Review

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Emerging Organic Surface Chemistry for Si Anodes

in Lithium-Ion Batteries: Advances, Prospects, and Beyond
Zidong Chen, Askar Soltani, Yungui Chen, Qiaobao Zhang, Ali Davoodi, Saman Hosseinpour,
Wolfgang Peukert, and Wei Liu*

vehicles [EVs] and consumer electronics).[2]

Due to its uniquely high specific capacity and natural abundance, silicon (Si) To date, lithium-ion batteries (LIBs) as
anode for lithium-ion batteries (LIBs) has reaped intensive research from both one of the most promising means of
academic and industrial sectors. This review discusses the ongoing efforts in energy storage have witnessed progressive
upgrades of cell energy density and cost
tailoring Si particle surfaces to minimize the cycle-induced changes to the inte-
reduction, enabling, for example, longer
gral structure of particles or electrodes. As an upgrade or alternative to conven- EVs travel ranges (>300 km/charge) and
tional coatings (e.g., carbons), the emerging organic moieties on Si offer new deeper penetration of renewables into grid
avenues toward tuning the interactions with various battery components that electricity. Despite the fast growing market
are key to electrochemical performances. The recent progress on understanding of LIBs[3] and the worldwide conspic-
uous rise in LIBs production, the practical
Si surfaces is reviewed with an emphasis on newly emerged diagnostic tools,
specific energy density of prevailing LIBs
which increasingly points to the critical role of organic components in stabi- adopting graphite anode is approaching
lizing Si. The detailed analysis on the chemistry–structure–performance rela- its theoretical limit, that is, ≈250 Wh kg−1
tionships in Si surface are discussed and the successful cases demonstrating when paired with high-energy ceramic
the functions of the organic layers are provided, that is, via tailored interac- cathode such as nickel cobalt manganese
tions toward electrolyte or binder or conductive agents, are recapped. Various oxides. Nevertheless, to meet the ever-
present relentless demand from end-users
synthetic strategies for designing the surface organic layers are discussed and
such as portable electronics and EVs, the
compared, highlighting the versatility and tunability of surface organic chem- battery ought to be upgraded to provide
istry. The holistic considerations and promising research directions are sum- 400–500 Wh kg−1, 700–800 Wh L−1 with
marized, shedding light on in-depth understanding and engineering Si surface lower cost (<9.5 US cents/Wh, expected
chemistry toward practical LIBs application. in 2030), and fast charge capabilities (>2C,
i.e., fully charged within 1/2 h).[4] To achieve
these goals, the core strategy for developing
1. Introduction next-generation LIBs is to exploit higher-capacity battery mate-
rials that are cheap and abundant.
Historical global climate change has called for utilization of Silicon (Si) is recognized to be one of the most appealing
renewable energy sources and more effective CO2 reduction choices of anode materials due to its inherent low-cost, nat-
plans in achieving “carbon neutrality.”[1] Energy storage tech- ural abundance, and the ultrahigh theoretical capacity of
niques, therefore, have become a pressing need in particular with 3590 mAh g−1 (based on Li15Si4) at low potential (<0.4 V vs Li/
grid-scale and mobile energy application scenarios (e.g., electric Li+).[5] Pioneering battery manufacturers like CATL and Tesla have

Z. Chen, A. Soltani, Y. Chen, W. Liu A. Davoodi, S. Hosseinpour

Institute of New-Energy and Low-Carbon Technology (INELT) Materials and Metallurgical Engineering Department
Sichuan University Faculty of Engineering
Chengdu, Sichuan 610065, China Ferdowsi University of Mashhad
E-mail: [email protected] Mashhad 91779, Iran
Z. Chen, Y. Chen, W. Liu A. Davoodi
Engineering Research Center of Alternative Energy Materials & Devices Department of Materials Science and Engineering
Ministry of Education Sichuan University – Pittsburgh Institute (SCUPI)
Sichuan University Chengdu, Sichuan 610065, China
Chengdu, Sichuan 610065, China S. Hosseinpour, W. Peukert
Q. Zhang Institute of Particle Technology (LFG)
Department of Materials Science and Engineering Friedrich-Alexander-Universität-Erlangen-Nürnberg (FAU)
College of Materials Cauerstraße 4, 91058 Erlangen, Germany
Xiamen University
Xiamen, Fujian 361005, China
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/aenm.202200924.
DOI: 10.1002/aenm.202200924

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already commercialized the utilization of small amounts of Si failure as: 1) SEI instability during which the SEI layer is con-
as an additive in graphite anode, reaching a cell energy level of stantly destroyed and regenerated, consuming large amounts
300 Wh kg−1 to enable longer travel ranges of EVs.[6] Nonetheless, of lithium ions; 2) Electrode swelling and disintegration during
to further improve cell metrics toward higher energy density, a repeated cycling in which particle fracture, electrode disintegra-
Si-based anode with increasing Si contents deems necessary. This tion, and continuous exposure of fresh, surfaces to the electro-
imposes severe challenges in juggling many aspects of anode lyte give rise to increasing active Li loss in SEI or “dead” SixLiy
attributes such as cycle-life, capacity, tap density, and cost.[7] alloy; and 3) Loss of electric contact by which active Si particles
Over the past two decades, tremendous efforts have been progressively lose electrical contact and evolve to dead Si.[9a,b,13]
devoted to the research of Si-anodes, making great headway The capacity loss in Si anode can also be considered as a com-
toward their application in commercialized LIBs.[8] A series of plex and intermixed process involving multiple mechanisms
previous authoritative review articles have given a thorough and such as active Li loss in SEI, Li-trap in bulk phase SixLiy, elec-
full appreciation of these aspects,[9] where the reported strate- trolyte dry-out, and formation of dead “Si.”[14]
gies and successful cases mainly focused on three prominent Prior studies showed that the problematic volume expan-
directions: 1) elaborate structural design of Si-particles that are sion is surmountable by the use of nanosized Si or decorated
more durable against stress and volume changes,[10] 2) novel Si particles with nanostructures. For instance, lowering the Si
electrode additives including polymer binder and conductive particle size down to the nanometer-scale could greatly alle-
agents (CAs) that improve electric conductive pathways and viate particle fracture by releasing the mechanical stress asso-
help to ensure electrode integrity,[11] and 3) advanced electrolyte ciated with electrochemical lithiation.[15] Though nanostruc-
systems that are more compatible with Si-based particles.[12] tured Si anodes can improve the cycle life of Si anodes, the
A shared feature of these strategies is that all reported perfor- associated synthesis and processing complexities, and relatively
mance improvements are in strong correlation with the sur- high material cost call for more efforts to meet the demands
face chemistry of Si or Si-based particles. For instance, inter- of large-scale applications.[6b,16] Any battery material evaluation
facial adhesion of binder molecules onto Si particles is highly must also consider possible low tap density and high specific
dependent on surface chemical groups of Si and strongly affects surface area (SSA) of nanosized electrodes made from nanopar-
battery cycle life. Similarly, improved cycle stability of Si anodes ticles, all of which are known to result in low volumetric energy
in novel electrolyte systems is rooted in chemical and structural density and severe initial Coulombic efficiency (ICE) loss.
attributes of the formed solid electrolyte interface (SEI) film, Moreover, progressive degradation of the electrical contact is a
which is predetermined by electrolyte decomposition on Si sur- known notorious aspect that impedes the application of nano-
face prior to bulk-phase lithiation of Si. Thus, since the surface Si.[17] Therefore, advanced processing of nanoparticulate struc-
chemistry in Si anodes is emerging as a pivot for the develop- tures covering the whole process chain from synthesis toward
ment of the next generation LIBs, summarizing and analyzing the final electrode structures at large scale are mandatory for
recent progress from correlational studies could be of unique any comprehensive functional optimization.
and practical value. To overcome these challenges, multidimensional nanostruc-
Given more and more evidence reported to date, we con- tures have been proposed, designed, and constructed.[17d] To give
sider that an organic artificial layer is an emerging key factor one recent example, Bachmann et al.[18] produced highly ordered
in achieving surface stability of Si anode, more effective than Si nanotube arrays directly grown on Cu collector. The amor-
traditional inorganic coating layers (e.g., carbon coating). In phous Si nanotube arrays exhibit superb electrochemical
this review, we will first summarize the ongoing progress in the activity without the aid of binder and CAs. Another pathway
understanding and engineering of Si surfaces for LIBs appli- toward improved performances could be Si-based alloys.[19] For
cation. Advanced analytical tools offering an in-depth insight instance, germanium (Ge)–Si alloys exhibit a superior electronic
into the surface local environment and cycle-induced evolution and ionic conductivity and the coexistence of Si and Ge in the
will be introduced. Then we focus on emerging organic surface properly formulated GexSi1−x phase results in a beneficial effect
chemistry modifications on the Si anodes that generate uncon- on the structural stability.[20] These strategies require proper
ventional SEI interface or physicochemical interactions with design and most importantly scale-up strategies for large scale
binder and/or CAs. Case studies to highlight recent advances applications. Increasing attention is paid to developing advanced
in this field will be discussed in detail, illustrating the key polymer binders[11c,21] or electrolyte systems[22] that contribute
concepts of organic surface chemistry design. In addition, we to improving the cycle performances of Si-based LIBs. We here
further discuss the guidelines of surface engineering and the note the high level of reactivity of Si/SixLiy (either in the form
associated metrics that are key to the end-use cell application. of nanoparticles or microparticles) with liquid electrolyte at
Prospects for future research directions and opportunities are cathodic potentials and the inherent stress fluctuation and accu-
also provided. mulation at the Si–CAs or Si–binder interfaces during cycling.
There are clear and strong correlations of the aforementioned Si
failures with the interfacial interaction between Si and electro-
2. Challenges and Progress for Silicon-Based Anodes lyte, electrode binder, and CAs. Hence surface chemistry design
and engineering of Si are in a uniquely critical position in devel-
It is well established that the large volume change (≈300%) in oping next-generation Si-anodes. We re-evaluated the reported
Si during electrochemical reaction Si + Li ↔ Si4Li15 is the root phenomenological findings to date and identified the interfacial
cause for a shortened lifespan of Si anodes. Previous studies instabilities on Si as the main mechanistic root cause of electrode
have categorized the main phenomenological roots of Si anode performance fading.

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Figure 1. Schematic illustration of interfacial failure mechanisms in Si anode. a) Si–electrolyte interface failure leads to SEI fracture and repeated
growth, consuming active Li and electrolytes. b) Si–polymer binder interface failure and associated stress accumulation lead to particle cracking, pul-
verization, and electrode disintegration. c) Si-conductive additive interface failure gives rise to loss of electric contacts.

One may categorize the cycle-induced interfacial evolution or as coating layers on current collectors[28] emerged as effec-
patterns of Si anodes and schematically summarized them tive means of releasing the cycle-induced stress, demonstrating
(Figure 1). The corresponding failure mechanisms can be great value not only for improving Si-anode performances but
described as: 1) Si–electrolyte interface failure: huge volume also for designing flexible LIBs. Si-current collector interactions
expansion during cycling leads to SEI fracture and the fresh provide new perspective but call for more exploration, and for
surface exposure toward electrolytes, causing parasitic side practical LIBs design <10 µm, thin Cu collector is by far the
reactions that consume active Li and electrolytes (Figure 1a); most realistic choice. Hence in this review this aspect is not
2) Si–polymer binder interface failure: polymer binders fail to pursued further.
provide enough mechanical constrains and adhesion to parti-
cles, resulting in progressive pulverization and disintegration
of the electrode during cycling (Figure 1b); 3) Si–conductive 3. Emerging Understanding of Si Surfaces
additives (CAs) interface failure: active particles lose electrical
contacts with CAs due to cycle-induced particle migration 3.1. Conventional Understanding toward Si Surfaces
and rearrangements, and/or electrode swelling and cracking
(Figure 1c). Since the Si particle surface simultaneously inter- Prior investigations have intensively studied the formation
acts with electrolyte, polymer binder, and conductive additives, and structure of SEI layer on the Si surface and concluded its
the actual fading of Si anodes could be regarded as intermixed critical role in electrochemical performances.[29] It is known
combinations of these interfacial failures with the predominant that the reduction of liquid electrolytes occurs before lithium
contributor(s) evolving with respect to particle/electrode struc- reaches the underneath Si core. Nevertheless, the resulting SEI
ture, electrolyte formula, cycling conditions, etc. dramatically affects the kinetics and reversibility of subsequent
It also should be mentioned that the detachment of Si active Si–Li alloying reactions. The composition and structure of SEI
particles from the current collector after repeated cycling is a on Si have been intensively investigated and have been found
widely reported phenomenon, pointing to the possibly critical to be a composite thin film consisting of inorganic LixPFy, LiF,
role of Si-current collector interactions.[23] In addition to binder Li2CO3, and organic Li-OR, LiO2C-OR, and poly(ethylene-oxide)
engineering, modification of current collectors,[24] 3D porous type polymer/oligomers stacking up with a “mosaic” struc-
current collectors,[25] and chemically bonding active materials ture.[30] The precise chemical content and spatial distribution
with current collectors[26] are reported to be effective in rein- of all SEI components relies on the electrolyte formulation and
forcing particle-current collect adhesion that improves the intrinsic characteristics of the Si surface.
electrochemical performance of Si-based anode. Moreover, Si particles are naturally covered by a native oxide (SiOx)
stretchable and/or flexible polymer as conductive substrates[27] layer resulting from oxidation by air. The role of the native SiOx

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layer in affecting Si anode performances is quite profound and Si is transformed to an amorphous state. In the SERS spectra,
complex. Earlier studies revealed that the native oxide layer will however, upon lithiation at 0.9 V versus Li/Li+, new bands at
be transformed to Li2O and LixSiOy during lithiation, hence 132, 162, 199, 443, 698, 1094, 1315, and 1475 cm−1 are observed
consuming active lithium which leads to lower ICE.[30c] The which are attributed to Li2CO3 from ethylene carbonate (EC)
thick SiOx surface layer consumes Li by being converted to reduction. Furthermore, an extra peak is observed in the SERS
electrochemically inert silicate and isolating the Si core from spectra at 1000 cm−1 at 1.5 V in the systems containing VC, sug-
lithiation. Hence, the Si nanoparticles (SiNPs) with thicker gesting the radical polymerization of VC before the reduction of
oxides layer are found to deliver lower specific capacity than EC. Hence, empowered by surface sensitive SERS with signal
their counterparts with thinner oxides layer.[31] Moreover, the enhancement by a factor of 106 compared to normal Raman,
SiOx native layer is often found to be terminated by hydroxyl the passivating effects of VC in the electrolyte can be under-
groups or chemisorbed moister. These protic species (OH or stood by the formation of highly elastic poly VC. Furthermore,
COOH) react with electrolytes and form unstable SEI that compared to normal Raman, SERS suggests an explicit para-
results in accelerated capacity decay.[32] Noticeably, positive digm of Si structure evolution during lithiation. With SERS, a
effects could also stem from the well-structured native SiOx much faster amorphization of Si in VC-containing electrolytes
surface. For instance, it is found that the native oxide layer sig- than in normal electrolytes was identified. This is not trackable
nificantly affects the electrolyte decomposition process on the with conventional Raman.
Si surface so that Si with native oxide layer gives rise to thinner In tip-enhanced Raman spectroscopy (TERS), not only the
and more compact SEI than the naked Si surface counterpart enhancement of the Raman signal (by the localized electro-
(generated by HF etching).[33] It is also demonstrated that the magnetic field) is utilized but also the application of a sharp
surface oxide layer helps the polymer binder (such as carboxy- tip provides this method with a high spatial resolution for
methylcellulose [CMC], polyacrylic acid [PAA], and sodium alg- mapping the distribution of both topographical and chemical
inate) to better adhere and graft onto Si particles, leading to variations of the electrode surface at nanoscale (Figure 2b). For
better cycle life.[34] instance, Nanda and Yang et al.[37] employed TERS to study SEI
One may view the native SiOx surface as a double-edged composition evolution of amorphous Si thin-film electrodes.
sword for Si anodes: on one hand, it prevents direct contact Using TERS they identified large quantities of organic species
between Si/SixLiy with electrolyte to passivate the surface and including poly(ethylene oxide) (PEO)-like oligomer and lithium
promotes binder adsorption on the surface of Si. On the other ethylene dicarbonate (LEDC) after the initial cycle. They also
hand, it consumes active Li and exerts mechanical constraints observed that the surface layer gradually evolves to be richer
and/or ion transport barriers that impede the lithiation reac- and richer in LEDC after five cycles and carboxylate (RCO2Li) +
tion of underneath Si. A recent study carried out by Zhu and fluorinated species (LixPOyFz) after 20 cycles. To extract detailed
Yang et al.[35] showed that, among surface oxide coating in the information and meaningful data from a large number of TERS
range of 1–10 nm, an optimal thickness of the surface oxide layer spectra, mathematical methods such as principal component
(≈5 nm) demonstrated the best cycle performance. A thinner analysis and multivariate curve resolution analysis are devel-
oxide coating layer was inclined to crack during cycling which oped. The authors used these methods to confirm that the dis-
led to fast capacity decay, while the thicker one would hinder the tribution of identified species on the Si surface is highly hetero-
electron and Li-ion transport, completely deactivating the Si core. geneous. The nanometer-level spatial resolution of TERS allows
the authors to propose a multilayer hybrid structure of SEI Si
in which each layer consists of various SEI species arranged in
3.2. Understanding Stemming from Novel Diagnostic Tools a mosaic manner where the organic species appear to be richer
and richer in the outmost layers.
Although the pivotal role of the surface film on Si in deter- As described, advanced spectroscopy provides avenues to pre-
mining its electrochemical performance is well recognized, the cisely probe the chemical structures of Si SEI. Other methods
thin (often in nanometers range), heterogeneous, and dynamic in which an electron beam is utilized to determine the chem-
nature of SEI on Si surface raises severe limitations for the ical composition can also be used with reasonably high spatial
precise description and in-depth understanding of the surface resolution in an electron microscope. However, direct imaging
toward chemistry–structure–performance relationship. Dif- or crystallographic analysis of the surface film is impeded by
ficulties in probing the interfaces between Si and Si–binder or its inherent frangibility to electron beam damage and low con-
Si–CAs further impede the rational design of Si surfaces. Hence, trast under commonly used microscopy techniques. To over-
to date, the ideal composition and structure of the surface film come this challenge, cryogenic electron microscopy (cryo-EM)
remain controversial. Thus, developing advanced diagnostic can be used which minimizes beam damage during imaging
tools which can offer site-specific or time-resolved information and offers an outstanding resolution of the near-atomic struc-
at the interface is the key to shedding light on these aspects. ture of even organic molecules. Cryo-EM initially made its
Hwang et al.[36] used normal Raman and surface-enhanced success in molecular biology and was later introduced in the
Raman spectroscopy (SERS) to observe the surface evolu- studies of battery materials. Figure 2c shows the schematic of
tion on Si, unveiling the key function of a SEI-modifying the cryo-transmission electron microscope (cryo-TEM) used by
electrolyte additive: vinylene carbonate (VC). As shown in Meng et al.,[38] adopting liquid nitrogen temperature (100 K) for
Figure 2a, normal Raman spectroscopy only shows one dis- transferring and viewing the post-cycled electrode.
cernable peak at 530 cm−1, the intensity of which gradually Very often EM investigations are complemented by other elec-
drops with decreasing voltage indicating that the crystalline tron beam-based analysis. For instance, Cui et al.[39] employed

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Figure 2. Novel diagnostic tools promote understanding of Si surface chemistry–battery operation relations. a) Surface-enhanced Raman spectroscopy
(SERS) tracks electrolyte decomposition products on the electrode surface. Adapted with permission.[36] Copyright 2014, Elsevier. b) Tip-enhanced
Raman spectroscopy (TERS) probes local chemical and topographical information and provides dynamic evolution of surface SEI with spatial resolu-
tion down to 10 nm. Adapted with permission.[37] Copyright 2019, Elsevier. c) Cryo-TEM avoids electron beam damage to sensitive species and enables
atomic-scale images in tracking structural evolution of both e-beam sensitive SEI and SixLiy alloys during cycling. Adapted with permission.[38] Copyright
2017, American Chemical Society. d) Cryo-TEM identifies organic components on the top most layer of SEI from FEC decomposition that is highly
beneficial in promoting Si cycle stability. Adapted with permission.[39] Copyright 2019, Elsevier.

cryo-TEM and electron energy loss spectroscopy (EELS) to visu- porous as a consequence of repeated Li+ insertion and extraction.
alize the SEI on Si anodes formed in EC electrolytes with elec- It is confirmed that in the initial cycles the SEI on the surface
trolyte additive fluorinated ethylene carbonate (FEC). As shown of Si possesses a core–shell structure. But with repeated cycling,
in Figure 2d, Cryo-STEM EELS mapping reveals that a bilayer electrolyte progressively permeated into pores contemporary
SEI was formed in EC/DEC electrolyte, consisting of an inner with “foaming” of Si. The gradual growth of the SEI inside Si
amorphous LixSiOy and an outer layer amorphous LEDC and contributes to the capacity loss, blocking electron and Li-ion con-
crystalline Li2O. However, these inorganic and organic species duction pathways, and forming regions of dead Si.
were inclined to decompose upon charging to 1 V. By contrast, Although detailed information on the characteristics of the
the SEI formed in the presence of 10% FEC also shows a bilayer Si electrodes can be obtained using ex situ experiments, the
structure, where the inner core of LixSiOy remained but a cross- studied surface may undergo changes before and during its
linked poly(VC)-rich organic outer layer replaced the LEDC and ex situ examinations. For instance, the vacuum condition in
Li2O. The cross-linked polycarbonate is stable against oxidation electron microscopy can potentially alter the surface struc-
and is highly elastomeric, effectively passivating the surface and ture as compared to it in the LIBs assemblies. Hence, to gain
inhibiting further decomposition of electrolytes. In a more recent insight into the evolution of surface characteristics, real-time
study adopting cyro-TEM carried out by Yoo, Li, Zhang, and and in situ characterization under operating conditions (e.g.,
Wang et al.,[40] Si nanowires were found to become increasingly in operando) of batteries is highly desirable. Grey et al.[41]

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Figure 3. Novel diagnostic tools precisely probed characteristics and evolution of Si surface during cell operation. a) Operando solid-state NMR
probes local chemical structure and dynamics in the working cells. Adapted with permission.[41a] Copyright 2013, American Chemical Society. b) NMR
identified cross-linked polymer-based SEIs from FEC or VC that greatly promotes life span of Si anode. Adapted with permission.[12b] Copyright 2018,
American Chemical Society. c) AFM with scanning spreading-resistance set-up enables resistance imaging and mechanical depth profiling of electronic
conductivity of Si surface. Adapted with permission.[42] Copyright 2019, Elsevier. d) In situ AFM measures the force spectroscopy between Si-cantilevers
and polymer films to emulate Si–binder interactions. Adapted with permission.[43] Copyright 2020, American Chemical Society.

adopted in situ nuclear magnetic resonance (NMR) spectros- to volume changes and prevents Si surface from side reaction
copy of 7Li to detect the Si–Li intermediate formed at various with electrolyte whereas the presence of SiC interfacial bond
states of charge (SOC). As shown in Figure 3a, the battery was improves the adhesion of SEI onto Si. The organic species in
placed inside the NMR coil. Using such an experimental con- SEI is hence thought to contribute to improved Coulombic effi-
figuration, the authors were able to collect the NMR spectra as ciency and cycling stability in LIBs.[12b,41]
a function of SOC in tracking the structural changes of Si. The Other complementary spectroscopy and electron micro­scopy
in situ 7Li NMR spectra are shown in the bottom-right corner investigations also have unveiled the chemical, structural,
in Figure 3a. The resonances in 14–18 ppm are attributed to and morphological attributes of Si surface. In particular local
lithium near the Si clusters while the resonance at −10 ppm, probe techniques, especially atomic force microscopy (AFM)
which appears at deep discharge, is assigned to phase Li15Si4. as a versatile tool to study the topography of surface character-
Furthermore, the resonance at 10 ppm appears below 30 mV istics and interfacial interaction forces with resolution down
indicating a side-reaction between Li15Si4 and electrolyte, to near-atomic scale, have been extensively used in in situ and
resulting in capacity loss. Grey’s group[12b] further employed ex situ characterizations of the Si-based anodes in LIBs. AFM
solid-state NMR to study SEI formed on Si. Using 13C NMR offers a golden platform to probe the site-specific properties
they identified that FEC or VC electrolyte additives help to of the surface films (e.g., modulus, elasticity, and electric con-
stabilize Si surface by forming SEI that contains cross-linked ductance) as well as the interfacial interactions between Si
PEO and aliphatic chains. Moreover, as revealed by 29Si NMR, and binder or Si and CAs. Stetson and Jiang et al.[42] employed
part of Si surface was covalently bonded to organic SEI compo- scanning spreading resistance microscopy (SSRM), which is
nents. The highly cross-linked ion-permeable PEO is durable based on the AFM operating in contact mode, to study the

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electronic resistivity of SEI of Si. Figure 3c (left panel) depicts challenging, fully unveiling the nature of a highly dynamic
the schematic diagram of SSRM measurement principle. In electrode surface layer is an unyielding pursuit in the battery
this method, the resistance is calculated through R = V/I in research community. NMR and X-ray absorption spectroscopy
which V refers to a voltage between the probe and sample and (XAS) are powerful and non-destructive tools often adopted in
I refers to the current through the probe. Then the resistivity scrutinizing the fine chemical structures even from a very lim-
is calculated through ρ = 4rRsp in which r and Rsp refer to the ited amount of specimens down to micrograms.[51] However,
radius of the contact area and the spreading resistance, respec- in general NMR and XAS are considered “bulk-level” charac-
tively. In Figure 3c (middle panel), a resistance depth profile terization techniques unable to probe surface-specific and site-
on the SEI formed on a model single-crystalline wafer Si specific information.
anode is shown, indicating that resistance undergoes a steep In fact, many aspects of electrode surface are imperceptible
reduction in resistivity (0–6 nm), followed by a stable plateau via “bulk-level” characterization methods, and a comprehen-
(6–20 nm) and finally a further decrease (20–55 nm). These sive and explicit understanding of Si surface relies on advanced
results clearly indicate that the conductivity of SEI changes in spectroscopic and microscopic tools with high spatial resolu-
the depth direction. Figure 3c (right panel) in contrast depicts tions. Therefore, surface sensitive diagnostic tools with high
a contact-mode height image and the corresponding resist- spatial resolution that may also allow electrochemical in situ
ance channel image, pointing to a highly insulating top sur- set-ups emerged as powerful tools in solving this issue. For
face layer and uniform resistivity distribution of the SEI in the instance, SFG spectroscopy is inherently surface sensitive and
lateral direction. has been proven to be a capable technique for the investigations
Huang, Cho, and Kim et.al[43] employed in situ AFM to study of electrode interface. SFG allows for the interrogation of mole-
the morphology and physical properties of polymer binder cules and their conformation at almost any interface without
immersed in a liquid electrolyte. (Figure 3d). They measured the inclusion of the information from the bulk molecules.[46]
force spectroscopy between Si-cantilevers and two polymer Under certain experimental configurations, electrochemical
films, poly(vinylidene fluoride) (PVDF) and Na-alginate, which operando SFG is also used to investigate the development and
are immersed in dimethyl carbonate (DMC) to simulate the structure of SEI.[44,47]
adhesive forces between Si anode with binders. Their observa- A number of spectroscopic techniques, such as SERS, TERS
tions indicated that Na-alginate demonstrates orders of magni- and scattering-type scanning near-field optical microscopy/
tudes higher elastic modulus and adhesive force with Si than nano-FTIR (s-SNOM/nano-FTIR), provide key information of
PVDF counterparts both in the dry state and wet-in-DMC states. surface chemical components with capabilities to probe local
That implies the differing capability of Na-alginate and PVDF area down to nanometer size (e.g., subject to AFM tip), consti-
to maintain the electrode integrity during cell preparation and tuting a substantial upgrade from conventional spectroscopies.
operation, helping to understand the underlying mechanism Serving as a complement to Raman, FTIR is more sensitive to
on why Na alginate binder achieved better performance than polar organic species however limited by its intrinsic spatial
PVDF. These results could provide effective guidelines in the resolution. Raman or micro-IR set-ups with beam size tuned
search of novel polymer binders for Si anode. Other analyt- down to µm-level could not resolve the nanoscale heterogeneity
ical tools such as nonlinear spectroscopy can further improve of SEI layer. Conversely, TERS and s-SNOM allows acquiring
understanding of the interfacial characteristics of the Si anodes. spectrums from the interested surface with nanometric lateral
For instance, Schlenkeret al.[44] investigated electrolyte redox resolution. Electron microscopic techniques such as in situ
products at active SiNP LIBs interfaces using sum frequency SEM and TEM provide highly site-specific morphological and
generation (SFG) spectroscopy and identified distinct lithia- chemical information of the surface. Combined with cryogenic
tion potentials for carbon monoxide evolution on nano-Si for set-ups, interrogation of the elemental arrangements on the
different electrolyte solvents. Due to its inherent surface sensi- surface under high-resolution TEM and EELS also become
tivity, SFG allows studying surfaces and interfaces, for example, feasible. AFM further offers opportunities in probing local-
during their functionalization with organic molecules, without ized morphologies and concurrent mechanical and/or electrical
the inclusion of the signal from bulk media. Indeed, the poten- properties, that may be highly useful in understanding the
tial of SFG in LIBs research is yet to be explored. Similarly, nanoscale ion and electron conduction.
other advanced characterization methods such as in situ TEM In summary, advanced microscopic and spectroscopic
or SEM in a liquid cell, tip and surface-enhanced IR spectros- methods give substantially high spatial resolution down to sub-
copy, and synchrotron-based spectroscopy will provide a real- nanoscale, whereas conventional spectroscopic methods are
istic picture of the surface characteristics of Si anodes in LIBs. more powerful in interrogating the fine chemical structures of
Given the nanometer-scale thickness and hierarchical hetero- the bulk material with limited lateral resolution. With electro-
geneity of the electrode interface, harnessing various analytic chemical in situ set-ups, real-time description of the dynamic
tools is at the core of the unremitting endeavor toward precisely nature of the surface layer becomes viable and thus its correla-
understanding the electrode interface.[45] Here we provide a tion with electrochemical performances could be assigned.[53,54]
comparative summary of the conventional or advanced surface Using the state-of-the-art microscopic and spectroscopic char-
analytic techniques, as tabulated in Table 1. Both microscopic acterization methods, separately or combined, it is now better
(SEM, AFM, TEM) and spectroscopic tools (FTIR, Raman, X-ray understood that the Si surface, either in the dry-state or in-cell
photoelectron spectroscopy [XPS]) are highly useful in cap- state, significantly affects many aspects of battery performances
turing various constitutive components in the electrode surface including capacity, cycle life, and rate capabilities. From these
layer and their spatial arrangement.[48] Although being quite advanced analytical studies, the importance of both surface

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Table 1. Comparison of analytical tools employed on electrode surface 4. Organic Surface Chemistry: Emerging Solutions
characterization.
to Practical Si anode
Methods Function Spatial resolution
Si is known to have low electrical conductivity
XPS Constitutive elements and their Surface probe depth:
(10−3–≈10−6 S cm−1 depending upon doping) and is intrinsically
valence states; <10 nm (XPS electrons escape depth)
unstable against liquid electrolytes in catalyzing electrolyte dec
allows depth profile (Ar+ etch)[48] Lateral resolution:
allows electrochemical in situ Hundreds of microns
omposition.[30a,34,55] These attributes give rise to inherently slow
set-ups[49] (X-ray beam size) lithiation/de-lithiation kinetics and continuously parasitic side
reactions during cycling. It is now well known that unremit-
FTIR Polar bonds (infrared adsorption), Surface and lateral probe dimension:
allows electrochemical in situ >Hundreds of microns
ting SEI build-up and active Li loss during cycling of LIBs leads
set-ups[50] (area integral spectra) to polarization growth, gas formation, and electrolyte dry-out
in Si anodes.[5b] Moreover, stemming from surface instabilities
NMR Chemical environment of C, H, F, Insensitive to surface/site-specific
Li, etc., information
and poor adhesion, de-bonding at the Si interface and electrode
allows electrochemical in situ cracking are shown to be other prevalent causes for loss of elec-
set-ups[12b] tric contact and shortened cycle life.[56]
XAS Valence states of element, Insensitive to surface/site-specific
In recent years, numerous efforts have been devoted to the
electron distribution, information surface engineering of Si anodes. For instance, inorganic spe-
bond distance, cies have been extensively utilized for surface modification of
and coordination[51] Si anodes or as an artificial coating for Si, examples of which
SFG Vibrational spectroscopies of Surface probe depth: include metal oxides (e.g., Al2O3,[57] TiO2,[58] and MgO[59]), metal
interfacial molecules; Molecular layer of the surface nitrides (e.g., TiN[60]), and metal sulfides (e.g., MoS2[61]). These
Allows electrochemical in situ Lateral resolution: artificial surface layers exhibit substantial inertness against
set-ups[44,47] a few micrometers liquid electrolytes and hence improve surface stability of Si
(laser beam size) anodes. In principle, these inorganic species serve a role analo-
s-SNOM/ Infrared signal of local species Surface probe depth: gous to the native SiOx layer of Si, that is, in isolating electro-
nano-FTIR Allows electrochemical in From tens to hundreds of lyte erosion, giving rise to SEI interface with favorable charac-
situ set-ups[52] nanometers teristics, and improving binder adsorption or wetting onto Si
Lateral resolution: anodes. Nonetheless, we note that exploring and understanding
Often around 20–30 nm these mechanistic aspects require further investigation beyond
(AFM tip determined) the structure–property research paradigm and call for the devel-
SERS Polar/non-polar bonds Surface probe depth: opment of advanced analytic tools.
(Raman shift), Ten of nanometers (SERS signal) Besides the abovementioned inorganic coatings, carbona-
allows electrochemical in situ Lateral resolution: ceous materials, possessing good electrical conductivity and
set-ups[36] Microns (Laser-beam size)
chemical stability with electrolytes, are widely adopted can-
TERS Polar/non-polar bonds (Raman Surface probe depth: didates as surface modifiers. For instance, the carbonaceous
shift) Ten of nanometers (TERS signal) coating can greatly enhance the inter-particle electrical condu
allows electrochemical ex situ Lateral resolution:
ctivity,[10e,15c,62] and more importantly, carbonaceous materials
set-ups[37] A few to tens of nm (AFM tip
are thought to form a stable SEI layer in a liquid electrolyte
determined)
(such as EC) and passivate the Si surface.[62b,63] A wide range
AFM Surface morphology and stiffness, Surface probe depth:
of approaches including spray drying,[64] ball milling,[65] hydro-
allows mechanical and electrical 0.1 nm to tens of µm (contact
thermal[66] chemical vapor deposition (CVD),[67] and electrospin-
analysis[42] mode)
Lateral resolution:
ning[68] are amongst the popular approaches for coating carbon
Down to 0.1 nm (tip-size) allotrope precursors onto Si. Precursors such as sucrose,[69]
pitch,[70] and polymer,[65,71] in solution-based synthesis route or
SEM and Morphology and elemental analysis Surface probe depth:
EDS allows electrochemical in situ A few µm (EDS)
acetylene,[63g] methane,[72] toluene[73] etc. have been frequently
set-ups[53] Lateral resolution: adopted for surface modification of Si anodes. Low-dimen-
Down to ≈1 nm (SEM) sional carbons including carbon nanotubes (CNT), carbon
TEM and Thickness or atomic contrast, Atomic scale resolution of surface
nanosheets, and graphene layers have also been explored as
EDS crystallographic periodicity (EDS); components wraps or cages for encapsulating active Si, providing superior
allows electrochemical in situ (TEM and EELS under Cryogenic stability, mechanical flexibility, and electrical conductivity.[74]
set-ups[54] operation) Ideally, the carbon coating layers should be thin to allow fast Li
allows cryogenic set-ups[39] ion transmittance while being mechanically robust to endure
large volume changes during cycling.
In view of applications, also the production and quality of
chemical structures and interfacial interactions were high- all other compounds must be considered at large scale and
lighted. Regardless of the characterization methods in use, reasonable costs. This is particularly challenging for CNTs
more and more shreds of evidence point to the key role of whose scale-up is notoriously difficult, if not impossible due
organic layers on the Si surface, which we will further discuss to the restrictions of the underlying aerosol processes, see,
in detail hereafter. for example, Toni et al.[75] The situation is much better for

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graphene nanosheets which can be produced in dispersing accompanied by novel surface synthetic or analytic tools that
devices, high pressure homogenizers, or stirred media ball provide insights into the engineering and evolution of uncon-
mills.[76] ventional interactions on the active Si particles.
According to the existing literature, progressive degradation
of carbon layer either during electrode calendaring or electro-
chemical cycling has called for more attention. Several studies 4.1. Organic Surface Coating Interacting with Electrolyte
have identified restricted lithiation kinetics,[77] and anisotropic
lithium transport,[54a,78] after the introduction of a carbonaceous As the structure–property correlation of SEI plays a vital role
layer onto Si anodes. Moreover, progressive cracking of surface in determining the cycle life of Si anodes, efforts have been
coatings during cycling,[73,79] or calendaring[80] have also been devoted to understanding the SEI formation mechanism on the
identified as one of the main challenges in surface engineering Si surface.[55,82] The surface of Si is known to participate in the
of Si anodes. Researchers often find themselves in a dilemma process of SEI formation, as a catalytic surface that gives rise
with inorganic coating as thin layers tend to break under stress to interfacial instabilities.[83] Hence, various methods have been
whereas thick layers tend to retard Li-transport. Here, we would adapted and developed to fabricate more stable and efficient
like to emphasize the importance of precisely controlling the anode materials with tuned surface chemistry.
thickness, uniformity, and mechanical properties of organic/ Atomic layer deposition (ALD), for instance, is a vacuum-
inorganic coating layers and note that despite the significant based technique that can be widely used for depositing ultra-
progress in the surface engineering of Si anodes, this point thin coatings layers onto the material’s surface with precise
still remains challenging thus far. Hence, further study in this control of film thickness down to atomic resolution.[84] ALD
regard is highly advocated. method can be adapted to deposit conformal and uniform coat-
Complementing inorganic coating and carbonaceous mate- ings and protective layers onto battery materials, showing capa-
rials, organic surface chemistry opens up wide opportunities bilities to restrict the volume changes and reduce the electrolyte
in tuning the surface functionality and electrochemical charac- decomposition at the interface.[85] Huang et al.[57a] fabricated
teristics of Si beyond conventional inorganic coating. In gen- an alumina-coated (Al2O3) Si anode via ALD in which Si elec-
eral, organic coatings could avoid direct contact between Si and trodes were coated with 20 and 40 ALD cycles of Al2O3 (≈2 and
liquid electrolyte to isolate possible parasitic side reactions on ≈4 nm coating layer, respectively). Interestingly, the relatively
the surface, a function analogous to that in inorganics.[81] More- thick Al2O3 coating with 40 ALD cycles completely blocked
over, here we list a series of key advantages of organic coatings the lithium-ion diffusion path, whereas, the sample of 20 ALD
over inorganic coatings for Si anodes in LIBs: cycles exhibited excellent cycle performance (maintain ≈98%
after 100 cycles) and enhanced Coulombic efficiency. Such a
1) Unlike “rigid” inorganic species, organic coatings are in- strong relationship between the cycle performance and coating
herently more flexible in enduring large strain and volume thickness signifies the importance of methods with which the
changes, and the mechanical properties of the organic coat- coating thickness and its homogeneity can be precisely tuned.
ing can be further tuned through polymerization, hyper- Kalisvaart and Mitlin et al.[60a] also employed ALD-grown elec-
branching, or cross-linking. trically conductive TiN coatings to improve the electrochemical
2) Organic layers can be designed with abundant reactive performance of Si nanowires. Deposition of a variety of inor-
groups to “bridge” with polymer binder or CAs. These spe- ganic coating materials, including TiO2,[86] Al2O3,[85d,87] TiN,[88]
cial surface interactions could give rise to interfacial adhesion and HfO2,[89] has so far been explored using ALD.
among Si/binder/CAs much stronger than the pure physical Being an analogy to ALD, molecular layer deposition (MLD)
adhesion, a key aspect in maintaining the integrity of Si elec- can also been utilized to deposit pure polymeric or inor-
trodes. ganic–organic hybrid thin films. For instance, Fedorov et al.[90]
3) Organic molecules comprising SiO/CO/CF bonds can showed that MLD grown films contain polymeric components
coordinate with lithium ions to allow facile Li-transport. In with CO and CC chains, endowing the film with inherent
particular, molecularly engineered polymers or oligomers of- flexibility to accommodate larger volume expansion in LIBs.
fer opportunities in facilitating and guiding Li-ion transport Moreover, these bonds allow swelling of liquid electrolytes and
through the interface; coordination with Li-ions, thus providing superior ion transport
4) Organic layers can be fabricated via synthesis routes that capability. As shown in Figure 4a, Yin and Sun et al.[49b] reported
do not involve complex equipment or high-temperature. In an MLD zincone coating on the Si electrode adopting the self-
some cases, these coatings can be implemented synchro- limiting reaction between ethylene glycol and diethylzinc. The
nously with slurry preparation and/or vacuum drying, pos- zincone layer is an inorganic–organic hybrid film the thick-
sessing inherent compatibility and cost-effectiveness as a ness of which can be easily controlled by the number of MLD
“drop-in” in the current battery industry. reaction cycles (10, 25, and 50 cycles respectively). The MLD
method enables controlling the characteristics of the coating
These aspects make organic coating an appealing and at the molecular level. The zincone coating with ten MLD
emerging methodology for tuning Si-based particles as LIBs cycles appears to be ≈3 nm as shown in the corresponding
anodes. Recent progress has shown promising advances in TEM image in Figure 4b. In this study, the ICE of Si@10-ZC
developing organic moieties for high-performance Si anode, (Si electrode with ten MLD reaction cycles) electrode was 80%,
improving its chemical and structural stability toward state-of- much improved compared to that of neat Si (73%). As shown
the-art electrochemical performances. These studies were often in Figure 4c, the Si@10-ZC electrode also displayed highly

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Figure 4. Growth of zincone thin films onto Si anode via molecular layer deposition (MLD). a) Schematic illustration of zincone-coated silicon electrode.
b) HRTEM images of Si electrode with ten MLD reaction cycles; note that the zincone film thickness is tuned by MLD reaction cycles. c) Cycle performance
of Si anodes with varying zincone film thickness. d) Comparison of fitted RSEI and Rct of EIS testing after 60 cycles of Si anode with or without zincone
coating. e) XPS spectra of silicon electrode with or without zincone coating after 50 cycles. a–e) Adapted with permission.[49b] Copyright 2020, Wiley-VCH.

desirable cycle stability with 1741 mAh g−1 after 100 cycles at component in the SEI of Si@10-ZC. LiF-rich SEI was thought
0.2 A g−1. Conversely, neat Si displayed only 563 mAh g−1 after to have high elastic modulus and ionic conductivity.[91] More-
identical cycle history. over, analyzing the Zn 2p3/2 spectrum the authors identified
As suggested by the authors, the zincone coating isolates the existence of metallic Zn on the top surface layer of cycled
Si from side reaction with electrolyte, greatly changing the Si@10-ZC. Based on the detection depth of XPS (2–≈3 nm),
Si–electrolyte interaction that leads to stabilized SEI interface this observation suggests that the SEI layer that is formed on
throughout prolonged cycling. This was evidenced by elec- top of zincone film is very thin (thinner than 2–≈3 nm).
trochemical impedance spectroscopy results on post-cycled The MLD-grown zincone coating layer improves the char-
electrodes in which reduced the SEI impedance (RSEI) and acteristics of Si anodes more effectively than the ALD-grown
the charge transfer impedance (Rct) were observed in zincone- zinc oxide (ZnO) coatings, with zincone coating offering
coated specimens (Figure 4d). Complementary X-ray XPS anal- inherent better flexibility and mechanical durability against
ysis (Figure 4e) suggests that the zincone coating layer greatly volume expansion. Besides, it was also shown that the ZnO
alter the composition of SEI. For instance, with zincone coat- components in the MLD-grown zincone layer would reduce to
ings, inorganic Li2CO3 appears to be much sparser pointing metallic Zn during cycling, further highlighting the key role of
to an inhibited reduction of the carbonate electrolyte solvent. the polymeric component in maintaining the structural integ-
From the F 1s spectrum, LiF appears to be the predominant rity of the surface film. We note that other MLD-grown organic

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coating like alucone[92] and titanicone[93] demonstrate supe- note that the inherent compatibility of iCVD with the thermal-
rior Li-ion conductance than ALD-grown inorganic films. One and solvent-sensitive substrates makes it a particularly attrac-
direct sign is that the 15 nm-thick zincone coatings (50 MLD tive approach for battery materials modifications.[50,97]
cycles) allow facile Li cycling of the underneath Si[49b] while On this account, Tenhaeff et.al.[50] exploited iCVD to coat
4 nm-thick ALD-Al2O3 completely blocks Li-ion flux and deac- cross-linked polymeric thin films on Si electrodes at a low
tivate the Si particles.[57a] temperature of 50 °C. Poly(1,3,5,7-tetravinyl-1,3,5,7-tetramethyl-
Besides the abovementioned physical layer deposition cyclotetrasiloxane) (pV4D4) was chosen as a surface modifier
methods, CVD is considered as a powerful tool for depositing and the polymeric coating material for its superior adhesion
various thin coatings.[94] CVD utilizes one or more vapor-phase with Si surfaces and ionic conductivity. The authors adapted
compounds or elements containing thin-film elements to laser interferometry for real-time thickness control of the
induce a chemical reaction onto the targeted substrate, How- deposited pV4D4 film at target thicknesses of 15, 25, 35, and
ever, traditional CVD often involves high processing tempera- 45 nm. Interestingly, thinner films (15 nm) give rise to only
ture (up to ≈1000 °C) far beyond the decomposition of organic modest improvement, less effective than the optimum thick-
materials, hence normal CVD is limited for growing inorganic ness (i.e., 25 nm) which results in the highest reversible capaci-
coatings. Alternatively, initiated chemical vapor deposition ties (789 mAh g−1 after 100 cycles), almost double that of the
(iCVD) is developed as a free-radical polymerization reaction neat Si electrode (404 mAh g−1 after 100 cycles). The improved
process to deposit functional polymer films.[95] The deposi- rate performance in pV4D4-coated electrodes (as observed
tion process of iCVD consists of four stages: injection, adsorp- in Figure 5b) suggests a facilitated Li-ion transport through
tion, collision, and polymerization. As illustrated in Figure 5a, pV4D4 film than traditional electrolyte-derived SEI.
the initiator and monomer are converted to radical species at The underlying mechanism related to the improved cycle
150–300 °C in the first step, and then the gaseous radical spe- stability of 25 nm pV4D4-coated Si could be ascribed to the
cies will be absorbed onto the substrate that is under constant differing surface SEI layer. The FTIR spectra of the post-
cooling. Subsequently, the collision of radicals with mono- cycled pV4D4-coated and uncoated electrodes are compared in
mers on the target surface occurs which triggers free radical Figure 5c. The existence of the 1264 cm−1 peak associated with
polymerization at a gentle temperature (10–40 °C).[96] One may the SiCH3 bend suggests that pV4D4 polymer film remained

Figure 5. Growth of polymer thin film onto Si via initiated chemical vapor deposition (iCVD). a) Schematic illustration of iCVD process. Adapted with the
permission.[96] Copyright 2017, Wiley-VCH. b) Rate performance of electrode with or without iCVD-coated polycyclosiloxane thin film. c–e) Comparison
on FTIR and XPS spectra of the post-cycled electrodes with or without polymer-coatings. b–e) Adapted with permission.[50] Copyright 2019, American
Association for the Advancement of Science.

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on the surface of the Si electrode after cycling. Besides, the of evidence that the COF coating layer may be regarded as a
much weaker absorption peaks of pV4D4-coated sample at pre-planted SEI that provides superior ion transport capability
1510 to 1410, 1416, and 864 cm−1, which are prominent in compared to the traditional electrolyte-derived SEI. Isolating
bare Si, are ascribable to the decomposition product of car- electrolyte contact with Si, the lithium-conducting COF coating
bonate electrolytes such as Li2CO3 and organic CO species. prevents excessive electrolyte reduction build up and enhances
XPS spectra for post-cycled electrodes (Figure 5d) further con- Li-transport kinetics. The cyclic voltammetry curves of pristine
firm the altered composition of SEI under pV4D4 film. With Si and Si@COF electrodes (shown in Figure 6c) corroborate
pV4D4-coating, the SEI layer is comprised of a sole hydro- this rationale. The noticeable reduction peaks in the voltage
carbon component, corresponding to the aliphatic backbone range of 1.0–≈1.4 V in the first cathodic scan of neat Si, points
and methyl groups in the pV4D4 and/or adventitious carbon. to the profound electrolyte reduction and formation of SEI on
The much lower concentration of Li2CO3 (≈290.1 eV) and the Si surface. In contrast, these SEI-related cathodic peaks
organic CO species (≈286.3 eV) in pV4D4-coated Si electrodes were absent in the initial cathodic scan of Si@COF, suggesting
suggests that the iCVD film greatly inhibits the formation of greatly inhibited electrolyte reduction.
carbonate electrolyte reduction product. On neat Si electrodes, Amongst the polymeric materials that have been used in
LiF (55.7 eV) and LixPFy/LixPFyOz (57 eV) are predominant surface modification of Si in LIBs, polymethyl methacrylate
complexes, suggesting further decomposition of LiPF6 salt and (PMMA) is the most abundant one. PMMA is an elastic polymer
carbonate solvents. with high lithium conductivity through swelling with liquid
As was mentioned earlier, iCVD allows the deposition of con- electrolytes and coordinating with lithium ions.[100] As depicted
formal pV4D4 film onto Si anode under relatively low processing in Figure 6d, Wang and Zheng et al.[49a] reported that during
temperature. This layer works as an effective artificial SEI in SiNPs’ encapsulation by PMMA via oil/water micro-emulsion
stabilizing Si anode surface. Compared to other thin film depo- polymerization, the thickness of PMMA coating on the Si sur-
sition techniques, the iCVD-grown film owes the advantage of face could be tuned by the dosage of MMA monomer. The
depositing ultrathin polymer films with tunable thicknesses that authors found the optimal amount of PMMA to be 4% with
are highly cross-linked. As cross-linked polymers are mechani- respect to SiPMMA composite, forming a uniform coating of
cally robust and insoluble against most of the solvents, the around 10 nm. The corresponding Si@PMMA electrode exhib-
iCVD-grown film could excel in structural and chemical stability ited a stable cycle performance over 1000 mAh g−1 of 200 cycles,
of the electrode throughout cycling. Furthermore, tuning the film while the pristine Si electrode faded rapidly after 120 cycles.
composition and properties could be achieved via copolymeriza- More surprisingly, Si@PMMA was able to deliver 66.2%
tion or co-coating with other functional components providing capacity retention at 10 C (42 A g−1) compared with the first cycle
iCVD grown films with a high level of tunability. at 0.05 C (Figure 6e), depicting much-improved rate-capability
Another category of the surface modification methods that over neat Si (≈10% retention). GITT results confirmed a doubled
can be applied to improve the surface characteristics of Si anodes Li-ion diffusion coefficient of Si@PMMA compared to the neat
in LIBs is the covalent-organic-framework (COF). COF is an Si electrode. The authors attributed the surprisingly high Li-ion
atomically organized 2D or 3D organic material that has shown diffusion kinetics in Si@PMMA to uniquely thin and stable
appealing potential as ion-storage composite electrode mate- SEI layers that were visualized by AFM topography. The surface
rials.[98] Due to the high porosity (often in a few nanometers), SEI on Si@PMMA appeared to be much thinner and flatter
highly ordered open channels, and possible π-conjugated frame- than that on neat Si as shown in Figure 6f. Moreover, Young’s
work, COF offers a wide opportunity to fabricate surface layers modulus of Si@PMMA electrode was twice that of Si electrode,
with superior ionic and electrical conductivity. Hence a structur- indicating that the PMMA shells prevented the building up of
ally engineered COF coating may be regarded as an ideal coating loosely packed SEI components. This aspect was consolidated by
material in isolating electrolyte side reactions while allowing fast XPS spectra (Figure 6g) in which the relatively low content of
Li-ion penetration and charge transfer on the Si interface. CO22−/CO32− of Si@PMMA electrode in C 1s spectra point to
As shown in Figure 6a, Ci and Lou et al.[99] reported a a suppressed electrolyte decomposition. Other SEI components
Li-ion-conducting COF as encapsulating layer for SiNPs. The such as LixSiyOz (102 eV in Si 2p spectra) and LixPOyFz (686.4 eV
COF shell (≈2 nm in thickness according to the high-resolution in F 1s spectra) were also found to be sparser in Si@PMMA
TEM imaging) was synthesized by solvothermal polymeriza- than in neat Si electrode, implying suppressed side reactions on
tion in the presence of SiNPs. Further lithium-ion exchange the Si surface by the PMMA layer.
with lithium acetate was adopted to obtain Li-ion conductance As was mentioned earlier, SEI is commonly formed upon a
of the polymer film, yielding a lithium conductive COF-coated self-limiting electrolyte decomposition reaction on the electrode
Si (Si@COF). The thickness of COF shell was tuned by con- surface, consisting of inorganic Li salts and organic species
trolling the mass ratio of Si and COF precursor. As shown in stacking in a mosaic fashion.[29a,101] The inherent heterogeneity
Figure 6b, COF coatings could stabilize Si particles to achieve of structure and site-specific ion-transport behavior in SEI
stable cycling performance at 1 A g−1, and ameliorate the ICE is thus recognized as a deteriorative factor toward stable
from 71% of neat Si to 82%. Accordingly, in the long-term cycling.[102] In contrast to the traditional carbon coatings which
cycling test, the Si@COF exhibited 1864 mAh g−1 at 2 A g−1 are in principle Li-reactive surfaces allowing SEI growth, the
and maintained more than 60% after 1000 cycles. Comparing organic artificial coatings are inert to Li throughout lithiation
Li-ion diffusion coefficient (DLi+) of the neat Si and Si@COF, and de-lithiation. Hence, the organic surface films may be
the authors found that the COF coating could promote Li-diffu- regarded as pre-planted artificial SEI with genuine structural
sion throughout the de-lithiation process. This provides shreds and chemical homogeneity.

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Figure 6. Growth of Li-conducting covalent-organic-frameworks (COF) on Si. a) Graphical illustration of coating COF on Si nanoparticles (Si@COF).
b) Cycling performance of neat Si and Si@COF electrode. c) CV curves of neat Si and Si@COF electrode depicting differing SEI formation behaviors.
a–c) Adapted with permission.[99] Copyright 2020, Elsevier. Capsulation of polymethyl methacrylate (PMMA) on Si via micro-emulsion polymerization.
d) Schematic preparation of Si with PMMA nano-capsules (Si@PMMA). e) Cycling performance of neat Si and Si@PMMA electrode. f) 3D-AFM
landscape of post-cycled neat Si electrode and Si@PMMA electrode. g) XPS spectra of post-300 cycles neat Si electrode and Si@PMMA electrode.
d–g) Adapted with permission.[49a] Copyright 2021, American Chemical Society.

A major finding of the above-discussed studies was that the form and then coated onto metal foil current collector. The
pre-planted organic layer significantly alters the electrolyte-reduc- resulting electrode structure is designed to achieve a combina-
tion/SEI formation processes on Si, which are a pivot in stabi- tion of high active material loading (commonly compacted by
lizing the subsequent electrochemical cycling. To date, it remains calendaring), good electric conductivity, and sufficient adhe-
ambiguous how these organic moieties coordinate with Li-ions sion for the coating layers. It should be noted that in commer-
and transport Li-ions through the interface. In the case of solu- cial cells, the anode side adopts a limited amount of binders
tion-grown PMMA layers, it is speculated that by solvents swelling (often lower than 5 wt%), such as CMC sodium and styrene
into the film’s macromolecular network, Li-ion motion could be butadiene rubber, to ensure desired energy density and inter-
achieved in the form of solvated complexes. Conversely, in the particle electric conductance.[103] Now it is well recognized that
case of COF, one may expect the stripping of the solvation sheath the failure of inter-particle and particle-current collector inter-
of the Li-solvent complex before Li-ion migrates into the organic facial adhesion will result in cracking and gradual electrode
interlayer, a behavior akin to Li transport in SEI. Hence, further disintegration, which is accountable for the fast capacity decay
studies are required to facilitate an in-depth understanding of the and sometimes “capacity-diving” type cell failure.[104] Given the
ion-transportation mechanism through these organic moieties, poor electric conductivity of pure Si, reaction area “hot-spots,”
providing guidelines for the rational design of surface layers. and stress accumulation on the electrode level may arise that
in return exacerbate electrode cracking and premature cell
failure.
4.2. Organic Surface Coating Interacting with Binder Enhancing the interfacial adhesion between active particles
and polymer binder is considered a well-known strategy toward
Common Si electrode consists of active material, conducting improving the cycle stability of Si anodes. Advanced binder sys-
agent, and polymer binder that are often mixed in the slurry tems such as CMC, PAA, and alginate were found to hydrogen

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bond with the hydroxyl groups (OH) on the Si surface, pro- As shown in Figure 7b, the PD-coated Si electrodes
viding reinforced adhesion to stabilize the electrodes against (Si@PD/PAA) exhibit an excellent cycle capacity of 1800 mAh g−1
interfacial failure and cycling-induced mud-cracking.[31b,105] at 1.5 A g−1 after 100 cycles. Conversely, the control group of neat
However, hydrogen bonding is often regarded as a fragile Si with the identical PAA binder (Si/PAA) demonstrates fast
interaction that is sensitive to electrochemical potentials and/ capacity decay after 30 cycles and shows about 500 mAh g−1 after
or large strain levels upon cycling. More importantly, protic 100 cycles. Other control groups, with either sodium alginate or
species (hydroxyl, carboxyl groups, etc.) could exacerbate elec- CMC binder, showed even more severe capacity decay from the
trolyte decomposition and SEI instabilities via a sequence of onset. Conversely, the Si@PD/PAA exhibits a higher capacity
auto-catalytic side reactions.[29a,106] These aspects could be more at a different current density than the control group. The excel-
problematic at practical batteries with elevated electrode mass lent rate capability in Si@PD/PAA implies that the ultrathin PD
loading, lean electrolyte dosage, and limited active Li, where the does not hinder ion conduction. The authors observed that the
gas formation and electrolyte dry-out are the main culprit for ultra-thin (3–4 nm thick) layer PD well covers the Si particles
cell failure.[107] on top of its native Si–O surface (Figure 7c). This implies that
To further improve the surface stability of Si, Yang et al.[108] the affinity between dopamine and native Si–O surface leads to
reported a surface in situ polymerization route to coat a thin adsorption of the monomer dopamine onto Si particles in the
polydopamine (PD) layer onto Si particles that could further initial step, hence the subsequent on-site polymerization reac-
bond with PAA binder. PD is known as natural polymeric glue tion ensures uniform and conformal coating onto Si.
that strongly adheres to most inorganic surfaces including The abovementioned PD mediating layer was chemically
ceramics, metals, and plastics due to its unique hydroxyl- bonded with the PAA binder through a condensation reaction.
rich nature.[109] As depicted in Figure 7a, the imide groups in This reaction route was evidenced by FTIR and XPS spectros-
PD react with carboxylic acid groups on PAA to form chemical copy. As is depicted in Figure 7d, the peak at 1645 cm−1 (N–H
bonds. Unlike directly bonding SiOH groups on Si particles deformation vibration) disappears in Si@PD/PAA electrode,
with PAA binder where hydrogen bonding is predominant,[110] suggesting that N–H in the surface PD film reacted with
the PD acts as an intermediating adhesive layer that forms COOH in PAA. In addition, the red-shift of PAA’s CO vibra-
strong covalent bonds with both Si and PAA. tion from 1714 to 1700 cm−1 in Si@PD/PAA corroborates the

Figure 7. Growth of polydopamine (PD) coating on silicon nanoparticles via in situ polymerization that tethers with poly(acrylic acid) (PAA) binder.
a) Graphical illustration of the interaction between PD-modified Si particles with PAA binder via cross-linking reaction. Inset: Chemical structure of
dopamine. b) Cycle performance of Si with various surface moieties and polymer binder. c) TEM images of Si nanoparticles with a surface oxide
layer and polydopamine layer coating. d) FTIR of PD-coated electrode materials and electrode with PAA binder. e) XPS N 1s spectra of cross-linked
Si-polydopamine/poly(acrylic acid) electrode. a–e) Adapted with permission.[108] Copyright 2016, American Chemical Society.

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condensation reaction between PAA and amide. In Figure 7e, tron transport considering the insulating nature of PVA. In
the peak at 399.6 eV in the N 1s spectra suggests the exist- contrast, inferior cycle performances were observed in a simple
ence of tertiary amine (NRCO) groups in Si@PD/PAA, mixture of Si and PVA in the electrode slurry, further high-
evidencing the condensation reaction between PD thin films lighting the critical role of forming covalent bonds between the
and PAA binder. It is identified that the SiOH moieties on PVA coating layer and Si particles.
the Si surface could result in a catalyzed electrolyte decompo- RBM serves as a high energy source to both coat PVA
sition reaction, and surface modification reactions consuming onto Si particles and trigger covalent bonding of Si with PVA
the surface SiOH groups, in general, improve surface molecules. In principle, it is known that polymer chains tend
stabilities.[32,111] to be scissored due to high-energy mechanical milling.[118]
The self-polymerization of dopamine onto a wide range of Nevertheless, the structure evolution and possible degrada-
both organic and inorganic materials was inspired by natural tion of PVA molecules during RBM treatment and the pre-
occurring adhesive versatility in mussels.[112] PD provides easy cise molecular structure of the resulting coating layer remain
and versatile routes to obtain adhesive surface thin films with intriguing. How many hydroxyl groups on the PVA layer were
abundant phenolic hydroxyl groups and amino groups. These consumed in RBM to form SiOC covalent bonds? And how
groups on the PD surface film can be further utilized toward do the remaining OH groups interact with electrolyte and Li+?
covalent bonding with a wide range of targets, endowing One may also underline the importance of a thorough under-
the coated particles with rich surface functionality. The few- standing of ionic transport through the PVA layer.
nanometer thin PD film has little negative influence on ionic Aside from forming adhesive films to bond with binder
and electrical conduction but greatly alters the interaction molecules, an alternative strategy to enhance Sibinder inter-
between Si and PAA binder. The strong adhesion between action would be growing binder molecules directly onto the Si
Si@PD and PAA can survive throughout prolonged cycling, surface. In Figure 9a, Belanger et al.[119] reported a chemically
greatly promoting cycle stability. A variety of natural abundant modified Si anode with a covalently attached polymer binder by
organic species with similar hydroxyl-amino structures, such directly initiating atom transfer radical polymerization (ATRP)
as 3,4-dihydroxy-L-phenylalanine,[113] plant polyphenols,[114] and of tert-butyl acrylate (t-BA) on the Si surface. The acid hydrolysis
tannic acid,[115] are also inclined to polymerize and form highly of polymerized t-BA yielded PAA molecules. This was achieved
adhesive thin films on inorganic surfaces. These organic moie- by a three-step reaction: 1) first, cleaning the Si surface with HF
ties are emerging as useful binders or coatings for Si anodes.[116] to generate hydroxyl-terminated particles surface; 2) grafting
We note that it is feasible to further tune these systems with a the initiator, that is, 1-(bromomethyl) benzene molecules, onto
variety of reactive groups via co-polymerization with functional the hydrogen-terminated Si surface; 3) on-site ATRP reaction of
monomers, providing a versatile platform for designing organic t-BA and later acid hydrolysis.
moieties on various battery material surfaces. Due to its electric insulating nature, it may be predicted that
As schematically illustrated in Figure 8a, Chen and Lu an excessive amount of PAA binder could deteriorate electric
et.al.[117] designed a covalently bonded polymer coating on the conductance in the electrode. Grafting PAA onto the surface
surface of nano-Si by reactive high-energy ball-milling (reac- of Si particles with self-adhesive properties however allows the
tive ball-milling [RBM]) of the mixture of micron-sized Si reduction of the dosage of binder in the electrode. It is found
(≈325 mesh) and poly(vinyl alcohol) (PVA). Compared with that the amount of grafted-PAA could be lowered down to
high-energy ball-milling in existing literature, which is usu- 5 wt%, a dosage profoundly lower than that of conventional
ally adopted to break down the particle size, in this work RBM PAA binder (10–≈20 wt%), while the Si can maintain good
was employed to produce sub-micron Si particles with PVA cycle performances (80% capacity at 0.34 A g−1 after 300 cycles,
coating layers that are chemically bonded onto the Si surface. Figure 9b). From SEM micrographs in Figure 9c,d, it is evi-
The coating material, PVA, was chosen due to its high tensile denced that the post-300-cycles Si electrode with grafted PAA
strength, flexibility, and abundant hydroxyl groups. Compared film exhibit slim and more uniformly distributed cracks, while
with ball-milled pure Si (without PVA), Si particles milled with down-reaching cracks appeared to be prevalent for the Si–PAA
the presence of PVA turned out to be much finer and smaller. physical mixture electrode after only 50 cycles. Electrode mud-
It was suggested that PVA “squeezed” in between newly frac- cracking was widely identified as the main culprit for capacity
tured Si surfaces prevents Si sub-particles from aggregating. diving (abrupt decay) of Si anodes, a phenomenon that arises
Using HRTEM (Figure 8b), the authors confirmed that the PVA from poor adhesion between active particles, polymer binder,
coating layer is only 5–10 nm thick in the sample containing and current collector.[121]
5% PVA. Grafting organic adhesive moieties to the surface of Si
Moreover, the RBM triggers the mechano-chemical reaction appears to be successful in many systems.[17a,111] Conductive
between the freshly exposed surface of Si particles and hydroxyl polymers arise recently as a novel group of binder candidates
groups in PVA, forming SiOC covalent bonds that were evi- that help to further improve electrode performances.[11d,122] An
denced in XPS Si 2p, C 1s, and O 1s spectra (Figure 8c) and intuitive direction in this path would be covalently grafting
FTIR (Figure 8d). The ratio of polymer and Si in RBM showed conductive polymers onto the Si surface, achieving both good
a profound influence on electrochemical performance. Si-5% adhesion and electric conductance for Si anodes. As shown
PVA electrode displayed the cycle performance of 1529 mAh g−1 in Figure 9e, Qian et al.[120] employed a silane coupling agent,
at 0.2 C after 100 cycles, with an ICE of 74.8%, shown in γ-glycidoxypropyl trimethoxysilane (GOPS), to construct a
Figure 8e. Higher PVA coating percentages led to more exces- cross-linked network between SiNPs and poly(3,4-ethylened
sive irreversible capacity in the initial cycle and hindered elec- ioxythiophene):polystyrene sulfonate (PEDOT:PSS) binder.

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Figure 8. Preparation of poly(vinyl alcohol) (PVA)-coated silicon via reactive ball-milling (RBM). a) Schematic diagram of the covalent bonding
between PVA and Si. b,c) HRTEM images and XPS spectra of PVA-coated Silicon particles. d) FTIR spectra of pristine PVA, ball-milled silicon particle,
and PVA-coated Si. e) Electrochemical cycling performance of ball-milled silicon, simple Si-PVA mixture, and RBM-prepared Si-PVA composites.
a–e) Adapted with permission.[117] Copyright 2020, American Chemical Society.

The addition of GOPS in acidic PEDOT:PSS aqueous solution 13.6%, respectively. This implies that even though PEDOT:PSS
gives rise to the ring-opening reaction of the epoxy groups of possesses excellent electrical conductivity, the poor elasticity of
GOPS with the sulfate groups (OSO3H) in the PSS chains. the rigid macromolecule backbones may lead to poor durability
Meantime, the methoxyl groups (OCH3) on the other end of against volume changes of Si. The electrode peeling testing
GOPS molecules will be hydrolyzed in the aqueous solution to confirmed that the introduction of cross-linking “bridge” GOPS
generate silanol groups (SiOH) that are reactive to SiOH improved the mechanical robustness and durability of the
of the Si particle surface. Hence, GOPS acts as cross-linking electrodes. XPS Ar+ etching depth analysis on the post-cycled
“bridge” molecules to covalently connect with conductive Si electrode is compared in Figure 9g,h. The signal of active
PEDOT:PSS binder on the one side and Si particle surface on Si–Si (≈99 eV) was detected on the Si–PEDOT:PSS electrode
the other side. after only one etching step. This is not indicative of a thin SEI
In Figure 9f, the electrodes with optimized synthetic condi- layer but implies a destroyed surface and continuous exposure
tions (10 mg GOPS react at 180 °C for 60 min, termed as SGP- of inner fresh Si toward electrolytes. Post-cycled SEM images
10-180-60) exhibit 1957.6 mAh g−1 at 1 A g−1 after 200 cycles, (inset of Figure 9g,h) point out severe cracks (≈3.7 µm) in the
corresponding to a capacity retention of 70.8%. In contrast, Si–PEDOT:PSS. Conversely, the cycled SGP-10-180-60 appears
the electrode with PAA binder or pure PEDOT:PSS binder dis- to be crack-free. Relatively constant uniform Si–O and Si–Si
played severe capacity decay with retention of only 19.1% and signals in SGP-10-180-60 emerged after three etching steps,

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Figure 9. a–d) Preparation of polyacrylic acid (PAA) layer covalently adhere to silicon via in situ atom transfer radical polymerization (ATRP).
a) Schematic illustration of polyacrylic acid (PAA) surface grafting onto silicon via ATRP. b) Cycle performance of silicon electrodes with/without PAA
grafting. c,d) SEM image of post-cycled silicon electrode with or without grafted PAA surface film, respectively. a–e) Adapted with permission.[119]
Copyright 2017, Elsevier. Liquid phase grafting reaction of poly(3,4-ethylene dioxythiophene)/poly-(styrene-4-sulfonate) (PEDOT:PSS) with Si particles.
e) Schematic illustration of chemically coupled Si/PEDOT:PSS. f) Galvanostatic cycling results of silicon electrode with PAA binder (Si–PAA-SP), with
PEDOT:PSS binder (Si-PEDOT:PSS), and with chemical coupled PEDOT:PSS (SGP-10-180-60). g,h) XPS Ar+ etching depth analysis and SEM images of
Si-PEDOS:PSS and SGP-10-180-60 electrode after 100 cycles. e–h) Adapted with permission.[120] Copyright 2021, Springer.

suggesting a uniform and stable surface layer (Figure 9h). changes of Si impose challenges of maintaining intimate
Besides, it is shown that under a lean electrolyte of 30 µL, the electric contact throughout cycling. In general, the opera-
SGP-10-180-60 delivers stable capacity for 800 cycles; however, tion of Si electrodes relies on the proper functioning of CAs.
Si–PEDOT:PSS control can only stand <40 cycles. Hence, here we highlight the interfacial interaction of Si with
CAs, and summarize endeavors in this regard as promising
emerged directions.
4.3. Surface Moieties Interacting with Conductive Agents As shown in Figure 10a, Marschilok and Reichmanis et al.[124]
employed a conjugated conducting polymer layer to anchor
CAs are known as indispensable components in commercial single-walled carbon nanotubes (SWCNTs) to the surface of
cells and play an important role in determining electrode SiNPs. The used polymer, poly[3-(potassium-4-butanoate)thio-
performances especially at larger charge rates or lower phene] (PPBT), is a water-soluble polymer with relatively high
working temperatures. Numerous studies have reported that electronic conductivity of ≈10−5 S cm−1.[125] A polyethylene glycol
a “binder-free” electrode configuration in which active Si is (PEG) coating was first introduced on the particle surface to
grown in situ on the conductive skeleton can achieve desirable further form carboxylate bonds with side carboxylic groups in
electrochemical performances such as fast charge/discharge the side chain of PPBT. The SEM image shown in Figure 10b
capabilities.[8a,63b,123] In such configurations, greatly enhanced confirms that SWCNTs are closely anchored on the surface of
electrical conductivity appears to be a critical beneficial aspect. nanoparticles. These interface interactions were confirmed by a
However, in situ Si growth involves complex synthesis routes newly emerged strong absorption peak at 1726 cm−1 in the FTIR
such as CVD growth of Si from SiH4, and the large volume spectra (Figure 10c) that was assigned to a CO stretching

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Figure 10. The carboxylated polythiophene layer facilitates the anchoring of single-walled carbon nanotubes (SWCNTs) onto silicon nanoparticles.
a) Schematic illustration of preparing poly[3-(potassium-4-butanoate) thiophene (PPBT) links to anchor SWCNTs on electroactive particles. b) Typical
SEM images of SWCNT-anchored particle. c) FTIR spectra of Si nanoparticles (SiNPs), PPBT polymer, and SWCNT-anchored Si nanoparticles with PPBT
links. d) Improved cycle performance of Si anode with SWCNT and PPBT links. e) SEM images of post-cycled silicon electrode with PPBT-anchored
SWCNT and bare silicon electrode (inset). a–e) Adapted with permission.[124] Copyright 2018, American Chemical Society.

vibration. Moreover, the PPBT-conjugated backbone physically Numerous other studies focused on the surface modifica-
interacted with the SWCNT surface through noncovalent π–π tion of SiNPs as such nanostructures hold great promise to
interactions. prevent particle cracking. Nevertheless, the relatively high
Comparing the cycle performance shown in Figure 10d, the cost of the production of SiNPs, high SSA, and low tap den-
authors showed that the electrode without SWCNT displayed sity have imposed great impediment toward practical applica-
rapid capacity fading in the initial 20 cycles. The electrode with tion. Micron-sized particles offer inherent advantages of low
unique PPBT linkages achieved a cycle capacity of 2003 mAh g−1 SSA and high tap density, which are vital components con-
after 100 cycles at 0.5 C (1.25 A g−1, the red line), a much more tributing to ICE and volumetric energy density, however, the
stable cycle capacity compared to all control groups. Conversely, inherent propensity of particle cracking calls for effective
introducing SWCNT by physically mixing with Si with the aid surface reconfiguration and protection. In Figure 11a, Wang
of physical surfactant (the blue line) yields electrode structure and Deng et al.[126] developed a hybrid electrode based on
without PPBT links, resulting in much inferior cycle stability. micron-sized SiOx particles (≈10 µm), featuring a double-layer
Figure 10e shows the SEM images of the post-cycled electrode. coating. The inner carbon coating was conducted by planetary
While the pristine Si electrode suffered from the growth of ball-milling with pitch followed by carbonization. The outer
thick SEI layers with cracked surfaces, the SWCNT-SiNPs elec- polymer composite coating layer was constructed by in situ
trode experienced much-alleviated electrode cracking. These polymerization of PEDOT after dispersing SiOx@C, SWCNTs/
observations highlight the pivotal role of intimate Si–CAs inter- Super P, and EDOT monomer in iron p-toluenesulfonate
actions in affecting not only the inter-particle electric pathway N-methylpyrrolidone solution. These composite particles are
but also electrode structure integrity throughout cycling. The denoted as SiOx@C@P_CS. The TEM image in Figure 11b
authors pointed out that van der Waals type physical interac- confirms that carbon and polymer dual coating covers the
tions did not provide sufficient adhesion in anchoring CAs SiOx surface. From the SEM image in Figure 11c, it is evi-
to survive from unremitting volume changes. In this study, dent that the conducting agents including SWCNT and
the critical function of the organic layer (PPBT and PEG) in Super P were filled in the polymer layer. In Figure 11d, the
“gluing” SWCNT on Si was highlighted. Without such “glues,” SiOx@C@P_CS shows the best-of-breed cycle performance
the detachment of SWCNT and electrode cracking became with 1019 mAh g−1 at 0.5 C after 1000 cycles, corresponding
prevalent. Nevertheless, it remains largely ambiguous how the to a capacity retention of 86.7% and ICE = 74.8%. This implies
“gluing layer” participates in the SEI formation. Moreover, the a synergy between the bottom carbon coating and the top
reported ICE (77%) is not ideal (in comparison, the ICE of neat polymer layer. As an echo, a recent study shows that attaching
Si without PPBT was 85.6%). In this sense, the organic PPBT additional epoxy moieties on top of the carbon coating layer of
layer contributes to the ICE capacity loss, likely with Li-ion irre- Si greatly promotes its cyclability, even under practical high-
versibly binding onto the polymer chains in the initial cycle. mass-loading conditions.[127]

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Figure 11. Conductive polymeric coating layers serve as a surface modifier for SiOx particles in addition to the carbon coating. a) Schematic illustration
of coating SiOx particles with carbon and PEDOT dual coating layers with conductive filler embedment. b) TEM image of dual-coated SiOx particles.
c) SEM image of carbon-polymer SiOx with conductive filler embedded in the PEDOT layer (termed as SiOx@C@P_CS). d) Cycle performance of pristine
SiOx, carbon-coated SiOx, and SiOx@C@P_CS electrode. a–d) Adapted with permission.[126] Copyright 2020, Elsevier. Bonding bridges between Si and
conductive agents. e) Schematic of Si particles with PEDOT:PSS coatings that better connects with reduced graphene oxide (rGO) conductive skeleton
(termed as H-Si-P/rG). f) Cross-sectional SEM image of the H-Si-P/rG electrode. g) TEM image of PEDOT:PSS-coated SiNPs. h) Cycle performance of
electrode with various surface coating and conducting agents. e–h) Adapted with permission.[128] Copyright 2019, American Chemical Society.

Lv, Kong, and Yang et al.[128] proposed an elaborate in situ The highly conductive PEDOT:PSS coating layer serves as
polymerization strategy to coat conductive PEDOT:PSS polymer a dual function component: as a high-performance binding
thin film onto hydroxylated SiNPs. The reduced graphene oxide layer and as an electrically CA. As shown in Figure 11h,
(rGO) layers were adopted as an additional conducting skeleton the hydroxylated SiNps-PEDOT:PSS coated-rGO electrode
that could form covalent connections with PSS molecules in (marked as H-Si-P/rG) exhibits the best cycle performance
the meantime. This idea is schematized in Figure 11e (marked (1337.6 mAh g−1 at the current density of 0.5 A g−1 after
as H-Si-P/rG). As discussed earlier, PEDOT:PSS is a commer- 500 cycles). Conversely, the electrode without hydroxy-
cially available water-soluble conductive polymer with high elec- lation (N-Si-P/rG) shows much quicker capacity fading
tronic conductivity (1000 S cm−1). However, it lacks mechanical (426.1 mAh g−1 after 500 cycles). It is suggested that the strong
strength, especially under large strain levels.[11d,129] The authors bonding between the hydroxylated SiNPs with PEDOT:PSS
adopt the in situ polymerization method to form conformal helps to form a flexible buffer layer and enhances the electron
PEDOT:PSS coating onto Si. The 2D rGO could serve as long- transfer. Besides, at identical cycling conditions, electrodes
range CAs and above all as additional mechanical support for adopting CNTs and Super P as CAs display low capacity reten-
reinforced electrode durability against volume changes.[17a,130] tion of 38.4% and 29%, respectively. The 2D rGO appears to
As illustrated in Figure 11f, the as-prepared electrode exhibits a have a profoundly better tolerance against the Si expansion.
segregated structure with SiNPs uniformly encapsulated in the These observations somehow echo with an interesting similar
interlayer space of interconnected rGO nanolayers. According study carried out by Wang et al.[131] where the mixture of SiNPs
to the TEM image shown in Figure 11g, the thickness of the and rGO were coated on a double-faced adhesive tape con-
PEDOT:PSS coating layer was ≈2 nm. Interestingly, without the taining acrylic acid, PVA, and organoSi. A pyrolysis process
hydroxylation treatment, no resulting polymer layer could be was adopted to form SiOC, SiC, and CuOC bonds
found on SiNPs pointing to the critical role of surface hydroxy- in the pyrolyzed carbon with Cu foil, Si NPs, and rGO. The
lation of SiNPs on conformal coating. modified electrode exhibited 968 mAh g−1 (maintained 63%)

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at 0.5 A g−1 after 200 cycles, much more stable than conven- 5. Revisiting the Approaches for Organic Surface
tional SiNPs electrode (116 mAh g−1 after 200 cycles). Chemistries
Based on the above discussions, achieving uniform coating
and intimate adhesion with CAs on Si particles are at the core As was described in details, the scalable implementation of
of surface engineering for improving the characteristics of the organic surface coating technologies is a critical factor for
anodes in LIBs. In this regard, strong interaction between Si the practical application of Si anodes in LIBs. A generic over-
particles with the polymer coating is a prerequisite for con- view of organic surface coating methods onto Si is given in
formal and uniform coating.[128] One may also see that a well- Figure 12, with all known methods being classified based on
tuned conformal organic surface layer could in effect enhance the corresponding surface reaction types. Scrutinizing the
the SiNPs surface adhesion not only with polymer binder but surface reaction routes using these methods and utilization
also with conductive supporting nanolayers. However, it is of complementary surface characterization techniques (vide
shown that even with well-tuned organic coating layers, the supra) greatly facilitate the understanding of the processes
relatively low-SSA SiOx anodes demonstrate relatively low ICE and the resulting structures and functionalities of the sur-
of 74.8%.[126] This implies the possible electrolyte instabilities face coating layer. Utilizing these methodologies and their
on the organic layers. This issue corresponds to the discussion in situ or post-process characterization in a multi-analytical
in Section 4.1 and rises a far-reaching question: how does the approach also allows us to give a generic comparison over
organic surface layer interact with liquid electrolytes in forming the pros and cons of these methods regarding the structural
SEI and what is the ideal structure of the organic layer that uniformity, scalability, and cost of the coating technique,
promotes favorable SEI? Hence, new diagnosis tools offering controllability over surface chemical or morphological struc-
in operando site-specific chemical and structural information tures, as well as effectiveness in improving cyclability of
on the surface layer would be highly useful in clarifying this Si anodes in LIBs. Associated comparisons of the reported
issue. In the following section, we have revisited the organic electrochemical performances adopting various surface coat-
surface chemistry modification methods that are applicable to ings are also tabulated in Table 2. In Figure 12, different
the Si anodes in LIBs with the emphasis on their pros and cons approaches for organic surface modification of Si anodes
in terms of efficiency, processability, scalability, and the possi- are classified as gas-phase, liquid-phase, or solid-phase
bility for commercialization. reactions.

Figure 12. Classification and comparison of viable approaches for organic surface coating based on gas-phase, liquid-phase, or solid-phase reactions.

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Table 2. Recent advances of Si anodes with various types surface modification.

Materials [Si size and contenta)] Surface layers [Thickness] Electrochemical performances Ref.
Mass loading [Area capacity] Half cell performances Full cell performance [Cathode]
Nano-Si C coating – 1355 mAh g−1, 75.2% 93.8% @ 0.5C, 200 cycles [63g]
(20 nm, 70.5%) (≈10 nm) @ (0.84 A g−1, 1000 cycles) (LiNi0.45Co0.1Mn1.45O4)
968 mAh g−1 @ 8.4 A g−1
Nano-Si C coating 1.2 mg cm−2 1123.0 mAh g−1,74.22% – [65]
(50–300 nm, 73.6%) (5−10 nm) (1.7 mAh cm−2 @ 0.1 A g−1) @ (0.5 A g−1, 500 cycles)
876 mAh g−1 @ 5 A g−1
Nano-Si C coating 0.3 mg cm−2 968 mAh g−1, 63% 78.7% @ 0.1 A g−1, 150 cycles [26]
(50–100 nm, 66.3%) (≈4.8 nm) (≈0.5 mAh cm−2 @ 0.2A g−1) @ (0.5 A g−1, 200 cycles) (NCM811)
1126 mAh g−1 @ 2 A g−1
Micro-sized SiOx dual coating of C 0.7≈8.7 mg cm−2 1019 mAh g−1,86.7% 82.8% @ 0.2C, 200 cycles [126]
(≈10 µm, ≈77%) and PEDOT (11.75 mAh cm−2 @0.1C) @ (0.75A g−1, 1000 cycles) (NCM811)
(≈30 nm+20 nm) 680 mAh g−1 @ 6A g−1
Nano-Si PEDOT:PSS coating ≈1 mg cm−2 1337.6 mAh g−1,45.7% – [128]
(<100 nm, 45%) (≈2 nm) (3.29 mAh cm−2 @ 0.09 mA cm−2) @ (0.5A g−1, 500 cycles)
2850 mAh g−1 @ 2A g−1.
Nano-Si Polydopamine coating 0.5 ≈2 mg cm−2 1800 mAh g−1 – [108]
(50–200 nm, ≈74%) (≈3–4 nm) (3.69 mAh cm−2 @ 1.0 mA cm−2) @ (1.5 A g−1, 100 cycles)
Nano-Si Zincone coating ≈1.05 mg cm−2 1011 mAh g−1 110 mAh g−1 @ 0.4C,100 cycles [49b]
(<100 nm, <80%) (3 nm) @ (1 A g−1, 500 cycles) (LiFePO4)
1052 mAh g−1 @ 2 A g−1
Nano-Si PVA coating ≈1 mg cm−2 1526 mAh g−1,≈50% – [117]
(≈200 nm, ≈66.5%) (≈5–10 nm) (3 mAh cm−2 @ 0.2 A g−1) @ (0.2 A g−1, 100 cycles)
801 mAh g−1 @ 3 A g−1
Amorphous silicon film pV4D4 coating (25 nm) – 789 mAh g−1,29.7% – [50]
@ (1 C, 100 cycles)
Nano-Si Grafted PAA coating 0.9–1 mg cm−2 ≈2000 mAh g−1,80% – [119]
(<100 nm, 74%) @ (0.34 A g−1, 300 cycles)
≈1000 mAh g−1 @ 17 A g−1
Nano-Si SWCNTs anchored 0.8–1.9 mg cm−2 2003 mAh g−1,77% – [124]
(50–70 nm, 76%) with PPBT @ (1.25 A g−1, 100 cycles)
≈2000 mAh g−1 @ 15 A g−1
Nano-Si Chemical coupled ≈0.8 mg cm−2 1957.6 mAh g−1, 70.8% 91.4% @ [120]
(50–100 nm, ≈73%) PEDOT:PSS (1.5 mAh cm−2 @ 0.2 A g−1) @ (2 A g−1, 200 cycles) 20 mA g−1, 60 cycles
760 mAh g−1 at 8.0 A g−1 (NCM523)
Nano-Si PMMA coating 0.5–1.2 mg cm−2 Over 1000 mAh g−1 – [49a]
(100 nm, 67.2%) (≈10 nm) (≈3.25 mAh cm−2 @ 2 g−1) (2 A g−1, 200 cycles)
66.2% (at 42 A g−1) of its initial
capacity (at 2.1 A g−1)

a)Si content = the mass of Si/(the mass of active materials + conductive agents + binder).

Gas-phase reactions offer the inherent advantage of conformal electrode preparation steps offering excellent scalability and
uniformity and the capability to tune the thickness of the coating cost-effectiveness. However, it remains challenging to precisely
layer down to the nanometer scale, for example, by changing tune film thickness and structures with satisfactory uniformity
the number of MLD reaction cycles or iCVD temperature/time. via liquid-phase reactions. Moreover, relative long reactions
Unlike carbon coating or inorganic coatings, such gas-phase time and residual monomers and oligomers in the system may
organic surface treatments do not involve high calcination tem- influence the electrochemical properties. In another form of
peratures. However, the requirement for expensive equipment liquid-phase reaction which is based on electrochemical reac-
and precursors are impediments to large scale applications. tions, the resulting polymer film can be better controlled by the
Liquid-phase reaction has advantages of low cost, ease of applied potential, current, and reaction time. Nonetheless, lim-
operation, and a low requirement on equipment. Spray drying, ited by the size of electrolytic bath, electrochemical approaches
rotary evaporation, or electrospinning could be potential show relatively inferior scalability.
approaches to form polymer coatings with decent scalability. Solid-phase reactions either with ball milling or mechanical
Besides, these methods are often compatible with slurry or mixing are widely used methods with clear advantages of low

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cost and scalability. Researchers also have identified mech- For the long-term goals targeting 500 Wh kg−1, Li metal
ano-chemical interplay in high-energy ball milling that trig- (3860 mAh g−1, 2061 mAh cm−3) is in general considered as the
gers a series of interfacial reactions between polymer and Si ultimate choice of anode materials despite the daunting chal-
(SiOC covalent bonding). Hence, one may expect uniquely lenge of dendrite control. Recent progress in achieving dense
strengthened adherence of polymer coating layers on Si when particulate Li deposition makes Li metal a more and more fore-
prepared through solid-phase methods. Si in any milling pro- seeable counterpart to Si-based anode.[136] Micron-sized pure Si
cess will be covered by an oxide layer. In protic solvents like particles with higher specific capacity and tap density are poten-
water or ethanol, grinding of Si might lead to increased porosity tial enablers for >400 Wh kg−1 cells thus shall be considered
due to mechano-chemically induced solvation. In higher alco- as anode active materials in competition with Li metal. Recent
hols, however, this effect can be avoided. Therefore, mechano- progresses have shown that novel polymer binder,[11c,21b,137] con-
chemistry in mills opens many interesting facets for tailoring ductive network,[74d,138] electrolyte formula,[22a] and cell stack
the powder properties.[132] Upon fracture, radicals are formed pressure[139] could significantly improve the cycle performance
which can be used for grafting of polymers onto the oxide sur- of pure micro-Si-based anode, which previously was doomed as
face.[133] Since polymer chains can be scissored and decomposed “mission impossible.” These advances on micro-Si anode actu-
at too high energy input, a subtle balance between grafting and ally all point to the critical role of Si surface chemistry, either by
decomposition must be maintained. Key parameters are the better interacting with binder and CAs, or forming a stable SEI
stress energy and stress numbers transferred to the particles. interface with electrolyte. As discussed earlier in greater detail,
In brief, stressing in mills occurs either by on-sided impaction these aspects in turn highlight the vital function of surface in
or by two-sided compaction of particles. In ball mills the latter micro-sized Si anodes and its great promise for developing
mechanism prevails. During mill operation, the balls are col- practical high-energy LIBs.
liding with each other upon which energy is transferred to the Successfully serving as a versatile tool in effectively tuning
entrapped particles between the balls. Most milling processes the electrochemical behaviors of Si anodes, organic surface
can be readily scaled-up from lab to full industrial production. moieties hold great promises for boosting the development of
Whereas mostly mechano-chemical effects are studied in the Si-based LIBs. However, even with significant signs of progress
dry state, mechanochemistry in liquids offer interesting options in this regard, many scientific and technological aspects require
since reactions of the liquid with the particles and the grafting further elucidation before the industry-scale deployment of
molecules open additional dimensions. For instance, proper such strategies. An in-depth understanding of the interactions
selection of the solvent in combination with mechanical energy between the Si surface with various substances is critical but
input may trigger enhanced solubility so that the porosity of yet to be explored; here we attempt to provide holistic consid-
the particles can be tuned.[132b] For uniform coating thicknesses erations on facilitating the transition from lab-scale advance-
and coating uniformity the stress conditions and reactions con- ments to practical battery industry. These aspects which are
ditions in the mill must be as uniform as possible. Only the schematized in Figure 13 will be elaborated below.
in-depth understanding of particle stressing in the context of
the mechano-chemical reactions will lead to the fabrication of
uniform and thin surface layers. 6.2. Particle-Level Consideration

6.2.1. Dynamic Surface and System-Specific Design

6. Prospects and Practical Considerations
Apart from neat Si anodes, many Si-containing systems
6.1. Perspectives toward Commercial Si Anode such as Si oxides (SiOx), Si–graphite/carbon composite
(Si–C composite), and Si-based alloys (SiNx, Si–Ge, and
In virtue of the high gravimetric and volumetric capaci- Si–metal alloys) have emerged as propitious and promising
ties of Si (3579 mAh g−1 and 2221 mAh cm−3 based on candidates of anode materials. Even though the Li storage
Li15Si4 with density = 1.20 g cm−3[134]) over prevailing graphite mechanism in these systems is intrinsically analogous, these
anode (372 mAh g−1 and 748 mAh cm−3 on LiC6 with den- materials display quite a different surface chemistry char-
sity = 2.20 g cm−3[135]), developing next-generation of high acteristics in the native state and at the charged state.[31c,140]
energy LIBs hinge on the commercialization for Si-based Despite the fact that many functional moieties have been
anodes. For near-term development, blending/compositing Si designed so far to chemically bond with native nano-Si sur-
with graphite to achieve increased anode capacity is an astute faces, bare nano-Si are never present in actual batteries but
strategy to exhaustively meet electrode criteria including volu- rather exist in the form of Si–C composite, SiOx, etc. In the
metric/gravimetric energy density, low electrode swelling, existing literature, as seen from Table 1, the high SSA nano-Si
high ICE, and fast charge rates. As the desire for longer travel is often chosen as active materials requiring a high dosage of
ranges and smaller battery packs persists, stepwise increase of organic species, which leads to a lowered active Si content in
Si content in commercial cells is ongoing and inevitable. Even the electrode (often <80 wt%). It should be noted that organic
assuming ideal homogeneous Si distribution, the varying Si surface modifications on various dense, low SSA Si-based par-
content in the electrode leads to different degree of volume ticles are rarely explored aspects. Hence, future exploration
changes and stress distribution on both particle and electrode regarding organic layers on various Si-containing micropar-
level, calling for more tunable and adaptive surface chemistries ticles could be highly valuable. Moreover, since the different
of Si. degrees of expansion-contraction of Si-based particles as

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Figure 13. Application-oriented considerations and future research directions for developing high-energy Si-anodes LIBs adopting organic surface
modifications.

cycling proceeds give rise to a varying landscape of surface alleviating these aspects.[144] In particular, fast and thorough
reconfigurations, system-specific design principles of the sur- drying of the electrodes after blade-coating or slot-die extrusion
face moieties and their dynamic evolution during cell opera- is a prerequisite for industry-scale electrode manufacturing. We
tion need to be clarified. note that residual acidic/protic species such as water on the
surface via chemisorption/physisorption will generate HF and
PF5 that erodes SEI and cause capacity fade.[140b,145] An ideal
6.2.2. Electric/Ionic Conductance at the Interface surface organic modifier layer should hence promote separa-
tion/dispersion rather than the aggregation of active parti-
High purity neat Si demonstrate electric conductivity cles in the slurry, and it should not lead to higher content of
(σe) and bulk phase Li-ion diffusion coefficient (DLi) of residual water and protic species (often requires less than tens
σe <10−4 S cm−1[141] and DLi ≈10−14–10−13 cm2 S−1,[142] respectively. of ppm) after electrolyte drying. It is highly practical to develop
These quantities are orders of magnitudes lower than car- a proper slurry formulation and electrode drying protocol for
bonaceous or graphite anodes (σe ≈ 103 S cm−1 with in-plane surface-tuned Si particles, which calls for an explicit description
σe = 104 S cm−1 and DLi ≈ 10−9 cm2 S−1).[143] The intrinsic low of the interactions between organic surface moieties with slurry
electric conductivity and Li-ion diffusivity of Si impose chal- solvents (often H2O) and dissolved binder chains.
lenges on gaining fast-charging capabilities. The remaining
open questions in this regard include: How did surface organic
moieties affect electron transport at the Si surface? Should it 6.3.2. Electrolyte Compatibility and Synergy
be thin enough to allow electron tunneling? Moreover, how to
structure the surface organic coatings so that would not impede Very recently, various novel electrolyte systems have emerged
Li diffusion but effectively shield-off electrolyte side reactions? to be more effective than conventional carbonate electrolytes
The design of a properly structured surface films entails an (1 m LiPF6 in carbonate solvents) in stabilizing Si anodes. These
in-depth understanding of the electron/Li+ transport mecha- systems include novel solvents,[22a,b] Li-salts,[12e] or electrolyte
nism through the interfacial layer. additives.[90,146] In recent reports, pristine Si particles are often
adopted as rather research objects than practical solutions.
Moreover, the development of synergism between organic
6.3. Electrode-Level Consideration surface moieties and advanced electrolyte systems remains
largely unexplored. It is important to note that to achieve high
6.3.1. Slurry Metrics energy density cells, electrolyte dosage should be no larger
than 5 µL mAh−1. Practical cells require area capacities levels
Viscosity and rheological behavior of the electrode slurry of 3–≈5 mAh cm−2, corresponding to mass loading levels of Si-
are critical for continuous high-speed mixing and roll-to- based active material in the range of 6–≈10 mg cm−2 assuming
roll coating during cell fabrication. The organic surface layer specific capacity levels of ≈500 mAh g−1. In principle, the
changes the particle–particle interactions and thus affects both organic surface moieties have to be both highly “electrolyte-
rheology and particle aggregation during drying. Both effects philic,” allowing ideal wetting, and also “electrolyte-inert” to
may lead to significant variations of slurry metrics and must minimize electrolyte side reactions. To explore these properties,
therefore be carefully tailored. Particle aggregation and agglom- it will be enlightening to elucidate both macroscopic and micro-
eration are the main marplots for achieving desirable electro- scopic wetting of electrolytes on various well-tuned Si surfaces.
chemical performances and numerous efforts are devoted to Finally, performance evaluation of surface-tuned Si anodes

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under practical battery conditions such as high area capacity anode choice for SSE-LIBs studies however it is now recog-
and limited electrolyte dosage is an essential step toward prac- nized that dendrite formation is even more prone to take place
tical application. in solid state batteries than in their liquid counterpart. Hence,
Si-based anodes can avoid Li deposition and eliminate the
dendrite risks, hence to be considered as intrinsically “safer”
6.4. Cell-Level Considerations anode choice. One major challenge in Si-based SSEs-LIBs that
requires substantial innovation is the poor solid-solid electrode/
6.4.1. Cathode-Si Crossover electrolyte interface.[149] Recent studies demonstrated notable
progress in Si-based SSEs-LIBs adopting gel-polymer electro-
For high-energy-density cell design, Si anodes pairing with lytes,[150] garnet-type[151] or sulfide solid electrolytes.[139,152] Sur-
high voltage ceramic cathodes (such as nickel-cobalt-manga- prisingly, with improved ionic conductivity of electrolyte and
nese/aluminum oxides, that is, NCM/NCA) would be a real- Si–SSE interfacial contact, stable full cell cycle performances
istic and prevailing choice. Transition metal (Ni2+/Co2+/Mn2+) with 99.9 wt% Coulombic efficiency could be achieved even at
dissolution, shuttling, and reduction onto Si surface greatly high current density (5 mA cm−2).[139] This implies that Si-based
affect the surface chemistry and cycle life of anodes.[147] How- particles can be seriously regarded as an anode choice alterna-
ever, whether the shuttling-reduction of transition metal ions tive to Li metal in solid state batteries. In this regard, the Si-
on Si anode will be suppressed by an organic surface layer surface design principles, for example, tuning ion and electron
remains an open question. Similarly, how the shuttled species conduction behaviors of the interface, may shed some light on
would react with the pre-planted organic moieties is unknown the path of developing next-generation SSE-LIBs.
to date. Nevertheless, a surface layer on Si that is immune to
or scavenges the shuttled species will be highly useful in this
regard. Moreover, recent studies highlight the impact of anode- 7. Summary
to-cathode shuttling species such as HF and POFx.[148] In this
regard, it is important to unravel whether the surface organic Si anodes represent a highly promising anode candidate for
species dissolve and crosstalk to the cathode side or not. Given high energy LIBs but suffer from intrinsic volume changes and
its profound impact on actual cell cycle performances, we structural instabilities. The fading-to-failing mechanism of Si
would like to highlight the importance of investigating the two- anode is multidimensional and intermixed. A unique perspec-
way crossover between cathodes and Si-anodes. As seen from tive is to overview all associated problems to interfacial insta-
Table 1, full-cell-based evaluations of surface-tuned Si are scarce bilities between Si and liquid electrolytes, polymer binders,
from existing literature and investigations on cathode-Si cross- and CAs. In this review, recent discoveries regarding the fun-
talk remain at a fairly early stage. damental recognition of Si anode SEI components and surface
functionality are discussed. Some critical aspects of the latest
development of advanced diagnostic tools in promoting in-
6.4.2. Operating Conditions depth understanding of Si anode surface are covered. The newly
unveiled aspect of Si surface science points to the critical role
Another interesting topic is related to further investigation on of emerging organic surface moieties in stabilizing Si anode.
the responses of surface chemical structures toward various cell We provide up-to-date advances reporting unparalleled advan-
operation conditions, such as temperatures, stack pressure, cur- tages of organic surface films in terms of flexibility, ample func-
rent densities, cut-off voltages, or storage at various open circuit tionality, ease of synthesis, and efficacy in improving Si cycle
potential or SOC. The open questions in this regard include: performances. Three main categories of design principles on
How do the surface organic moieties react to extreme condi- organic surface chemistry for Si are discussed and compared in
tions such as overheating or internal short-circuit? Is it possible detail with representative case studies, emphasizing the inter-
for the organic surface layer to improve cell safety character- action of artificial Si surface with liquid electrolyte, polymer
istics against abuse conditions such as nail penetration and binders, and CAs. Throughout this review, we give comprehen-
thermal runaway? It would be of particular significance if such sive considerations in transforming lab-scale advances toward
surface organic species could be designed to auto-transform industrial applications. The unresolved scientific and tech-
into ion-impermeable/insulating layers or self-decompose into nological aspects regarding surface engineering with organic
fire-extinguishing gases in response to abuse conditions. Fur- moieties are also pointed out, highlighting research directions
ther chemical and structural engineering offer immense oppor- that are most intriguing and potentially fruitful. With further
tunities in achieving the versatile functionality of the surface intensive research and development endeavors, organic surface
film. chemistry could be deemed as a highly promising avenue for
accelerating the commercialization of Si-based anodes for high-
energy LIBs.
6.5. Outlook in Solid-State Batteries

Replacing the flammable organic electrolytes with solid-state Acknowledgements

electrolytes (SSEs), that is, quasi-solid or all-solid-state, the W.L. acknowledges financial support of Natural Science Foundation
SSEs-LIBs provides great advantages to ease the safety risk of of China (NSFC-51702223) and International Collaborative Project of
high energy batteries. Li metal has been the most prevalent Chengdu (2019-GH02-00031-HZ). S.H. and W.P. acknowledge DFG

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funded collaborative research center CRC 953 – Carbon Allotropes and [12] a) S. Q. Huang, S. W. Wang, G. H. Hu, L. Z. Cheong, C. Shen,
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Zidong Chen is currently a postgraduate student studying under Prof. Wei Liu’s supervision at the
Institute of New Energy and Low-Carbon Technology (INELT) at Sichuan University. He received
his B.Sc. in materials science and engineering from Sichuan University in 2021. His research
interests focus on the development of novel anode materials for lithium-ion batteries.

Askar Soltani received his B.Sc. in Mechanical Engineering from Zanjan University and M.Sc. in
materials science and engineering from Azad University of Tehran-Science and Research branch in
Iran. He is currently a Ph.D. candidate at Sichuan University in China to work on Li-ion batteries.
He is an enthusiastic researcher in the field of electrochemistry and has presented many scientific
talks at international conferences. His future research is focused on renewable energy storage.

Yungui Chen, Ph.D., born in 1960, is a professor at Sichuan University. He is the chief scientist
of the New Energy and Low-carbon Technology Discipline, the chairman of the Professors
Committee of the Institute of New Energy and Low-Carbon Technology (INELT), Sichuan
University, and the director of the Engineering Research Center of Alternative Energy Materials
and Devices, Ministry of Education, P. R. China. His research interests include magnesium alloys,
titanium alloys, hydrogen storage materials, electrode materials, and batteries.

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Qiaobao Zhang is a professor at the Department of Materials Science and Engineering, College
of Materials, at Xiamen University. He obtained his Ph.D. degree from the City University of
Hong Kong in 2016 after then he joined Xiamen University. His current research focuses on the
fundamental issues relevant to energy storage systems including Li/Na/K ion batteries, especially
on the key electrode materials, interfacial properties, and in situ techniques. He has published
more than 130 papers, 21 of which are highly cited, and attracted more than 9000 citations with an
h-index of 52.

Ali Davoodi received his B.Sc. and M.Sc. in materials science and engineering from Shiraz
University and Shahid Bahonar University of Kerman, Iran, respectively. He completed his
Ph.D. at the Royal Institute of Technology (KTH), Sweden, where he worked on the corrosion of
aluminum alloys. He carried out post-doctoral work at Technische Universität Hamburg (TUHH)
and Harvard University, respectively. He is now an associate professor at Ferdowsi University of
Mashhad (FUM), Iran, and Sichuan University-Pittsburg Institute (SCUPI), China, working on
electrochemistry, corrosion, and battery. He has 87 peer-reviewed papers with an h-index of 32.

Saman Hosseinpour is the surfaces and interfaces group leader at the Institute of Particle
Technology at Friedrich-Alexander University Erlangen-Nuremberg and an adjunct professor of the
department of materials and metallurgical engineering at Ferdowsi University of Mashhad (FUM),
Iran. He performed his Ph.D. studies at the Royal Institute of Technology (KTH) in Sweden with a
focus on corrosion, materials degradation, and surface science followed by a postdoc stay at the
Max Planck Institute for Polymer Research (MPIP) in Mainz, Germany. In 2016, he received the
prestigious Morris Cohen Graduate Award for the best doctoral thesis in corrosion science and
electrochemistry worldwide.

Wolfgang Peukert is the director of the Institute of Particle Technology at the Friedrich-Alexander
University Erlangen-Nuremberg, Germany. He has so far coordinated several large research
projects, including the Cluster of Excellence “Engineering of Advanced Materials”, and is the
founder of the Interdisciplinary Center for Functional Particle Systems. His research interests
focus on key aspects of particle science and technology, with special emphasis on product
design and formulation of nanoparticles. He has received several awards, is a member of
national academies, and has a track record of more than 400 scientific publications. His motto is
“innovation occurs at the interfaces.”

Adv. Energy Mater. 2022, 12, 2200924 2200924 (30 of 31) © 2022 Wiley-VCH GmbH
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Wei Liu is a professor at the Institute of New Energy and Low-carbon Technology (INELT) of
Sichuan University. He received his Ph.D. in polymer science and engineering from Sichuan
University in 2016. From 2014 to 2015, he worked as a visiting scholar at the University of
Massachusetts, Amherst. At present, his research interests include materials and membranes
involved in energy storage devices, with his main focus devoted to the multidimensional
architectures and interfaces for high-energy anodes of Li/Na batteries (carbons/silicon/alkali
metals). Dr. Liu also serves on the Early Career Board for Chinese Chemical Letters, a CCS journal.

Adv. Energy Mater. 2022, 12, 2200924 2200924 (31 of 31) © 2022 Wiley-VCH GmbH