage compared to average delithiation potential of ca. 0.4 V vs. Li/Li+ in graphite-
the earlier used PVdF in NMP. based composites appears as a very suitable approach for the
realization of next-generation lithium-ion anodes.21,256,257
4.3 Introducing silicon for enhanced energy densities 4.3.1 The rst step: understoichiometric SiOx. Under-
stoichiometric SiOx (with x < 2) provides several advantages
A rather recent (industrial) development is the introduction of compared to elemental silicon, since it is much cheaper and
small amounts (up to ca. 8 wt%252) of silicon or under- easier to be handled at ambient atmosphere due to the lower
stoichiometric silicon oxide (SiOx, with x < 2) to graphite reactivity. While the precise composition of under-
composite electrodes,253,254 since pure graphite anodes have stoichiometric SiOx is still under debate, there is strong
essentially reached their maximum performance concerning evidence that it might be considered as a nanoscopic mixture of
energy density thanks to the intensive research and
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4.3.1.1 Design of elaborated nanostructures. To mitigate the
negative impact of the large volume changes of the added SiOx,
the reduction of the particle size to the nanoscale is considered
a very viable approach. Nonetheless, several issues have to be
addressed with respect to a meaningful application of nano-
sized materials: (i) the high surface area leads to an increased
electrolyte decomposition and lithium loss; (ii) the low tap
density results in decreased volumetric energy densities; (iii) the
handling of nanomaterials at the commercial scale provides
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severe processing and safety issues; and (iv) the overall cost for
the synthesis and processing, including the nal incorporation
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into the graphite-based electrodes, have to be kept as low as
possible.266–270 In an attempt to address these issues (at least
Fig. 12 Comparison of the gravimetric and volumetric capacity of partially), Doh et al.,271 for instance, reported a 1 : 1 ball-milled
graphite and selected alloying elements such as zinc, aluminum, lead, mixture of graphite and SiO comprising moreover a carbon
magnesium, tin, and silicon (the volumetric values refer to the fully- precursor that was subsequently carbonized at elevated
lithiated state, according to ref. 21 and 361, in order to be of practical
temperatures. Such composite provided a capacity of
relevance, but do not consider other important factors such as the
volume of the dislocated electrolyte362). 500 mA h g1 aer 100 cycles with a capacity retention of about
82%.272 Similarly, Lu et al.273 reported carbon-coated Si–SiO2–C
composites by ball-milling a mixture of SiO, graphite, and coal
pitch (serving as carbon source), followed by a high temperature
elemental Si, SiO2, and some intermediate phase comprising treatment which leads to the formation of an amorphous
less oxygen,258,259 as proposed by Temkin in 1975.260 The higher carbon coating around the composite particles. Such material
the oxygen content, the lower the reversible capacity,258 since provided stable cycling for 90 cycles with a capacity of more
only the elemental silicon is reversibly alloying with lithium, than 700 mA h g1. Using furfuryl alcohol as precursor for the
while the simultaneously formed lithium silicate remains carbon coating, scientists from Toshiba published a detailed
inactive upon the subsequent delithiation.21,261–265 This is analysis of a similar ball-milled SiO/graphite composite. Mixed
summarized in the following reaction mechanism, separating with graphite such composite exhibited a reversible capacity of
the initial irreversible contribution of 608 mA h g1 and the about 700 mA h g1.274 The dispersion of nanometric (5–10 nm)
reversible contribution of 1708 mA h g1, resulting in a theo- silicon clusters throughout the sample was considered essential
retical ICE of maximum 73.7% – not considering any electrolyte for maintaining the structural integrity of the isotropic
decomposition: composite particles with a size of 5–20 mm, while the combined
silicate/carbon matrix effectively buffered the volume changes
608 mA h g1
4SiO þ 17:2Li ! 3Si þ Li4 SiO4 upon de-/lithiation, resulting in a capacity retention of 85%
1708 mA h g1 aer 200 cycles and a CE approaching 100% aer several cycles.
! 3Li3:75 Si þ Li4 SiO4
Following a simple sol–gel synthesis and subsequent carbon
coating based on glucose as carbon precursor, other groups
While the high initial irreversibility is certainly an issue, the prepared hierarchically structured carbon-coated SiOx/C
higher density matrix of Li4SiO4 (2.39 g cm3 – compared to composites.275–277 Such materials revealed specic capacities
1.18 g cm3 for Li3.75Si) acts as an effective buffer for the occurring between ca. 675 mA h g1 (ref. 275 and 276) and about
volume changes, limiting it to about 160% compared to almost 800 mA h g1 (ref. 277) aer 100 cycles, in all cases corre-
300% for elemental silicon.262,265 Moreover, the presence of the sponding to a capacity retention of about 84% with an average
lithium silicate phase may enhance the lithium diffusion into the CE of above 99%, suggesting that the external carbon shell
nano silicon domains by creating additional phase boundaries stabilized the interface with the electrolyte. In 2014, Park et al.278
within the mixed structure.265 Taking these considerations into followed up the approach from Toshiba and employed a scal-
account, the major strategies to overcome the intrinsic limitations able sol–gel process for the synthesis of a SiOx/C composite in
of adding SiOx to graphite composite electrodes are: (1) the design which silicon nanodots were embedded into the SiOx matrix.
of elaborated nanostructures, including the incorporation of The connement of nanometric Si into the matrix could buffer
secondary carbon phases, to improve the electrochemical perfor- the severe volume changes as proven by cross-sectional SEM
mance and buffer the volume changes, (2) the development of analysis of the cycled electrodes, the height of which only
industrially relevant pre-lithiation techniques to tackle the low changed by 37% aer 100 cycles. Simultaneously, the uniform
ICE, and (3) the development and optimization of additional cell carbon coating layer on the nanospheres allowed for an excel-
components such as the binding agent and the electrolyte lent rate capability with more than 800 mA h g1 delivered at 2C,
composition, targeting enhanced mechanical properties of the i.e., more than 90% of the capacity at 0.05C. The stabilized
electrode and a stabilized electrode/electrolyte interphase (see also electrode/electrolyte interphase in combination with the buff-
Section 3.2.2). ered volume changes enabled an average CE above 99.5% and
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a good capacity retention of 78% aer 100 cycles with a revers- use of carbon-coated SiOx as sole anode active material in full-
ible capacity of 740 mA h g1. cells with LiNi0.8Co0.15Al0.05O2 (NCA) cathodes. Despite an
To briey summarize, the carbon coating fullls several impressive capacity retention of >80% aer 500 cycles in an
functions: (i) it acts as a buffer for the volume variations operational voltage range of 2.5 V to 4.2 V, the ICE remained
occurring; (ii) it stabilizes the electrode/electrolyte interphase; rather low with less than 65%. Such low ICE, however, would
(iii) it serves as an electronically conductive, percolating exclude any meaningful commercial application,266,285 as the
network throughout the electrode (in addition to/combination extra lithium comes with a lot of additional mass in the
with the subsequently added conductive agent). commonly used lithium transition metal oxide cathodes.
Given the aforementioned studies, the application of such 4.3.1.2 Pre-lithiation strategies. To overcome the limitation
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coating in combination with the realization of nanostructured in energy density due to the rather low ICE, different strategies
SiOx/carbon composites appears indispensable for the have been developed to either compensate this initial loss by
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successful implementation of SiOx in commercially viable providing some additional lithium source inside the cell (in
electrodes. In fact, it has been reported that carbon coating addition to the cathode) or to address this issue prior to the cell
content needs to be as high as 50% to achieve stable cycling assembly by forming partially lithiated phases already during
performance with a reversible capacity above the synthesis or at the electrode level. Following the “synthesis
500 mA h g1,279–281 while nanometric carbon coatings cannot approach”, Veluchamy et al.286 pre-lithiated SiOx by blending it
effectively suppress the formation and propagation of particle with LiOH and subjected this blend to 550 C before ball-
cracking and a continuous SEI reformation.282 The latter issue is milling the resulting mixture with graphite. The partial forma-
frequently overlooked in half-cell studies, where the lithium tion of Li4SiO4 in the pretreated material helped to reduce the
counter electrode provides a large reservoir for additional rst cycle irreversible capacity from 55% for the non-
lithium cations, but becomes immediately apparent when prelithiated composite to 44% and allowed for an improved
studying new anode materials in full-cells. This effect is illus- cycling stability. Another rather simple, but effective “synthesis
trated also in Fig. 13 for different CEs (from 99.0% to 99.995%) approach” relies on the in situ mechano-chemical reduction of
on the full-cell level, i.e., with a limited amount of lithium in the SiOx by ball-milling it together with lithium metal.287 As a result,
cathode. In literature, however, only a few full-cell studies have the ICE was increased to 81% with a reversible capacity of
been reported. Yamada et al.283 prepared negative electrodes around 770 mA h g1 at a dis-/charge rate of 0.1C and the CE
based on a mixture of 50 wt% SiOx, 21 wt% graphite, and 9 wt% was approaching 99% aer 50 cycles. Nevertheless, the rate
carbon bers, subsequently coated by 20 wt% of carbon via capability of such composite remained improvable; for
physical vapor deposition (PVD), and compared this elaborated instance, at 1C, the reversible capacity was less than
mixture with a simple 1 : 1 blend of SiOx and graphite. The 360 mA h g1, presumably due to an insufficient active material
combination of the elaborated mixture with blended LiNi1/3Co1/ utilization.
3Mn1/3O2/LiCoO2 (NCM/LCO) cathodes revealed an anode Work on the “electrode pre-lithiation approach”, similar to
capacity of ca. 700 mA h g1 aer 100 cycles, corresponding to the frequently employed lab-scale approach of rst pre-
a capacity retention of remarkable 85%. On the contrary, the lithiating the electrode in half-cell conguration prior to the
simple anode blend showed only 20% capacity retention aer full-cell assembly (Fig. 14a),112,288–291 was inter alia reported by
just 20 cycles in the same lithium-ion conguration. The large Kim et al.,292 who developed a scalable roll-to-roll process for the
amounts of carbon, though, allow for only limited improve- pre-lithiation of the electrode prior to the full-cell assembly by
ments in energy density. Hence, Kajita et al.284 investigated the spraying an electrolyte solution onto the electrode tape and
bringing it in contact with lithium foil with a separator in-
between (Fig. 14b), followed by the application of an external
short circuit. The incorporation of a resistor in the external
circuit allowed for the controlled lithiation of the SiOx-based
electrode. To conrm the suitability of this approach, the
authors assembled a pre-lithiated SiOx//NCA full-cell with elec-
trodes that had a commercially relevant areal capacity of
>2.0 mA h cm2. Such cells showed a remarkable ICE of 95%
and a specic energy above 500 W h kg1 (1080 W h L1), thus,
exceeding the internal graphite-based reference by more than
10%. In a very similar way, the company Nanoscale Compo-
nents designed a pre-lithiation bath, in which negative elec-
trodes are pre-lithiated from a lithium-salt containing solution,
potentially via a roll-to-roll process.293,294 To demonstrate the
general feasibility of this approach, Chevrier et al.295 realized
Fig. 13 Illustration of the impact of the average CE for the full-cell
2 Ah 18650-type cylindrical cells with large fractions (up to
capacity retention by varying the average CE from 99.0% (in black) over
99.9% (in red) and 99.99% (in yellow) to 99.995% (in green). The 55 wt%) of 3 M Si alloy negative electrodes (see also Section
horizontal blue line indicates the common end-of-life (EoL) criterion 4.3.2) with precisely dened lithium reservoirs. As a result, they
of 80% capacity retention. could achieve a gain in energy density as high as 11% over their
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Fig. 14 Pre-lithiation approaches for SiOx-based anodes (though generally applicable also to other active materials): (a) lab-scale pre-lithiation
in coin-type half-cells using a lithium metal counter electrode. (b) Continuous electrochemical pre-lithiation on large-scale via a roll-to-roll
process employing a quasi-half-cell configuration with the SiOx-based anode wetted by an electrolyte and moving continuously across
a stationary Li–metal counter electrode with a stationary separator; the application of an external short circuit or generally a current allows for
a controlled pre-lithiation of the electrode to a specified potential and/or capacity (figures redrawn from ref. 292). (c) Deposition of lithium–
metal powder, comprised in a PVdF solution, onto the polymer separator (1), followed by the evaporation of the solvent (2) and wetting with the
electrolyte (3). Subsequently, the separator is placed on the readily cast electrode (4) and the lithium powder reacts with the SiOx-based
electrode coating (5) (figure inspired by ref. 296). (d) Addition of stabilized lithium metal powder (SLMP©) onto the readily made electrode and its
activation by calendaring/pressing (figure redrawn from ref. 299). (e) Compensation of the initial irreversibility of SiOx-based anodes by coupling
them with carefully balanced LR-NCM cathodes in order to utilize the initially released Li2O along the first cycle high-voltage activation step upon
charge (figure redrawn from ref. 302).
baseline cells with a capacity retention of 80% aer 500 cycles. It separator coating layer. In fact, such improvement was observed
should be noted that such approaches are generally applicable not only for SiOx-based electrodes, but also pure graphite (93%
also to any other active material and can lead to further vs. 89%) and anodes based on elemental silicon (87% vs. 67%).
enhanced energy densities even for standard graphite-based Nonetheless, the handling of the lithium-containing separator
electrodes. Nonetheless, they require the installation of rela- is certainly a challenge for industry – not only with regard to its
tively large space with a protected atmosphere (either noble high reactivity, but even more the severe safety issues in case the
gases or at least dry air – depending on the reactivity of the pre- separator gets damaged upon processing. A method that is
lithiated compounds) and adds another processing step to the presumably easier to be implemented at industrial level is the
cell assembly. pre-lithiation approach reported by Gao et al.,297 employing the
Similarly, also the “compensation approach” is generally incorporation of commercially available stabilized lithium
independent of the active material chemistry. Hwang and metal powder (SLMP® (ref. 298)). As depicted in Fig. 14d, the
Yoon296 developed such a methodology by dip coating a poly- SLMP® particles can be simply added onto the electrode –
propylene separator with a thin lm of lithium powder either directly as powder or in form of a suspension – and
dispersed in PVdF to pre-lithiate SiOx/graphite (1 : 1) electrodes activated by calendaring/pressing to break the stabilizing
(Fig. 14c). The subsequent characterization in lithium-ion cells coating.299,300 Thanks to the pre-lithiation of the anode, full-cells
with LCO as cathode active material revealed that the ICE could with an NCM cathode provided an improved energy density by
be increased from 66% in case of the uncoated separator to an up to 30% compared to reference full-cells comprising pure
impressive value of 89% for an optimized lithium content in the (and non-prelithiated) graphite as anode.299 In a more recent
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study, the application of SLMP® for a SiOx/graphite demon- development of enhanced binders has become a research eld
strated an impressive ICE as high as 98.5% (vs. 68% without pre- on its own, covering the development of complex functional
lithiation) and highly stable half-cell cycling with an average CE polymers and their interaction with the active material
of 99.4% and capacity retention of 95% of the initial surface316–318 as well as the (carbon-coated) current
905 mA h g1 aer 200 cycles.300 Nevertheless, it has to be kept collector,319,320 as comprehensively reviewed in detail very
in mind that during this process metallic lithium is spontane- recently by Li et al.321 and Bresser et al.234
ously reacting with the electrode active material, thus, requiring Accordingly, we would like to just briey highlight herein
strict safety measures such as working under dry air/protective that an ideal binder for Si- and SiOx-based anodes should fulll
atmosphere. Additionally, achieving a precise control concern- the following requirements: (i) display only weak interactions
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ing the homogeneity of the pre-lithiation is certainly not trivial, with the electrolyte in terms of swelling and changes of the
which calls for additional safety measures to prevent a local mechanical properties, while providing high (electro-)chemical
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overcharge.301 stability; (ii) maintain efficient Li+ diffusion pathways to the
While these pre-lithiation strategies are anticipated to be of particle surface without forming blocking layers; (iii) provide
great importance for the development of next-generation potential binding sites to rmly attach to the active material
anodes in combination with, e.g., Ni-rich NCM or even future particles, e.g., by hydrogen bonding between functional groups
cathodes such as oxygen or sulfur (if not using metallic such as carboxylate and hydroxyl groups, as well as the current
lithium),22 another potential cathode candidate for next- collector – ideally accompanied by self-healing properties to re-
generation LIBs can, indeed, serve as internal lithium source establish the contact between the volume-changing particles
itself (without simply losing capacity): LR-NCM. In this regard, and the current collector.
Yamano et al.302 reported a well-conceived study on SiOx//LR- 4.3.2 The (potentially) second step: silicon–metal alloys.
NCM full-cells, attempting to compensate the anode and An elegant way to overcome the initial capacity loss due to the
cathode irreversible capacity simultaneously by making use of irreversible formation of lithium silicate, while still conning
the initial Li2O removal from the LR-NCM structure the electrochemically active silicon in a high-density matrix that
(Fig. 14e).303,304 Carefully adjusting the mass loading of the two buffers the volume variations occurring, is the use of silicon–
electrodes by taking into consideration the initial irreversible metal alloys21 in combination with graphite.322 Early studies
capacity allowed for compensating the rst cycle irreversible reported the formation of an electrochemically active silicon
capacity on the anode side and the resulting full-cells demon- phase within a matrix of inactive NiSi2 and NiSi, uniformly
strated very stable cycling performance. The same concept also distributed on the surface of graphite particles. Such composite
applies for the overlithiated spinel-structured lithium nickel exhibited stable cycling at ca. 700 mA h g1.323,324 The additional
manganese oxide, as demonstrated by Axmann and co- introduction of titanium into the alloy resulted in a super-
workers,305 where the extra-lithium introduced during solid- elastic Ni–Ti alloy that appeared advantageous for accommo-
state synthesis can be used to compensate the irreversible loss dating the volume expansion of the electrochemically active
of, e.g., silicon-containing carbon composites with a net-gain of silicon within the alloy matrix.325–328 Nonetheless, the ICE still
25% in specic energy as compared to regular graphite/ remained improvable, which was assigned to the formation of
LiNi0.5Mn1.5O4 (LNMO) full-cells. SiOx, TiOx and NiOx during the rst cycle as a result of the
Eventually, any approach that shall be commercially imple- reaction with the electrolyte, but could be improved by sub-
mented will have to be cost-efficient and safe (at least as safe as jecting the alloy material to a nitridation treatment.329 Further
the current technology). Therefore, especially the approaches optimization – especially with respect to the long-term cycling
involving the use of metallic lithium will have to be critically stability – was realized by utilizing different metals such as Al,
assessed – even though industry might benet of the experi- Fe, and Mn. Obrovac et al.330 reported a capacity retention of
ences towards the development of lithium–metal batteries, 68% aer 500 cycles with a very high CE of 99.96% in an 18650-
which is presently attracting great attention again.306–308 type cell, containing active silicon dispersed in an inactive Si–
Insightful review articles on this subject have recently been Al–Fe phase together with an active Sn3Mn phase to improve the
published by Aravindan et al.309 and Holtstiege et al.,310 to which lithium diffusion in the alloy. The proper selection of the
the interested reader is kindly referred at this point. amount and type of graphite as well as the (post-)processing,
4.3.1.3 Development of advanced binding agents. Similar as however, were found to be crucial for obtaining such remark-
for pure graphite electrodes (see Section 4.2), the development able performance – also with regard to the subsequent calen-
of advanced binding agents has been intensively studied in the daring of the electrodes which is essential for achieving high
past years also for Si-containing composites. In contrast to pure volumetric energy densities.331,332 When incorporating about
graphite, however, these composites are much more 30% of graphite into the anode blend, the full-cell energy
demanding due to the extensive volume variation upon de-/ density could be improved by ca. 15% compared to pure
lithiation. A suitable candidate (at least for rather low mass graphite anodes.332 Further studies by Marinaro et al.333 sup-
loadings) turned out to be CMC with promising results reported ported such remarkable performance by assembling prototype
for both Si- and SiOx-based anodes.247,311 Following these 1.2 A h Si-alloy/graphite//NCM523 lithium-ion pouch-cells with
results, the search for suitable binders was further extended an areal electrode capacity of more than 3.7 mA h cm2 and
towards other water-processable polymers such as PAA,312,313 a stable capacity for about 300 cycles before the EoL was
poly(vinyl alcohol) (PVA),314 and alginate.315 Nowadays, the
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reached. Still, though, the ICE and average CE remained the continuous improvement of such composites, though
improvable with about 75% and 99.88%, respectively. taking into account, of course, also the overall electrode
4.3.3 The nal target: elemental silicon. Another possi- composition and their fabrication.
bility to potentially overcome the low ICE of SiOx and Si–metal Generally, a limitation of the silicon content to maximum
alloys, though more challenging with respect to the synthesis 30–50% accompanied by a limitation of the lithium concen-
and handling, is the use of “pure” elemental silicon (commonly, tration within the silicon phase was reported to be advanta-
though, covered by a thin layer of silicon oxide), since there is geous with respect to cycling stability.337 In addition,
no lithium silicate or inactive metal oxide formed initially.21 The a reduction of the silicon particle size below 150 nm helps to
overall reaction at room temperature is as follows:21,334,335 address the detrimental impact of the large volume variation, as
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3578 mA h g1
there is no signicant particle cracking observed anymore,
4Si þ 15Li ! Li15 Si4 though simultaneously the overall specic surface area of the
Open Access Article. Published on 07 May 2020. Downloaded on 12/3/2023 1:02:51 PM.
composite has to be kept low to avoid extensive electrolyte
Nevertheless, the extensive volume variation of up to 280%, decomposition at the electrode/electrolyte interface.338,339 At the
inducing great mechanical stress on the composite electrode, same time, the synthesis and particle design are ideally kept
the electrode/electrolyte interface and interphase, and the rather simple to facilitate the commercial application of such
whole cell, provides a great challenge that still remains to be materials at reasonable cost and allow for achieving suitable
overcome.21,336 Since these issues, however, are essentially the electrode mass loadings. This trade-off is schematically illus-
same as for SiOx and Si–metal alloys, the strategies to address trated in Fig. 15. Trying to address these aspects, Lee et al.340
them are basically the same, i.e., (1) the design of smart nano- mixed silicon nanoparticles with an average size of about
structures, (2) the development of pre-lithiation strategies, and 100 nm and NG akes (5 mm) in a pitch containing solution
(3) the development and optimization of advanced binding via ball milling to obtain a spheroidized carbon matrix aer
agents and electrolyte additives (see also Section 4.3.1). carbonization. While the silicon nanoparticles were distributed
Accordingly, we will focus in the following particularly on those randomly in the composite, the thin graphite akes tended to
studies dealing with the interaction of silicon and graphite and align in parallel, which provided an enhanced structural
stability and to some extent buffered the volume variation
Fig. 15 Schematic summary of the trade-off between the advantages of a reduced particle size for the silicon active material and the
accompanying challenges with respect to particle pulverization, active material surface, electrolyte decomposition at the electrode/electrolyte
interface, mechanical properties of the electrode, and packing density (figure inspired by and redrawn from ref. 338 and 339).
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within the spherical composite particles. However, such displayed a high ICE of 91.6% and retained 97.2%
a rather uncontrolled and random composition might lead to (420 mA h g1) of the initial capacity in half-cells aer 100
a pronounced inhomogeneity of the different compounds that cycles. When evaluated in prototype full-cells with LCO as the
can potentially induce local structural damages and/or voltage cathode active material, an ICE of 89.7% was recorded and the
differences, causing electrode cracking and lithium plating in capacity retention aer 400 cycles was 67%.345
the worst case, respectively.338 In fact, the choice of the mixing Further improvement was suggested to be achievable by
method (and conditions) is decisive for the eventual structure of optimizing the bonding between the carbonaceous species and
such silicon/graphite composites. For instance, the mechano- the silicon particles346,347 as well as the overall electrode
chemical milling of silicon and graphite in a ratio of 20 : 80 composition and the nature of the binder. To optimize the
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was demonstrated to result in the surface decoration of silicon overall electrode composition, Beattie et al.348 designed a theo-
on graphite, while a treatment by rotational impact blending retical model based on geometrical considerations, i.e., the
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yielded silicon encapsulated graphite particles.341 And packing density and the volume variations occurring, targeting
although the ICE was relatively high for both composites with the realization of electrodes with minimized particle movement
about 86%, the electrochemical performance was rather in order to achieve high active material mass loadings. This
different. The one with silicon decorated on the graphite model predicts that electrodes with a silicon content of
surface exhibited signicantly better capacity retention and <20 vol% may cycle stably for hundreds of cycles with specic
overall electrode stability. The inferior performance of the capacities of around 660 mA h g1 despite a very high binder
other sample was ascribed to the damage of the graphite content of up to 56 wt%. Experimental data showed that even
particles and inter-particle cleavage due to the large expansion higher capacities could be achieved by increasing the silicon
of the encapsulated silicon aggregates. In fact, the synthesis of content to 33 vol%, which could not be predicted by the model,
such Si/carbon/graphite multicomponent structures does not as it does not consider electrode porosity. However, the elec-
need to be complicated, following the results reported by Kim trode porosity and its reduction by calendaring play a critical
et al.342 Based on commercial silicon nanoparticles and NG role, especially, when it comes to the evaluation of energy
microspheres, composites with a varying silicon content of densities, which – in most cases – is inferior to that of highly
10 wt%, 15 wt%, and 20 wt% were prepared via a simple and densied graphite anodes.21,332 Nevertheless, also Bridel et al.349
cost-efficient synthesis route. These composites exhibited an reported superior performance for rather high binder contents
ICE of ca. 80%, stable cycling at capacities of about with an optimum ratio of 1 : 1 : 1 for the silicon/carbon/polymer
600 mA h g1, 650 mA h g1, and 700 mA h g1, respectively, composition. Their study, moreover, revealed the importance of
and excellent rate performance with approximately 88% of the the chemical nature of the binder by comparing CMC, PAA,
initial capacity at a dis-/charge rate of 5C (3250 mA g1). The amylose, and chitosan; precisely, the interaction of the binder
authors ascribed this superior electrochemical performance with the silicon active material. According to their results,
to the hierarchical structure of the composite with the silicon hydrogen bonding was advantageous over ester-type covalent
nanoparticles homogeneously covering the graphite particle bonding, as it enables self-healing properties, i.e., a reversible
surface and the realization of an amorphous carbon layer on bonding to the silicon surface upon the extensive volume vari-
top, which effectively accommodates the volume expansion ations. The best performance was achieved with long-chain
and simultaneously maintains good electrical contact CMC, delivering almost the full capacity of silicon for more
throughout the composite. Comparable results were obtained than 100 cycles with an average CE of 99.9%. However, the
for similar composites within which the silicon nanoparticles porosity of such electrodes was very high, leading to rather low
(100 nm) were uniformly distributed on the micrometric volumetric capacities. In a follow-up study, the CMC binder was
graphite particle surface, both together encapsulated by an further optimized to promote hydrogen bonding over covalent
additional carbon coating,343,344 suggesting that such bonding by adjusting the slurry pH with hydrochloric acid.
composite architecture is generally advantageous for Despite the still rather high porosity of around 60%, the authors
achieving good electrochemical performance. However, care could nearly double the volumetric capacity compared to clas-
has to be taken that this carbon coating does not get too thick sical graphite electrodes with only 25% porosity.350 Following
and that the graphite particles do not block the lithium these ndings, Yim et al.351 performed a detailed investigation
transport to the silicon nanoparticles, as these are commonly on practical full-cells with silicon/graphite blend negative
particularly active at elevated dis-/charge rates.345 Nonethe- electrodes. Based on their own theoretical model, they rstly
less, a comparison of such composites blended with optimized the silicon : graphite : binder ratio in order to limit
commercial graphite and taking into account commercially the composite volume expansion to 40%, which was chosen as
relevant electrode characteristics, i.e., an electrode density of the available free “void” within a commercial battery composite.
>1.6 g cm3, an areal capacity of >3 mA h cm2, and a low As a result, they obtained a practical ratio of 9 : 81 : 10 with
binder content of <3 wt%, revealed that such composites can a theoretical reversible capacity of 692 mA h g1. Subsequently,
indeed meet the requirements of industry if the silicon and they also calculated the energy density improvement in full-cells
carbon surface layer on the graphite particles is sufficiently comprising NCM, LCO, or LNMO as positive electrode active
thin and if the composite particles have a similar size, tap material in dependence of the amount of silicon in the
density, and surface area as the pure graphite used for composite. For the optimum amount of silicon in the anode
obtaining the blend. The best performing composite composite (9 wt%), theoretical improvements of 18%, 23% and
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34%, respectively, could be achieved. However, the model fails (different from the additive-free electrolyte), which better
to take into account also the irreversible capacity, which accommodates the volume changes and facilitates rapid ion
substantially varies with the silicon content. Thus, an accord- transport, presumably originating from the rather high Li+
ingly optimized full-cell with the theoretically almost ideal ratio concentration in the SEI. Moreover, the conducted dQ/dV
retained only 63% of the initial capacity aer 50 cycles. analysis showed that the addition of VC and FEC suppressed
Following a purely experimental approach, Schott et al.352 the loss of cyclable lithium and electrochemically active silicon.
studied the inuence of the lithiation procedure and particle Nevertheless, in all cases, signicant capacity fading was
size of commercial silicon nanoparticles as an additive to observed due to the continuous shi of both the anode and
enhance the specic capacity of graphite electrodes starting cathode voltage window to higher values upon cycling. For the
This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
from a silicon content of 5 wt%. They found that stable cycling negative electrode, the eventual shi above 0.15 V vs. Li/Li+
can be achieved for relatively small particles with a diameter of rendered the lower potential plateaus of graphite no longer
Open Access Article. Published on 07 May 2020. Downloaded on 12/3/2023 1:02:51 PM.
30–50 nm and applying a slightly elevated cut-off potential of accessible, which largely contributed to the fading recorded.
50 mV for the lithiation process when using a CCCV (constant Interestingly, Dupré et al.356 showed that this fading is not
current, constant voltage) protocol – presumably due to the only necessarily related to active material degradation, as the single
partial utilization of graphite and silicon. In fact, the applica- electrodes, aer a comparable full-cell study, revealed stable
tion of a lower lithiation potential of 5 mV did not result in any capacities as high as the initial values in subsequent half-cells
signicant improvement despite the increased risk of lithium tests. Hence, the authors concluded that the major reason for
metal plating, while the complete lithiation also leads to a more the fading was the continuous loss of cyclable lithium due to
severe volume expansion when forming the fully lithiated parasitic reactions at the anode/electrolyte interface. This
Li15Si4 phase.353 Aer an extrapolation of the expected capacity nding is in line with a study by Dahn and co-workers who
values for higher silicon contents, Schott et al.352 also studied observed a continuous consumption of the (10 wt%) FEC
electrodes with a ratio similar to that suggested previously by additive upon cycling and, once it had been completely
Yim et al.351 The resulting electrodes containing 10 wt% of consumed aer about 400 cycles, the full-cells were fading
silicon were able to compensate for the incomplete utilization rapidly.357 Based on these results they concluded that the
of graphite when applying the higher cut-off potential of 50 mV, presence of FEC prevents the transesterication of the EMC co-
with silicon contributing with more than 50% to the total solvent, which in absence of FEC leads to steady increase in cell
specic electrode capacity of ca. 650 mA h g1.352 Eventually, the polarization.
authors pointed out that stable cycling with a capacity of more
than 600 mA h g1 could be expected for electrodes containing
only 8 wt% of silicon, while further improvement was antici- 5. Conclusive summary and
pated for electrodes comprising a different matrix than graphite perspective
that would also be electrochemically active in such slightly
elevated potential region.352 Graphite is and will remain to be an essential component of
Another approach to enhance the electrochemical perfor- commercial lithium-ion batteries in the near- to mid-term
mance relies on the earlier discussed pre-lithiation of the anode future – either as sole anode active material or in combina-
(see Section 4.3.1). This has been demonstrated, for instance, tion with high-capacity compounds such as under-
for a composite of hard carbon (40 wt%) and silicon nano- stoichiometric silicon oxide, silicon–metal alloys, or elemental
particles (15 wt%) mixed with graphite (45 wt%).354 Without pre- silicon. As a matter of fact, important EV manufacturers,358
lithiation, this composite showed stable cycling above material suppliers,285 and cell producers359 have recently
600 mA h g1 with a capacity retention of 92% aer 150 cycles. announced that such graphite-containing composites will mark
The ICE, however, was only 80%. Introducing 7.5 wt% or the state-of-the-art for next-generation lithium-ion batteries,
8.3 wt% of SLMP© into the composite electrode (see Fig. 14d) providing signicantly enhanced energy densities compared to
allowed for increasing the ICE to remarkable 86% and 93%, the current technology.
respectively. Finally, by introducing FEC as a suitable electrolyte Nonetheless, despite the extensive research in the past
additive, the authors realized high-areal capacity anodes decades, there are still several aspects that remain to be
(>2.0 mA h cm2), pointing towards the possibility to scale-up understood concerning, e.g., the detailed de-/lithiation mecha-
the process and meet commercial requirements. nism, the reactions occurring at the electrode/electrolyte inter-
Focusing on the optimization of the electrolyte composition face, and the impact factors that limit the rapid intercalation of
for silicon-comprising anodes, Abraham et al.355 conducted lithium cations into the graphite lattice. In fact, very recent and
a detailed EIS analysis of full-cells based on 15 wt% silicon/ so far unpublished data indicate that the desolvation energy at
graphite blend negative electrodes and NCM532 positive elec- the SEI plays a decisive role and its careful control by modifying
trodes. The comparative investigation of different electrolyte the electrode/electrolyte interface might enable substantial
additives revealed that the incorporation of 10 wt% FEC or VC improvements for the fast charging of the resulting lithium-ion
led to an improvement in capacity retention aer 50 cycles from cell. Besides, the recycling of graphite as potentially critical raw
40.2% to 65.4% and 67.5%, respectively. The introduction of material still needs to be enhanced as well, while synthetic
these additives enabled the formation of a stabilized SEI, graphite as alternative provides several advantages, but also
showing hardly any increase in impedance upon cycling shortcomings. Accordingly, there is plenty of room for further
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