batteries

Review
A Review of the Application of Carbon Materials for Lithium
Metal Batteries
Zeyu Wu, Kening Sun and Zhenhua Wang *

Beijing Key Laboratory of Chemical Power Source and Green Catalysis, School of Chemistry and Chemical Engineering,
Beijing Institute of Technology, Beijing 100081, China
* Correspondence: [email protected]

Abstract: Lithium secondary batteries have been the most successful energy storage devices for nearly
30 years. Until now, graphite was the most mainstream anode material for lithium secondary batteries.
However, the lithium storage mechanism of the graphite anode limits the further improvement of the
specific capacity. The lithium metal anode, with the lowest electrochemical potential and extremely
high specific capacity, is considered to be the optimal anode material for next-generation lithium
batteries. However, the lifetime degradation and safety problems caused by dendrite growth have
seriously hindered its commercialization. Carbon materials have good electrical conductivity and
modifiability, and various carbon materials were designed and prepared for use in lithium metal
batteries. Here, we will start by analyzing the problems and challenges faced by lithium metal. Then,
the application progress and achievements of various carbon materials in lithium metal batteries are
summarized. Finally, the research suggestions are given, and the application feasibility of carbon
materials in metal lithium batteries is discussed.

Keywords: lithium metal batteries; carbon materials; composite anodes; current collectors

1. Introduction
Citation: Wu, Z.; Sun, K.; Wang, Z. A
Review of the Application of Carbon The use of fossil fuels has made invaluable contributions to the development of
Materials for Lithium Metal Batteries. human society. However, problems such as resource depletion and environmental pollution
Batteries 2022, 8, 246. https:// force human beings to develop new energy systems and adjust the energy structure [1].
doi.org/10.3390/batteries8110246 New systems such as wind, hydro, solar, and fuel cells are expected to provide clean
and sustainable energy for human society. As an effective way to store and transfer
Academic Editor: Junsheng Zheng
energy, electrochemical energy storage has gradually become an indispensable part of the
Received: 15 October 2022 transformation of energy structure [2,3]. Since the advent of lithium-ion batteries in the
Accepted: 15 November 2022 19th century, they have become an irreplaceable energy storage device in various fields [4,5].
Published: 18 November 2022 With the unremitting efforts of researchers, the safety performance, specific energy, and
Publisher’s Note: MDPI stays neutral
cycle life of lithium-ion batteries were greatly improved, but they are still far from meeting
with regard to jurisdictional claims in
the development needs of electric vehicles and portable electronic devices [6,7]. The human
published maps and institutional affil- pursuit of high specific energy, long life, and fast charging batteries has never stopped.
iations. In the current commercial lithium secondary batteries, high nickel cathode materials can
provide a specific capacity of 220 mA h g−1 and an energy density of 800 W h kg−1 [8].
However, the intercalation cathode material is limited by the crystal volume and element
quality. Its specific energy is difficult to further improve. In this case, research to improve
Copyright: © 2022 by the authors. the energy density of batteries has mainly focused on the anode side. Widely used graphite
Licensee MDPI, Basel, Switzerland. materials have low specific capacity and energy density (specific capacity 372 mA h g−1 ,
This article is an open access article energy density 300–400 W h kg−1 ). Lithium metal anodes with high specific capacity
distributed under the terms and (3860 mA h g−l or 2061 mA h cm−3 ) are considered to be the best choice for next-generation
conditions of the Creative Commons lithium battery anodes [9–11]. In particular, Li-S and Li-O2 batteries assembled with
Attribution (CC BY) license (https://
high specific energy cathodes such as S or O2 can provide specific energies as high as
creativecommons.org/licenses/by/
650 W h kg−1 and 950 W h kg−1 , respectively.
4.0/).

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Batteries 2022, 8, 246 2 of 24

Lithium metal anodes were extensively studied long before graphite anodes, but were
not effectively used until now. There are three main problems faced by Li metal anodes:
(1) The depositing/stripping of Li metal during cycling is accompanied by a huge change
in its volume, which leads to changes in the internal pressure and structure of the battery.
(2) The side reactions that occur continuously with the battery cycle consume the effective
components in the electrode and the electrolyte, resulting in a decrease in the coulombic
efficiency of the battery or even failure. (3) Lithium metal tends to grow dendrites in
liquid electrolytes. The formation of lithium dendrites has serious consequences: the
larger specific surface area leads to more reactions with the electrolyte; the fracture of
dendrites during cycling will cause part of the lithium metal to detach from the collector
and become “dead lithium”, resulting in a decrease in electrode capacity.; dendrites may
also penetrate the separator and contact the positive electrode to short-circuit the battery
and cause thermal runaway. The above problems have become the bottlenecks that limit
their commercialization [12,13]. Paul Albertus et al. [14] believe that the application of a
lithium battery needs to maintain an average Coulomb efficiency of 99.98% in 1000 cycles
to reach the commercial level, and the current lithium metal anode is still far from this goal.
After more than 40 years of continuous research and deepening understanding of
lithium metal electrodes, various strategies to control dendrite growth and improve the
efficiency of lithium metal electrodes were proposed. These strategies have made various
modifications and designs mainly from the perspectives of electrolytes, separators, SEIs,
current collectors, composite electrodes, and solid electrolytes.
Electrolyte regulation For the electrolyte development of the lithium metal battery,
the composition and structure of SEI are mainly regulated by changing the lithium salts
and additives in the electrolyte [15]. In recent years, high-concentration and localized
high-concentration electrolytes based on a solvated structure design have obtained lithium
metal batteries with high Coulombic efficiency by promoting the decomposition of anions
and reducing the reduction of free solvents [16–20]. However, expensive lithium salts and
diluents hinder its further application. In addition to forming SEI, the electrolyte can also
inhibit the growth of lithium dendrites by forming an electrostatic screen shielding layer
on the surface of the lithium metal electrode. Cs+ , Rb+ , and other cations can suppress the
formation of lithium dendrites by adsorbing on the surface of lithium metal to form an elec-
trostatic shielding layer, thereby enabling the uniform deposition of lithium metal [21,22].
Separator modification: In the design of the lithium metal battery separator, the main
purpose is to improve its Young’s modulus to suppress the growth of lithium dendrites and
to design the separator with uniform pores to obtain uniform lithium ion flux [23–26]. In
addition, immobilizing inorganic materials or organic groups on the separator can obtain
separators with specific functions, which can improve the safety and cycling stability of
lithium metal batteries [27,28]. Utilizing the pore structure of the separator can also assist
in adjusting the solvation structure of the electrolyte to obtain a functionalized separator
with a wide electrochemical stability window and a stable SEI structure [29].
Artificial SEI The composition and structure of the SEI film on the surface of Li metal
electrodes can be directly and effectively adjusted in situ by changing the composition
of the electrolyte [30]. Artificial SEI layers can also be constructed on Li metal surfaces
by ex situ methods [31,32]. Various organic polymers, inorganics, and organic–inorganic
composite SEIs can provide high mechanical properties to suppress dendrite growth, high
lithium ion conductivity to reduce polarization, and thus, improve the stability of lithium
metal electrodes during battery cycling [33–38].
Current collector design Electrodeposition of lithium metal is closely related to its
current density, and a large specific surface area can effectively reduce the local current
density to inhibit dendrite growth [39]. Adding lithiophilic or nucleation-inducing sub-
stances to the current collector can also reduce the nucleation overpotential or uniform Li
metal deposition. Metals and carbon materials such as Cu and Ni with excellent electronic
conductivity are the two most common current collector materials [40–42]. In addition,
 density to inhibit dendrite growth [39]. Adding lithiophilic or nucleation-inducing sub-
stances to the current collector can also reduce the nucleation overpotential or uniform Li
Batteries 2022, 8, 246 metal deposition. Metals and carbon materials such as Cu and Ni with excellent electronic 3 of 24
conductivity are the two most common current collector materials [40–42]. In addition,
carbon materials have the characteristics of light weight, high electronic conductivity, and
easy modification
carbon materialsand haveare
theone of the excellent
characteristics current
of light collectors
weight, for lithiumconductivity,
high electronic metal anodes. and
Solid-state electrolytes: Solid-state electrolytes mainly
easy modification and are one of the excellent current collectors for lithium include organic polymer elec-
metal anodes.
trolytes, inorganicelectrolytes:
Solid-state ceramic electrolytes,
Solid-stateand organic–inorganic
electrolytes composite
mainly include electrolytes
organic polymer [43–
elec-
48]. Solid-state
trolytes, electrolytes
inorganic ceramic are considered
electrolytes, andtoorganic–inorganic
be the technical direction
compositewith the most
electrolytes po-
[43–48].
tential to enable
Solid-state lithium are
electrolytes metal batteriestotobe
considered bethe
applied.
technicalSolid-state
directionelectrolytes
with the most arepotential
believedto
toenable
provide high modulus
lithium and migration
metal batteries numbers
to be applied. close to
Solid-state unity without
electrolytes causingtolithium
are believed provide
dendrite growth. However, in the research of organic and inorganic
high modulus and migration numbers close to unity without causing lithium dendrite solid electrolytes, it
is growth.
found that short circuit or thermal runaway caused by dendrite growth
However, in the research of organic and inorganic solid electrolytes, it is found is still inevitable
[49–51].
that short circuit or thermal runaway caused by dendrite growth is still inevitable [49–51].
Various
Variousnew newmaterials
materialsand andtechnologies
technologies were
were tried
triedtotosolve
solvethe
the problems
problems faced
faced byby
lithium
lithiummetal
metalbatteries,
batteries,but
butthethecommercialization
commercialization of of lithium
lithium metal electrodes is
metal electrodes is still
stillfull
fullof
ofchallenges.
challenges. Compared
Compared to to other
other materials,
materials,carbon
carbonmaterials
materialshave haveexcellent
excellentelectrical
electrical and
and
thermal
thermal conductivity.
conductivity. Their
Their structural
structural plasticity
plasticity and
and easy
easymodification
modification allow
allowthemthem toto
bebe
designed
designed in ina variety
a variety of shapes
of shapes andand
have specific
have functions.
specific WithWith
functions. the rise
theinrise
materials sci-
in materials
ence and and
science nanotechnology,
nanotechnology, carbon
carbonmaterials
materialsof different
of differentdimensions
dimensions (0–3D)
(0–3D) andand different
different
scales
scales(nano-millimeter)
(nano-millimeter) were
were developed
developed and
and played
played a huge
a huge role inin
role lithium
lithium metal
metal batteries
batteries
(Figure
(Figure1).1).InInlithium
lithiummetal
metalbatteries,
batteries,carbon
carbon materials
materials are mainly
mainly used
usedas ascurrent
currentcollectors
collec-
tors to disperse
to disperse current
current andand heat.
heat. In In addition,
addition, carbon
carbon materials
materials cancan also
also bebe used
used as as addi-
additives
tives or artificial SEI to participate in lithium metal electrodes to inhibit dendrite growth
or artificial SEI to participate in lithium metal electrodes to inhibit dendrite growth and
and improve battery life.
improve battery life.

.
Figure 1. Various strategies applied by carbon materials in lithium metal batteries.
Figure 1. Various strategies applied by carbon materials in lithium metal batteries.
This review will start from the inherent scientific issues of metallic lithium anodes
andThis
introduce
reviewthe
willproblems
start fromand challenges
the of metallic
inherent scientific lithium
issues electrodes.
of metallic Then,anodes
lithium various
applications of carbon and its derivatives/composites in lithium metal batteries
and introduce the problems and challenges of metallic lithium electrodes. Then, various are sum-
marized. Finally, the research of carbon materials in lithium metal batteries is discussed
and suggestions for its development direction are provided.

2. Issues and Challenges of Lithium Metal Anodes

2.1. Nucleation of Lithium Metal
Lithium metal anodes undergo reversible plating and stripping during battery cy-
cling. In each charging process, lithium atoms go through a process from nucleation to
 applications of carbon and its derivatives/composites in lithium metal batteries are sum
marized. Finally, the research of carbon materials in lithium metal batteries is discuss
and suggestions for its development direction are provided.

Batteries 2022, 8, 246 2. Issues and Challenges of Lithium Metal Anodes 4 of 24

2.1. Nucleation of Lithium Metal
Lithium metal anodes undergo reversible plating and stripping during battery c
cling.
growth. The nucleationIn each
statecharging process,
and growth lithium
pattern of atoms
Li metal go through a process
have a huge effectfrom nucleation
on its
growth. The nucleation
deposition/dendritic morphology. state and growth pattern of Li metal have a huge effect on its de
osition/dendritic morphology.
The nucleation process of Li metal is controlled by the properties of the deposition
The nucleation
substrate, multiphysics, and SEI. Yanprocess of Licompared
et al. [52] metal is controlled by theprocess
the nucleation properties of the depositio
of lithium
substrate, multiphysics, and SEI. Yan et al. [52] compared the
metal on different metal substrates and found that there is an obvious overpotential when nucleation process of lit
ium metal on different metal substrates and found that there is
lithium metal is deposited on the surface of a copper current collector, that is, the energyan obvious overpotent
when
used to overcome thelithium metal is deposited
heterogeneous nucleationon(Figure
the surface
2a). Inofcontrast,
a copper the
current collector,
deposition of that is, t
Li metal on the Au surface first forms a Li-Au alloy above 0 V, and then, there is almost no the dep
energy used to overcome the heterogeneous nucleation (Figure 2a). In contrast,
sition of Li during
nucleation overpotential metal on thedeposition
the Au surfaceprocess
first forms a Li-Au
below alloy above
0 V (Figure 2b). 0They
V, and then, there
also
almost no nucleation overpotential during the deposition process below 0 V (Figure 2b
verified the deposition process of lithium metal on more than ten current collectors and
They also verified the deposition process of lithium metal on more than ten current co
proved that the properties of the current collector have a significant impact on the lithium
lectors and proved that the properties of the current collector have a significant impact o
metal nucleation process (Figure 2c,d).
the lithium metal nucleation process (Figure 2c,d).

Figure 2. VoltageFigure 2. Voltage

distributions of distributions
galvanostaticofLigalvanostatic
deposition on Li deposition
copper (a) on
and copper (a) and
gold (b) gold (b) substra
substrates
(EWEof
(EWE is the potential is the
the potential
working of the working
electrode) electrode)
(c) Voltage (c) Voltage distributions
distributions of variouswith
of various materials materials with
certain solubility in Li during Li deposition, (d) Displacement voltage distributions
a certain solubility in Li during Li deposition, (d) Displacement voltage distributions for various for various m
terials with negligible solubility in Li [52].
materials with negligible solubility in Li [52].

In addition to the properties of the deposition substrate, the presence of various

physical fields can have an effect on the nucleation of lithium metal. Han et al. [39]
observed the nucleation state of Li metal on copper substrates at different temperatures
and current densities by SEM (Figure 3a). At low temperature and high current density, the
nucleation density of Li metal is higher and the particles are smaller. Further, Pei et al. [53]
combined the analysis of the homogeneous nucleation equation and the SEM experimental
results to conclude that the size of the lithium metal nuclei is inversely proportional to the
overpotential, and the nucleus number density is proportional to the third power of the
overpotential (Figure 3b–d).
 fields can have an effect on the nucleation of lithium metal. Han et al. [39] observed the nucle-
ation state of Li metal on copper substrates at different temperatures and current densities by
SEM (Figure 3a). At low temperature and high current density, the nucleation density of Li
metal is higher and the particles are smaller. Further, Pei et al. [53] combined the analysis of
the homogeneous nucleation equation and the SEM experimental results to conclude that the
Batteries 2022, 8, 246 5 of 24
size of the lithium metal nuclei is inversely proportional to the overpotential, and the nucleus
number density is proportional to the third power of the overpotential (Figure 3b–d).

Figure
Figure 3.
3. (a)
(a) Nucleation
Nucleation states
states of
of Li
Li metal
metalononcopper
coppersubstrates
substrates at
atdifferent
different temperatures
temperatures and
and current
current
densities
densities [39]. (b) Schematic diagram of the relationship between critical Li core radius and areal
[39]. (b) Schematic diagram of the relationship between critical Li core radius and areal
core
core density
density and
and Li
Li deposition
deposition overpotential.
overpotential. (c)
(c) Experimental
Experimental voltage
voltage distributions
distributions of
of Li
Li deposition
deposition
on Cu at different current densities. (d) Schematic illustration of the size and density of Li nuclei
on Cu at different current densities. (d) Schematic illustration of the size and density of Li nuclei
deposited on Cu at different overpotentials [53].
deposited on Cu at different overpotentials [53].
The
The use
use of
of lithium
lithium metal
metal deposition
deposition materials
materials with
with low
low nucleation
nucleation overpotential
overpotential and
and
effective
effective current density is an important way to regulate lithium metal nucleation. Carbon
current density is an important way to regulate lithium metal nucleation. Carbon
materials
materials with
withhigh
highspecific
specificsurface area
surface and
area conductivity
and conductivitycancaneffectively disperse
effectively the cur-
disperse the
rent
current density and, thus, make lithium metal deposition more uniform. Compared met-
density and, thus, make lithium metal deposition more uniform. Compared with with
als suchsuch
metals as Cuas and Ni, carbon
Cu and Ni, carbonmaterials are lithiophilic.
materials The The
are lithiophilic. lithiophilicity of carbon
lithiophilicity ma-
of carbon
terials cancan
materials be enhanced
be enhancedafterafter
doping or chemical
doping treatment.
or chemical treatment.Lithiophilic deposition
Lithiophilic sub-
deposition
strates can induce more uniform nucleation and growth of lithium
substrates can induce more uniform nucleation and growth of lithium metals. metals.

2.2. Growth of Dendrites and Formation of “Dead Lithium”

In terms of material properties, Li metal has a low surface energy and a high diffusion
barrier (calculated about 0.14 eV [54]). During deposition, lithium metal tends to form
a larger surface area to reach the lowest surface energy state. At the same time, lithium
atoms have high diffusion energy on the bulk surface, which makes it difficult for atoms
formed by lithium ions to obtain electrons to diffuse on the surface and form a uniform
and flat structure. The natural properties of lithium metal determine that it tends to grow
Batteries 2022, 8, 246 6 of 24

one-dimensionally, that is, to grow into dendrites [55,56]. The growth of lithium dendrites
is mainly affected by factors such as electric field strength, lithium ion flux, current density,
temperature, and pressure [56]. The widely accepted space charge model can well explain
the growth of Li dendrites in the liquid electrolyte. Chazalviel et al. [57] believed that the
space charge layer in dilute solution led to the formation of dendrites. Specifically, at the
initial stage of deposition, lithium ions on the electrode surface gain electrons and become
atoms. However, the lithium ions in the convection region cannot reach the electrode
surface quickly due to the slow diffusion rate, and a concentration gradient of lithium ions
is formed on the electrode surface at this time. The existence of the concentration gradient
resulted in the formation of a space charge layer on the electrode surface. At this time, the
uneven surface of the electrode leads to uneven distribution of electrons at the interface.
Under the combined action of the electric field and ion field, lithium ions will preferentially
deposit at the protrusions (lithium metal nucleation sites or dendrite tip), a phenomenon
also known as the “tip effect”. This growth mode is quantified by Sand and summarized as
Sand’s Time formula to predict the critical condition for dendrite growth [58]:

C0 ezc 2 µ a + µc 2
τs = πD ( ) ( ) (1)
2J µa

µ a Dc + µ c D a
D= (2)
µ a + µc
where e is the electron charge, J is the effective electrode current density, zc is the number of
cationic charges, and C0 is the initial concentration of Li salt. µc and µa are the anion and
cation (Li+) mobilities, D is the bipolar diffusion coefficient, Dc and Da are the cation and
anion diffusion coefficients.
It can be seen that reducing the current density can increase the onset time of lithium
dendrite growth so as to achieve the effect of inhibiting the growth of dendrites. Yoon et al. [59]
analyzed the relationship between the current density and deposition capacity of lithium
metal and the growth of lithium dendrites and showed that with the increase in current
density, the critical discharge required to form dendrites first increased and then decreased.
In addition to current density, compressive stress is also an important factor controlling
dendrite growth. Monroe and Newman predicted that shear moduli over 109 Pa could
inhibit dendrite growth [60]. Temperature can affect the growth process and morphol-
ogy of dendrites through the diffusion and surface reaction of Li ions. The study by
Hitoshi Ota et al. [61] found that dendrite growth is more serious at a lower temperature.
In different electrolyte systems, dendrites appear with different morphologies, indicat-
ing that the morphology of lithium dendrites is also controlled by the electrolyte and the
SEI derived from the electrolyte. The presence of defects induces Li metal deposition on
current collectors or SEIs at defects, dislocations, grain boundaries, and even contaminants.
Under the combined action of many influencing factors, lithium dendrites can appear as
needle-like, mossy-like or tree-like. The growth of dendrites mainly leads to three adverse
consequences: penetrating the separator and contacting the positive electrode, resulting
in a short circuit or even thermal runaway of the battery; the larger specific surface area
aggravates the reaction between the electrode and the electrolyte, which consumes the
electrolyte in the battery; lithium dendrites form “dead lithium” after fracture, resulting in
the loss of lithium inventory.
“Dead lithium” formed after lithium dendrites break cannot continue to participate
in the electrochemical process because they are separated from the current collector. The
loss of active material will lead to the decrease in battery capacity, and the large amount
of “dead lithium” wrapped by SEI on the electrode surface will also hinder the mass
transfer process and cause the increase in polarization. The composition of SEI and “dead
lithium” in pulverized lithium anodes can be quantitatively analyzed by titrimetric gas
chromatography [62] and nuclear magnetic resonance spectroscopy [63]. This study found
 “Dead lithium” formed after lithium dendrites break cannot continue to participate
in the electrochemical process because they are separated from the current collector. The
loss of active material will lead to the decrease in battery capacity, and the large amount
of “dead lithium” wrapped by SEI on the electrode surface will also hinder the mass trans-
Batteries 2022, 8, 246 fer process and cause the increase in polarization. The composition of SEI and “dead lith-
7 of 24
ium” in pulverized lithium anodes can be quantitatively analyzed by titrimetric gas chro-
matography [62] and nuclear magnetic resonance spectroscopy [63]. This study found that
the the
that “dead lithium”
“dead thatthat
lithium” loses activity
loses duedue
activity to detachment
to detachment from thethe
from current collector
current collectoris is
an
important factor leading to battery capacity decay.
an important factor leading to battery capacity decay.
InInthis
thiscase,
case,the
thegrowth
growthof oflithium
lithiumdendrites
dendritescan
canbebeinhibited
inhibitedby
byreducing
reducingthe
theeffective
effective
current density. Carbon materials with high specific surface areas can disperse
current density. Carbon materials with high specific surface areas can disperse the currentthe current
density, thereby reducing the local current density to obtain a dendrite-free lithium
density, thereby reducing the local current density to obtain a dendrite-free lithium metal metal
anode.At
anode. Atthe
thesame
sametime,
time,carbon
carbonmaterials
materialswith
withgood
goodmechanical
mechanicalstrength
strengthasasartificial
artificialSEI
SEI
can also inhibit the growth of lithium dendrite.
can also inhibit the growth of lithium dendrite.

2.3.Solid
2.3. SolidElectrolyte
ElectrolyteInterphase
InterphaseofofLithium
LithiumMetal
MetalAnode
Anode
Thesolid
The solidelectrolyte
electrolyteinterphase
interphase(SEI)(SEI)isisaapassivation
passivationinterface
interfacelayer
layerformed
formedby bychemi-
chem-
icaland
cal andelectrochemical
electrochemicalreactions
reactionson onthethesurface
surfaceofofthe thenegative
negativeelectrode.
electrode.Similar
Similartotothe
the
solid-stateelectrolyte,
solid-state electrolyte, the
the SEI
SEI acts
acts to
toconduct
conductlithiumlithiumions
ionsand andblock
blockfurther
furtherreactions be-
reactions
tween the active material and the electrolyte. Lithium metal and the electrolyte will form
between the active material and the electrolyte. Lithium metal and the electrolyte will
an SEI
form anfilm through
SEI film a chemical
through reaction
a chemical at the
reaction atmoment
the moment of contact. ThisThis
of contact. is because the elec-
is because the
trochemical window
electrochemical window of of
general
generalorganic
organicelectrolytes
electrolytesisisabout
about 1–4.7
1–4.7 V (relative to
V (relative to Li
Limetal
metal
potential),and
potential), andthetheelectrode
electrodepotential
potentialofofLi Limetal
metalisislower
lowerthan
thanthethereduction
reductionpotential
potentialofof
electrolytes[64,65].
electrolytes [64,65].Goodenough
Goodenoughetetal. al.[2]
[2]explained
explainedthis thisphenomenon
phenomenonusing usingthethemolecular
molecular
orbital theory. As shown, the thermodynamic stability of the electrolyte is determinedby
orbital theory. As shown, the thermodynamic stability of the electrolyte is determined by
itslowest
its lowestunoccupied
unoccupiedorbital
orbital(LUMO)
(LUMO)and andhighest
highestoccupied
occupied orbital
orbital (HOMO)
(HOMO) (Figure
(Figure 4).
4).
Whenthe
When theelectrochemical
electrochemicalpotential
potentialof ofthe
theelectrode
electrodeisishigher
higherthan
thanthetheLUMO
LUMOor orlower
lower
thanthe
than theHOMO,
HOMO,the thecontact
contactbetween
betweenthe theelectrode
electrodeand andthe
theelectrolyte
electrolytewillwillnonolonger
longerbe beaa
thermodynamicallystable
thermodynamically stablestate.
state.AtAtthis
this time,
time, thethe electrode
electrode will
will react
react with with
thethe electrolyte
electrolyte to
to form SEI. The presence of SEI complies with the electrochemical potentials of the elec-
form SEI. The presence of SEI complies with the electrochemical potentials of the electrode
trode
and and electrolyte
electrolyte so that so
nothat no further
further reactions reactions
can take can take place.
place.

Figure4.4.Schematic
Figure Schematicdiagram
diagramofofopen
opencircuit
circuitenergy
energyininliquid
liquidelectrolytes.
electrolytes.ΦΦ Aand
andΦΦ Care
arethe
theanode
anode
A C
and cathode working potentials, respectively. E g is the electrolyte thermodynamic stability window.
and cathode working potentials, respectively. Eg is the electrolyte thermodynamic stability window.
μ A > LUMO and/or μ C < HOMO indicate that the SEI layer needs to be formed to reach a kinetically
µA > LUMO and/or µC < HOMO indicate that the SEI layer needs to be formed to reach a kinetically
stable state [2].
stable state [2].

The native SEI formed by chemical reaction is often not enough to maintain stability
during the electrochemical process, so the lithium metal electrode will also reduce the
electrolyte through an electrochemical reaction to form SEI. During the electrochemical
process, not only the new electrolyte is reduced to increase and thicken the SEI but the
structure and composition of the original SEI also change. In addition, continuous cracking
and regeneration of SEI also occurs due to the volume change and non-uniformity of
 The native SEI formed by chemical reaction is often not enough to maintain stability
during the electrochemical process, so the lithium metal electrode will also reduce the
Batteries 2022, 8, 246 electrolyte through an electrochemical reaction to form SEI. During the electrochemical8 of 24
process, not only the new electrolyte is reduced to increase and thicken the SEI but the
structure and composition of the original SEI also change. In addition, continuous crack-
ing and regeneration of SEI also occurs due to the volume change and non-uniformity of
plating/stripping
plating/stripping ofofLiLimetal.
metal.AsAs shown
shown in in Figure
Figure 5, Cohen
5, Cohen et [66]
et al. al. [66] believed
believed thatthat during
during
the deposition of lithium metal, the growth of lithium dendrites would also break the SEI, the
the deposition of lithium metal, the growth of lithium dendrites would also break
and the
SEI, andfresh lithium
the fresh metal metal
lithium wouldwould
continue to reacttowith
continue thewith
react electrolyte to form the
the electrolyte SEI. the
to form
When the lithium metal is peeled off, the brittle SEI film will rupture to expose the fresh the
SEI. When the lithium metal is peeled off, the brittle SEI film will rupture to expose
lithium
fresh metal.metal.
lithium At thisAttime,
thisthe exposed
time, lithium lithium
the exposed metal will continue
metal to react with
will continue the elec-
to react with the
trolyte to form a new SEI.
electrolyte to form a new SEI.

Figure 5.
Figure 5. Description
Description of
of the
the morphology
morphologyand
andfailure
failuremechanism
mechanismofofLiLielectrodes
electrodesduring
duringLiLideposi-
deposition
tion and dissolution, with dendrite formation and heterogeneous Li dissolution accompanied by
and dissolution, with dendrite formation and heterogeneous Li dissolution accompanied by surface
surface film destruction and repair [66].
film destruction and repair [66].
The ideal SEI is believed to have high insulating properties, high lithium selectivity,
The ideal SEI is believed to have high insulating properties, high lithium selectivity,
and ionic conductivity; to be as thin as possible; with high strength and resistance to ex-
and
pansionionic
andconductivity; to be astothin
contraction stresses; as possible;
be insoluble with highover
in electrolytes; strength
a wideand resistance
range of op- to
expansion and contraction stresses; to be insoluble in electrolytes; over
erating temperatures, and with stability under potential [67]. The active material and elec- a wide range of
operating
trolyte components consumed to form the SEI lead to a decrease in battery capacity and and
temperatures, and with stability under potential [67]. The active material
electrolyte
even failure. components
The formationconsumed to formofthe
and evolution SEISEI arelead to a by
affected decrease in battery
many factors, suchcapacity
as
and
electrolyte composition, current collector material, temperature, electrolyte salt concen-such
even failure. The formation and evolution of SEI are affected by many factors,
tration,
as reduction
electrolyte current rate,
composition, side reactions,
current collectorimpurities, and uneven current
material, temperature, distribution.
electrolyte salt concen-
The low thickness, complex structure, heterogeneous composition, and dynamic proper-
tration, reduction current rate, side reactions, impurities, and uneven current distribution.
ties (spatial
The and temporal
low thickness, complex variations
structure,ofheterogeneous
morphology and composition)
composition, andofdynamic
SEI poseproperties
chal-
lenges toand
(spatial a comprehensive understanding
temporal variations of SEI [30].
of morphology and composition) of SEI pose challenges to
With the development
a comprehensive and innovation
understanding of SEI [30].of characterization techniques, people’s un-
derstanding
With theofdevelopment
the structure and and innovation
compositionofofcharacterization
SEI is constantlytechniques,
changing. Since SEI under-
people’s is
an insoluble
standing substance
of the formed
structure andby the in situ reaction
composition of SEI is of constantly
lithium metal with the Since
changing. electrolyte,
SEI is an
its chemical
insoluble composition
substance formedis dependent
by the in onsituthe formulation
reaction of themetal
of lithium electrolyte
with (salt anion,
the electrolyte,
solvent,
its additives,
chemical concentration,
composition and solvation
is dependent on the structure).
formulation In addition, factors such(salt
of the electrolyte as cur-
anion,
rent density, cut-off voltage, capacity utilization, temperature, and pressure
solvent, additives, concentration, and solvation structure). In addition, factors such as also have cer-
tain effects
current on thecut-off
density, composition
voltage, ofcapacity
SEI [30]. utilization,
In the classictemperature,
carbonate electrolyte with LiPF
and pressure also 6have
certain effects on the composition of SEI [30]. In the classic carbonate electrolyte with
LiPF6 as lithium salt, SEI is mainly composed of organic alkyl lithium carbonate (ROCO2 Li,
(ROCO2 Li)2 ), inorganic lithium salts (LiF, Li2 CO3 , Li2 O), and a small amount of fluorophos-
phate (LiPOx Fy )) [68–70]. There are three main models for the structure of SEI: the bilayer
model [71], the mosaic model [72], and the mosaic pudding model [30,73] (Figure 6). Aur-
bach’s analysis based on Raman, FTIR and XPS found that the SEI is a mixture of various
organic and inorganic substances, and that the inorganic-rich inner layer (in contact with
Li) and the organic-rich outer layer (in contact with the electrolyte) constitute the two-layer
 as lithium salt, SEI is mainly composed of organic alkyl lithium carbonate (ROCO 2 Li,
(ROCO 2 Li) 2 ), inorganic lithium salts (LiF, Li 2 CO 3 , Li 2 O), and a small amount of fluoro-
phosphate (LiPO x F y )) [68–70]. There are three main models for the structure of SEI: the
Batteries 2022, 8, 246 bilayer model [71], the mosaic model [72], and the mosaic pudding model [30, 73] (Figure 9 of 24
6). Aurbach’s analysis based on Raman, FTIR and XPS found that the SEI is a mixture of
various organic and inorganic substances, and that the inorganic-rich inner layer (in con-
tact with Li) and the organic-rich outer layer (in contact with the electrolyte) constitute the
structure
two-layer of structure
the SEI. The mosaic
of the model
SEI. The believes
mosaic modelthatbelieves
the SEIthat
on the
thesurface
SEI on of
thelithium
surfacemetal
of
is lithium
composed metal is composed of different lithium salts with mosaic-like morphology and
of different lithium salts with mosaic-like morphology and stacking, and its
inner layerand
stacking, is inorganic components,
its inner layer is inorganicand the outer and
components, layertheisouter
mainly organic
layer components.
is mainly organic
Incomponents.
recent years,Inbased
recent years, based on the application of cryo-transmission electron mi-
on the application of cryo-transmission electron microscopy, more
croscopy, more researchers believe that the structure of SEI occurs when some single crys-
researchers believe that the structure of SEI occurs when some single crystals of inorganic
tals of inorganic
lithium salts are lithium
dispersed saltsinare
andispersed
amorphous in anstructure,
amorphous andstructure, and the first-prin-
the first-principles density
ciples density
functional theory functional theory
calculations andcalculations
experiments and experiments
have proven that have proven that
amorphous amor-
regions and
phous
grain regions and
boundaries aregrain boundaries
the main routesareforthe main ion
lithium routes for lithium
transport [74].ion transport [74].

Figure6.6.SEI
Figure SEImodel:
model:(a)
(a) Multilayer
Multilayer model
model [71];
[71];(b)
(b)Mosaic
Mosaicmodel
model[72]; (c)(c)
[72]; Raisin pudding
Raisin model
pudding [30].
model [30].

Theregulation
The regulationofofthe
the electrolyte
electrolyte directly
directlyaffects
affectsthe
thecomposition
composition and
andstructure
structureof the
of the
anodes’SEI
anodes’ SEIand
andisisone
one of
of the
the simplest
simplest and
and most
mosteffective
effectiveways
waystotoimprove
improve thethe
SEI. The
SEI. The
designand
design anduse
useofofan
anartificial
artificial SEI
SEI can
can compensate
compensatefor forthe
theshortcomings
shortcomings ofof
natural
naturalSEISEI
andand
obtaina astable
obtain stableinterface
interfacestructure
structure and
and dendrite-free
dendrite-free lithium
lithiummetal
metalanode.
anode.

3.3.Recent
RecentProgress
Progress
3.1. ElectrolyteAdditives
3.1. Electrolyte Additives
TheFermi
The Fermilevel
levelofofLiLi metal
metal isis lower
lower than
than most
mostcommon
commonorganicorganicelectrolytes,
electrolytes, which
which
leadstotothe
leads theinevitable
inevitablereduction
reduction in in Li
Li salt
salt and
andsolvent
solventmolecules
moleculesonon the anode
the anode surface
surface to to
forma solid
form a solid electrolyteinterphase
electrolyte interphase(SEI).
(SEI).AsAsananimportant
importantcomponent
componentofofthe theelectrolyte,
electrolyte,the
theofuse
use of additives
additives can improve
can improve the the various
various properties
properties ofof anodesby
anodes byforming
formingSEI, SEI, changing
chang-
ing
the the solvated
solvated structure,
structure, or changing
or changing the electric
the electric double
double layer
layer structure
structure [75–78].
[75–78].
Differentfrom
Different fromgeneral
general electrolyte
electrolyte additives,
additives,carbon
carbonmaterials
materials have
haveelectronic
electronic conduc-
conduc-
tivityand
tivity andcan
canpromote
promotelithium
lithium metal
metal nucleation
nucleationwhen whenused usedasasadditives.
additives. Cheng
Cheng et al. [79][79]
et al.
usedoctadecylamine-treated
used octadecylamine-treatednanodiamondsnanodiamondsasasadditives additivesinin lithium
lithium metal
metal batteries.
batteries. Nan-
Nanodiamonds
odiamonds withdiffusion
with low low diffusion barriers
barriers provide
provide nucleation
nucleation sites
sites forfor
LiLi metal,inducing
metal, inducingthe
the uniform
uniform deposition
deposition of Li of metal.
Li metal.TheThenanodiamond-decorated
nanodiamond-decorated electrolyte electrolyteenables
enables stable
stable
cycling of Li|Li symmetric cells at 2.0 mA cm and
−2 − 2 1.0
cycling of Li|Li symmetric cells at 2.0 mA cm and 1.0 mA cm for 150 h and mA cm −2 for− 150
2 h and 200 h, 200
re- h,
spectively. A Coulombic efficiency of 96% was obtained in Li|Cu
respectively. A Coulombic efficiency of 96% was obtained in Li|Cu cells. The addition cells. The addition of
surfactants is bound to affect the battery. Hu et al. [80] added graphene
of surfactants is bound to affect the battery. Hu et al. [80] added graphene quantum quantum dots into
the into
dots electrolyte to continuously
the electrolyte control thecontrol
to continuously growththe morphology of lithium metal.
growth morphology Graphene
of lithium metal.
quantum dots with a smaller size can be uniformly dispersed in
Graphene quantum dots with a smaller size can be uniformly dispersed in the electrolyte the electrolyte without
modification.
without modification.

3.2. Separator Modification

In lithium batteries, the separator mainly functions to separate the electrodes and
allow the electrolyte to pass through. It is a simple and valuable direction to improve
lithium metal battery performance by modifying separators. Coating carbon materials
on the separator surface is a simple and effective strategy. Carbon materials with higher
mechanical strength has an inhibitory effect on dendrite growth. In addition, the porous
carbon material with high specific surface area can control the lithium ions passing through
the separator to be uniformly redistributed and, thus, deposit uniformly on the electrode
Batteries 2022, 8, 246 10 of 24

surface. For example, Xu et al. [81] used carbon nanosheet coatings with cubic cavities to
suppress dendrite growth (Figure 7a,b). Connected cubic carbon channels enable stable
Li metal battery cycling by modulating Li deposition behavior. Li|Li symmetric cells
cycled for over 2600 h at 6 mA cm−2 and 2 mA h cm−2 , while Li|Cu cells achieved an
average Coulombic efficiency of 98.5% at 2 mA cm−2 and 2 mA h cm−2 . Li et al. [82]
coated a thin layer of ultra-strong diamond-like carbon (DLC) on the negative side of the
polypropylene (PP) separator (Figure 7c). The coating not only has a high modulus t to
inhibit the growth of lithium dendrites but also undergoes in situ chemical lithiation with
lithium metal in the battery, transforming into an excellent three-dimensional lithium ion
conductor to redistribute lithium ion flux. The dual role of the DLC/PP separator enables
the Li|Li symmetric cell to achieve stable cycling for over 4500 h at a current density of
3 mA cm−2 . Wang et al. [83] coated carbon fibers on the surface of separators for lithium
metal batteries. The presence of carbon fibers improves the spatial electric field on the Li
metal electrode surface and effectively suppresses the tip effect during dendrite growth.
This study also provides new insights into the mechanism of action of carbon materials to
modify the separator.
There are a large number of functional groups on the surface of carbon nanomate-
rials such as graphene oxide, and chemical reactions can be used to modify or modify
these functional groups to obtain materials with specific functions. Li et al. [25] coated
polyacrylamide-grafted graphene oxide nanosheets (GO-g-PAM) on one side of a commer-
cial PP separator (Figure 7d). The robust GO backbone improves the mechanical strength,
and the brush-like PAM chains on the graphene oxide surface contain a large number
of polar groups such as C=O, N-H, etc., which provide functions for the efficient adhe-
sion and uniform distribution of Li ions at the molecular level. Furthermore, the gaps
between the stacked 2D molecular brushes provide a fast pathway for electrolyte diffusion.
Liu et al. [84] coated the surface of the separator with functionalized nanocarbons modified
with lithium p-benzenesulfonate groups and stabilized the deposition of lithium metal
by inducing the opposite growth of lithium dendrites from the current collector and the
separator (Figure 7e). In Li|LFP coin cells, this method can achieve long-term stable cycling
(800 cycles with 80% initial capacity retention and 97% Coulombic efficiency).

3.3. Artificial SEI

The native SEI on the surface of Li metal electrodes is often difficult to adapt to the
huge volume changes and electrochemical reactions of the electrodes during cycling. An
artificial SEI used in situ and ex situ was designed to obtain a more stable interface structure.
Carbon materials have good mechanical strength and good chemical/electrochemical
stability. Carbon materials with different structures and their composites are designed as
an artificial SEI to stabilize the electrode–electrolyte interface.
Cui et al. [37] used a monolayer of interconnected amorphous hollow carbon nanospheres
as an artificial SEI layer to cover the Li metal surface (Figure 8a,b). The highly insulating
top surface of the hollow carbon nanospheres promotes the deposition of metallic Li under
the carbon nanospheres. The carbon layer as SEI can easily adapt to the volume change of
Li metal during cycling. The Li|Cu half-cell assembled with ether electrolyte maintained a
Coulombic efficiency of 99% for 150 cycles at a current density of 1 mA cm−2 and an areal
capacity of 1 mA h cm−2 .
Graphene has excellent mechanical properties. The presence of defects and functional
groups gives it excellent processability properties. Graphene and its derivatives or compos-
ites have received extensive attention as strategies for artificial SEI-stabilized lithium metal
anodes [85–87]. Zhou et al. [88] covered the Li metal surface with several layers of parallel
aligned graphene (Figure 8c). Flexible graphene films can adapt to the volume change of
lithium metal during cycling. The Li|Li symmetric cell with this artificial SEI can operate
for 1000 h at a current density of 5 mA cm−2 and a deposition capacity of 2.5 mA h cm−2 .
Batteries 2022, 8, 246 11 of 24
Batteries 2022, 8, x FOR PEER REVIEW 11 of 26

Figure 7. (a) Schematic illustration of Li-ion deposition in batteries with pristine separators or
7. (a) Schematic
FigureCNCC-coated illustration of Li-ion deposition in batteries with pristine separators or CNCC-
separators. (b) SEM and TEM images of the CNCC coating [81]. (c) Schematic illus-
coated tration of Li dendrite growth
separators. (b) SEM andinTEM
pristine PP andof
images LMB
thebased
CNCC on DLC/PP
coating separator [82].
[81]. (c) (d) Schematic
Schematic illustration of Li
illustration of Li ion deposition on electrodes with microscopic surface roughness [25].
dendrite growth in pristine PP and LMB based on DLC/PP separator [82]. (d) Schematic illustration (e) Growth
of dendrites in blank cells and FNC cells [84].
of Li ion deposition on electrodes with microscopic surface roughness [25]. (e) Growth of dendrites
in blank3.3.cells
Artificial
and SEI
FNC cells [84].
The native
Benefiting from SEIthe
on the surface
simple of Li metal electrodes
preparation processisandoftengood
difficult to adapt to the
modification properties of
huge volume changes and electrochemical reactions of the electrodes during cycling. An
graphene,
artificial SEI used in situ and ex situ was designed to obtain a more stable interface struc- collectors
a graphene artificial SEI combined with three-dimensional current
can provide higher
ture. Carbon Coulombic
materials have goodefficiency
mechanical for lithium
strength metal
and good batteries. Xie et al. [89] grew
chemical/electrochemical
stability. Carbon materials with different structures and
graphene on the surface of nickel foam by chemical vapor deposition(CVD), their composites are designed asand lithium
an artificial SEI to stabilize the electrode–electrolyte interface.
metal was uniformly deposited between the nickel foam and graphene (Figure 8d). The
Cui et al. [37] used a monolayer of interconnected amorphous hollow carbon nano-
graphene-based artificial SEI layer can inhibit the growth of dendrites and improve the
spheres as an artificial SEI layer to cover the Li metal surface (Figure 8a,b). The highly
cycling stability
insulating topof the battery.
surface Oncarbon
of the hollow this basis, Wangpromotes
nanospheres et al. [35] composited
the deposition graphene ox-
of me-
ide andtallic Li under thetocarbon
P(SF-DOL) formnanospheres.
an artificial The
SEIcarbon layer
layer. as SEI
The can easily
addition of adapt to the with Li-ion
polymers
volume change
conductivity provides of Li the
metal during cycling.
artificial The Li|Cu
SEI with half-cell
flexibility andassembled
Li-ion with ether elec- (Figure 8e).
conductivity
trolyte maintained a Coulombic efficiency of 99% for 150 cycles at a current density of 1
Combined with the three-dimensional copper foam current collector, the lithium metal bat-
mA cm−2 and an areal capacity of 1 mA h cm−2.
tery protected by this
Graphene artificialmechanical
has excellent SEI maintains an average
properties. The presenceCoulombic efficiency
of defects and of 99.1% over
functional
300 cycles
groups atgives
a current density
it excellent of 4.0 mA
processability h cm−2Graphene
properties. and a deposition capacity
and its derivatives of 2.0 mA cm−2
or com-
(Figureposites
8f). Inhave received extensive
addition, graphene attention
can alsoas strategies for artificial
be composited withSEI-stabilized
Prussian lithium
blue [90], LiF [91],
etc. asmetal anodes
artificial SEI [85–87].
layers Zhou et al. [88]dendrite-free
to obtain covered the Li metal surface
Li metal with several layers of
batteries.
parallel aligned graphene (Figure 8c). Flexible graphene films can adapt to the volume
change of lithium metal during cycling. The Li|Li symmetric cell with this artificial SEI
3.4. Current Collector Design
can operate for 1000 h at a current density of 5 mA cm−2 and a deposition capacity of 2.5
3.4.1. Lithium
mA h cm−2.Metal Anode Using Carbon Material as Current Collector
As anBenefiting
importantfromcomponent
the simple preparation
of lithiumprocess and good
batteries, modification
current properties
collectors not of
only play the
graphene, a graphene artificial SEI combined with three-dimensional current collectors
role ofcan
transferring electrons between active materials and external circuits but
provide higher Coulombic efficiency for lithium metal batteries. Xie et al. [89] grew
also diffuse
the heat generated inside the battery [92]. Meanwhile, the 3D current
graphene on the surface of nickel foam by chemical vapor deposition(CVD), and lithiumcollector design
can not only tolerate the huge volume change of Li metal during cycling but also achieve
uniform Li deposition by reducing the current density. The properties of current collectors
play an important role in the nucleation and deposition morphology of Li metal. Compared
with metal materials, carbon materials have the advantages of low specific gravity and
high abundance, as well as excellent electronic conductivity and lithiophilicity [93]. Thanks
to their good plasticity and modifiability, various scales and various functionalized carbon
materials were designed as current collectors for lithium metal batteries [94–98]. The large
specific surface area can effectively reduce the local current density. At the same time, the
lithiophilicity of carbon materials can be improved through surface modification to induce
the uniform deposition of lithium metal. According to the morphological characteristics
of the carbon material monomer, it can be divided into several categories from 0D to 3D.
 Batteries 2022, 8, x FOR PEER REVIEW 12 of 26

Batteries 2022, 8, 246 12 of 24

metal was uniformly deposited between the nickel foam and graphene (Figure 8d). The
graphene-based artificial SEI layer can inhibit the growth of dendrites and improve the
cycling stability of the battery. On this basis, Wang et al. [35] composited graphene oxide
Among andthem, 0D carbon
P(SF-DOL) to form anmaterials mainly
artificial SEI layer. include carbon
The addition spheres,
of polymers withcarbon nanoparticles,
Li-ion con-
carbonductivity
quantum provides
dots,the artificial
etc.; SEI with
1D carbon flexibility mainly
materials and Li-ion conductivity
include carbon (Figure 8e).
nanotubes, carbon
Combined
nanowires, carbonwith fibers,
the three-dimensional
etc.; 2D materialscopper mainly
foam current collector,
include the lithium
graphene, metal nanosheets,
carbon
battery
etc.; 3D protected
materials by thisinclude
mainly artificial SEI maintains
porous an average
carbon, Coulombic
aerogel, efficiency of 99.1% structures
and three-dimensional
over 300 cycles at a current density of 4.0 mA h cm–2 and a deposition capacity of 2.0 mA
built from various carbon materials. Studies using carbon of different dimensions as current
cm–2 (Figure 8f). In addition, graphene can also be composited with Prussian blue [90], LiF
collectors are summarized
[91], etc. as and tolisted
artificial SEI layers obtainin Table 1. Li metal batteries.
dendrite-free

Figure 8. (a) Schematic illustration of the deposition of lithium metal in the presence of a stable SEI
8. (a)created
Figurelayer Schematic illustration of the deposition of lithium metal in the presence of a stable SEI
by the hollow carbon nanosphere layer-modified copper substrate. (b) SEM image of
hollow carbon
layer created by the nanospheres after initial
hollow carbon SEI formation
nanosphere [37]. (c) Morphological
layer-modified copperchanges and schematic
substrate. (b) SEM image of
hollow carbon nanospheres after initial SEI formation [37]. (c) Morphological changesonand schematic
diagrams of graphene films on Li metal anodes [88]. (d) Schematic illustration of Li deposition
bare copper foil, nickel foam, and 3D graphene@Ni foam. (e) Schematic illustration of molecular-
diagrams
levelof graphene
design films on Li metal
of polymer-inorganic anodes
SEI using [88].
reactive (d) Schematic
polymer composites illustration of Liofdeposition on
[89]. (f) Efficiency
Li|Cu foil,
bare copper 3D cells with foam,
nickel RPC artificial
and 3D SEIgraphene@Ni
protection at a capacity
foam. of mA h cm−2 [35].
(e)4.0Schematic illustration of molecular-level
design of polymer-inorganic SEI using reactive polymer composites [89]. (f) Efficiency of Li|Cu 3D
3.4. Current Collector Design
cells with RPC artificial SEI protection at a capacity of 4.0 mA h cm−2 [35].
3.4.1. Lithium Metal Anode Using Carbon Material as Current Collector
As an important component of lithium batteries, current collectors not only play the
Table 1. Performance
role of lithium
of transferring electronsmetal batteries
between using carbon
active materials materials
and external as current
circuits but alsocollectors.
dif-
fuse the heat generated inside the battery [92]. Meanwhile, the 3D current collector design
can not only tolerate Half
the huge
Cellvolume change of Li metal
Performance during cycling
Operating but also achieve
Conditions
Current Collectoruniform Li deposition by reducing the current density. The properties
(Current Density/mA ·cm−2collectors
of current , Reference
(Cycle Number/h, CE) −2 )
play an important role in the nucleation and deposition morphology of Li
Areal Capacity/mA h · cmmetal. Com-
pared with metal materials, carbon
Au@hollow carbon sphere 300, 98%materials have the advantages
0.5,of1 low specific gravity [52]
S-doped carbon nanospheres 220, −97.5 % 0.5, 1 [99]
0D Nitrogen-doped hollow porous carbon spheres 270, 98.5% 1, 1 [100]
hollow carbon spheres modified with evenly
400, 98.4% 1, 1 [101]
dispersed Ni2 P nanoparticles
graphitic carbon tubes 350, 99.3% 0.5, 1 [102]
hollow carbon fiber 350, 99.5% 0.5, 2 [103]
Lotus-root-like Ni–Co hollow prisms@carbon fibers 250, 98% 3, 1 [104]
1D
Li/carbon nanotube hybrid 150, 95% 1, 0.5 [105]
hollow carbon fiber 350, 99.5 0.5, 2 [106]
oxygen-rich carbon nanotube 200, 99% 2, 1 [107]
Batteries 2022, 8, 246 13 of 24

Table 1. Cont.

layered reduced graphene oxide - - [108]

oxygen-codoped vertical carbon nanosheet arrays 325, 98% 0.5, 1 [109]
2D
S-doped graphene 180, 98.23% 1, 0.5 [110]
3D fluorine-doped graphene 150, 98% 2, 1 [111]
Nitrogen-doped amorphous Zn–carbon
800, 98% 1, 1 [112]
multichannel fibers decorated with carbon cages
3D
Au nanoparticles@graphene hybrid aerogel 175, 91.2% 1, 1 [113]
Carbon nanofiber-stabilized graphene aerogel film 100, 98.5% 3, 1 [114]

Although different morphologies of carbon materials can be used as current collectors

for lithium metal electrodes, in order to obtain large specific surface area and porosity, most
strategies are to design materials into 3D structures. The 3D carbon structure provides a
larger specific surface area to reduce local current density, higher porosity, and mechanical
strength to accommodate the volume change in Li metal during deposition and exfoliation.
Infusion of molten lithium metal into 3D current collectors is the most common method,
but this also requires the current collector itself to have a certain lithiophilicity [115].
Lin et al. [108] obtained graphene oxide films with good lithiophilicity through Li-assisted
reduction vacuum filtration and then injected molten lithium into the uniform nano-gap
of the graphene films (Figure 9a). The layered graphene can not only adapt to the huge
volume change of Li metal but also stabilize the deposition and interface structure of Li
metal. The mass fraction of graphene in the electrode is only 7%, which ensures the high
specific capacity of the electrode.
In addition to the simple use of carbon materials to build 3D conductive frameworks,
the modification of carbon materials and their surfaces can obtain current collector materials
with special functions. Modification methods mainly include: doping, deposition, and
chemical group modification.
Doping is a common means of modifying carbon materials. Elements such as N, O,
and S can be doped into carbon materials to improve their lithiophilicity. Zhang et al. [116]
designed a N, S co-doped ordered mesoporous carbon nanospheres as a deposition sub-
strate for Li metal electrodes. The experimental and computational results show that the
synergistic effect of N/S double doping enhances the surface electronegativity of the carbon
spheres and lowers the nucleation energy barrier of Li-Au on the surface of the carbon
spheres, enabling uniform nucleation in the initial stage, thereby inducing branch-free
crystalline Li deposition. At the same time, N and S elements also help to form a more
stable SEI layer, which prolongs the cycle life (400 h) of lithium metal symmetric batteries
at high current density (20 mA h cm−2 ).
In addition to doping, loading lithiophilic metal materials on the surface of carbon
materials can induce nucleation and reduce overpotential [117,118]. Li et al. [119] and
Tian et al. [120] coated the carbon cloth with Au and Ag layers, respectively, and then
placed the metal-coated side away from the separator when assembling the battery. Lithium
metal preferentially nucleates and grows at the metal coating during deposition. At the
same time, the upper part of the porous skeleton of the carbon cloth also provides enough
space to buffer the volume expansion of metallic lithium.
There are a large number of active functional groups on the surface of carbon materials
such as graphene oxide and carbon nanotubes. Using these active sites to design chemical
reactions can obtain carbon materials with specific functions. For example, Gao et al. [121]
introduced benzenesulfonyl fluoride molecules on the surface of reduced graphene oxide
aerogels (Figure 9b). During the metal deposition process, the labile molecules not only gen-
erate metal-coordinated benzenesulfonate anions to guide homogeneous metal deposition
but also introduce lithium fluoride into the SEI to improve the SEI composition on the Li
surface. High-efficiency lithium deposition with low nucleation overpotential is achieved
at a current density of 6.0 mA cm−2 . Niu et al. [106] designed a lithium anode structure
Batteries 2022, 8, 246 14 of 24

based on an amine-functionalized mesoporous carbon fiber framework (Figure 9c). The

introduction of amine groups enhanced the wettability of carbon fibers to lithium metal,
which enabled the smooth deposition of lithium metal on the surface of carbon fibers.
The
Batteries 2022, 8, x FOR PEER full cell assembled with this anode can maintain stable cycling for 200
REVIEW cycles
15 of 26 at a low
N/P ratio (< 2).

Figure 9. (a) Preparation of the layered Li-rGO composite film [108]. (b) Schematic illustration of the
9. (a) Preparation
Figurestabilized of the
lithium deposition layered
interface usingLi-rGO
the activecomposite film benzenesulfonyl
organic molecule [108]. (b) Schematic
fluoride illustration
of the (BSF) [121]. (c)
stabilized Schematic
lithium illustration interface
deposition of the self-smoothing
using the behavior
activeoforganic
the lithium–carbon
moleculeanode
benzenesulfonyl
[106].
fluoride (BSF) [121]. (c) Schematic illustration of the self-smoothing behavior of the lithium–carbon
anode [106]. It is worth noting that either excess Li metal or excessively heavy current collectors
will weaken or even offset the advantages of Li metal’s high specific energy. Therefore,
Itthe
is design
worthofnoting
thin andthat
light either
and lithium-lean/lithium-free
excess Li metal oranodes has practical
excessively heavy application
current collectors
value. The
will weaken ordesign
evenofoffset
the 3D the
current collector is one
advantages of of
Lithe most widely
metal’s highused and promising
specific energy. Therefore,
solutions
the design for carbon
of thin materials
and light andinlithium-lean/lithium-free
lithium metal batteries. anodes has practical application
value. 3.4.2.
The Graphite–Lithium
design of the 3D current
Metal collector
Composite is one of the most widely used and promising
Electrode
solutions for carbon materials in lithium metal
In recent years, a graphite-lithium metal composite batteries.
electrode was proposed to sim-
ultaneously obtain the intercalation capacity of the graphite anode and the conversion
3.4.2. Graphite–Lithium
capacity of the lithiumMetal metal Composite
by depositingElectrode
a certain amount of lithium metal on the
graphite electrode [122]. The
In recent years, a graphite-lithium use of 3D porous
metalgraphite
composite hostselectrode
is expectedwas to alleviate
proposedthe to simulta-
volume expansion and dendrite growth problems of Li metal. Compared with the general
neously obtain the intercalation capacity of the graphite anode and the conversion capacity
lithium metal anodes using metal or carbon materials as current collectors, LiC 6 formed
of theby lithium
graphitemetal by depositing
intercalation is consideredatocertain
have goodamount of lithium
lithiophilicity metal metal
[123]. Lithium on the graphite
can obtain
electrode [122].lower
The nucleation
use of 3D overpotential on the surface
porous graphite hostsofisLiC 6 , resulting
expected toinalleviate
more uni- the volume
form deposition.
expansion and dendrite In addition,
growth theproblems
current collector
of Li material
metal. occupies
Compared morewith
mass the
and general
vol- lithium
ume in the electrode, which weakens the advantage of the high specific volume of the
metal anodes using metal or carbon materials as current collectors, LiC6 formed by graphite
metal lithium electrode. The use of graphitized carbon materials with lithium intercalation
intercalation is considered
ability combined with lithiumto have
metal isgood lithiophilicity
expected [123].limitation
to break the capacity Lithium metal can obtain
of graph-
lower ite anodes and
nucleation provide electrodes
overpotential withsurface
on the higher effective
of LiC6capacity.
, resulting It isin
worth
morenoting that deposition.
uniform
ordinary
In addition, lithium
the currentmetal batteries often
collector use anoccupies
material excess of lithium
more massmetal as andthevolume
negative elec-
in the electrode,
whichtrode,
weakensthereby ignoring
the the volume/mass
advantage of the highratiospecific
of the negative
volumeelectrode
of the in the battery.
metal The electrode.
lithium
lithium-free design of the composite anode is expected to improve the specific capacity of
The use of graphitized carbon materials with lithium intercalation ability combined with
the full cell. From a practical point of consideration, the graphite–lithium metal composite
lithium metal uses
electrode is expected
a commercialto break theanode
graphite capacity
as the limitation of graphite
lithium deposition substrateanodes
withoutand provide
changing
electrodes withthehigher
existing production
effective process.
capacity. Graphite has the advantages
It is worth noting that of high abundance
ordinary lithium metal
and often
batteries low cost,
useandantheexcess
use of graphite as themetal
of lithium deposition
as the substrate of lithium
negative metal has
electrode, high
thereby ignoring
the volume/mass ratio of the negative electrode in the battery. The lithium-free design
of the composite anode is expected to improve the specific capacity of the full cell. From
a practical point of consideration, the graphite–lithium metal composite electrode uses
a commercial graphite anode as the lithium deposition substrate without changing the
existing production process. Graphite has the advantages of high abundance and low cost,
Batteries 2022, 8, 246 15 of 24

and the use of graphite as the deposition substrate of lithium metal has high application
feasibility. The design of the composite electrode is actually a compromise between the
advantages and disadvantages of graphite and lithium metal. The specific capacity of
graphite is improved while maintaining the stability and safety.
Although graphite-lithium metal composite anodes have many advantages compared
with graphite anodes or lithium metal anodes, they also face many difficulties and chal-
lenges. Graphite was intensively researched and widely used as a mature lithium-ion
battery anode. After Li metal is deposited on the graphite surface, the excess Li coating
quickly fails in common carbonate-based electrolytes, resulting in a rapid decrease in
battery capacity [124].
Graphitized carbon materials with various structures and functions have begun to
be used as active substrates for lithium metal. These graphitic materials mainly function
as 3D current collectors in electrodes [125]. A composite electrode with a higher capacity
was obtained by depositing lithium metal into the voids of artificial graphite by Cui et al.
(Figure 10a) [126]. Wan et al. [125] deposited Li metal on a 3D framework wrapped by
graphitized carbon spheres, and the full cell assembled with LiFePO4 achieved a lifespan of
1000 cycles using an anode with 5% Li pre-deposited by electrochemistry. Zuo et al. [127]
reported that the graphitized carbon fiber electrode can be used as a multifunctional 3D
current collector to enhance the lithium storage capacity. Intercalation and electrode-
position
Batteries 2022, 8, x FOR PEER REVIEW
reactions can provide areal capacities up to 8 mA h cm−2 without
17 of 26
significant
dendrite formation.

Figure 10. (a) Voltage variation of Li metal deposition in bulk artificial graphite [126]. (b) Schematic
Figure 10.and(a) Voltage
specific energyvariation of Li
of the hybrid metal deposition
Li-ion/Li-metal in bulk
battery [122]. artificial graphite
(c,d) Characterization [126]. (b) Schematic
of the mor-
phological
and specific energyevolution
of theofhybrid
lithium intercalation and electroplated
Li-ion/Li-metal batterygraphite
[122]. electrodes. (e) Electrochem- of the morpho-
(c,d) Characterization
ical performance of the lithium–graphite composite battery with localized highly concentrated elec-
logical evolution
trolyte [128].of
(f)lithium
Schematicintercalation
illustration of theand
effectselectroplated
of NG and BMG graphite
structures onelectrodes.
Li deposition (e)
and Electrochemical
carbon of
performance structure evolution [129].
the lithium–graphite composite battery with localized highly concentrated elec-
trolyte [128].The(f) focus
Schematic illustration of the effects of NG and BMG structures on Li deposition and
of graphite–lithium metal composite anode research is on the construction
of stable SEI and the maintenance
carbon structure evolution [129]. of battery capacity. In order to construct a more robust
SEI, Wu et al. [131] obtained a graphite–lithium metal composite anode with a longer cycle
life by coating PVDF on the surface of the graphite electrode. By changing the carbon ma-
trix or electrolyte, a uniform and stable in situ SEI can be effectively constructed. Wang et
al. [132] fluorinated the edge of mesocarbon microspheres to obtain an LiF-rich stabilized
SEI. Benefiting from the extensive research on lithium metal anodes in recent years, elec-
trolyte systems suitable for lithium metal anodes were also used in graphite–lithium metal
Batteries 2022, 8, 246 16 of 24

However, the research on graphite–lithium metal electrodes often ignores the capacity
contribution of graphite itself, which also makes the volume-specific energy advantage
of composite anodes not effectively utilized. In recent years, Dahn et al. [122] proposed
the concept of lithium ion–lithium metal composite batteries. They believe that the use
of graphite–lithium metal composite anode can increase the volume energy density of
the anode from 530 W h L−1 to 890 W h L−1 (Figure 10b). However, the composite
anode used by Dahn mainly deposits lithium on the surface of graphite to form a double-
layer structure, and no further studies on the distribution of lithium were carried out.
Zhang et al. [128] explored the boundary values for Li plating on graphite (Figure 10c–e).
Combined with thermal monitoring, SEM, TOF-SIMS, and other characterizations, the
properties of graphite–lithium metal electrodes with different lithium contents were tested.
Their results show that the electrode surface has the most uniform lithium distribution
when depositing lithium metal with a graphite capacity of 25%. Of course, the boundary
value is affected by many conditions such as temperature, magnification, porosity, etc., and
more work is needed to verify.
From a material point of view, reducing the particle size of graphite is considered
to be more effective to obtain a more stable structure and a larger specific surface area
(Figure 10f) [129]. The study of Chen et al. [124] showed that the capacity attenuation of
graphite–lithium metal composite anodes mainly comes from the accumulation of dead
lithium and the decrease in graphite capacity. The results of in situ X-ray microtomography
analysis also confirmed this statement [130]: the main reason for the decrease in capacity
after lithium deposition from graphite is that the graphite under the lithium metal layer is
affected by mass transfer and cannot achieve the effective intercalation of lithium ions.
The focus of graphite–lithium metal composite anode research is on the construction of
stable SEI and the maintenance of battery capacity. In order to construct a more robust SEI,
Wu et al. [131] obtained a graphite–lithium metal composite anode with a longer cycle life
by coating PVDF on the surface of the graphite electrode. By changing the carbon matrix or
electrolyte, a uniform and stable in situ SEI can be effectively constructed. Wang et al. [132]
fluorinated the edge of mesocarbon microspheres to obtain an LiF-rich stabilized SEI.
Benefiting from the extensive research on lithium metal anodes in recent years, electrolyte
systems suitable for lithium metal anodes were also used in graphite–lithium metal anodes.
Lithium salts such as LiBF2 (C2 O4 )- LiBF4 [122], LiFSI [124,133] were used in composite
electrodes and obtained more stable SEI and higher Coulombic efficiency. Zhang et al. [128]
used a localized highly concentrated electrolyte to promote more uniform Li deposition,
and the full cell matching NCM532 achieved a capacity retention of 80.2% after 500 cycles.

3.5. Carbon Materials in Solid-State Batteries

In lithium metal solid-state batteries, especially inorganic ceramic solid-state batteries,
the solid–solid contact between the electrolyte and the two electrodes is poor, and some elec-
trolyte materials have poor compatibility and affinity with lithium metal. In order to obtain
a stable structure, the use of carbon materials as interface layers or current collectors can
improve the interface stability and affinity of lithium metal anodes with solid electrolytes.
Feng et al. [134] obtained a pure air-stable surface on Li6.75 La3 Zr1.75 Ta0.25 O12 (LLZTO) by
thermal decomposition vapor deposition (TVD) (Figure 11a). Benefiting from the amor-
phous structure of low graphitized carbon (LGC), instantaneous lithiation is achieved,
and the impedance of the Li/LLZTO interface is reduced to 9 Ω cm−2 . Chen et al. [135]
carbonized a mixture of phenolic resin and polyvinyl butyral on the surface of LLZTO to
obtain a porous hard carbon layer (Figure 11b). The multi-layered pore structure of the
hard carbon layer provides capillary force and large specific surface area, which, coupled
with the chemical reactivity of the carbon material with Li, facilitates the penetration of
molten Li with the garnet electrolyte. The Li/LLZTO interface exhibits a low interfacial
resistance of 4.7 Ω cm−2 and a higher critical current density at 40 ◦ C. Lee et al. [136] mixed
silver and carbon nanoparticles to make anodes, and during the deposition and exfoliation
of Li metal, the silver and carbon nanoparticles moved away from the electrolyte and closer
Batteries 2022, 8, 246 17 of 24

to the electrolyte, respectively (Figure 11c). The gradient electrode structure provides both
nucleation sites and interfacial protection layers for Li metal deposition. The pouch cells
assembled with silver pyroxene Li6 PS5 Cl exhibited high energy density (900 W19hofl−
Batteries 2022, 8, x FOR PEER REVIEW
1
26 ) and
superior cycle life (1000 cycles, Coulombic efficiency 99.8%).

Figure 11. (a) Amorphous low graphitized carbon stabilized Li/LLZTO interface [134]. (b) Li/LLZTO
Figure 11. (a) Amorphous low graphitized carbon stabilized Li/LLZTO interface [134]. (b) Li/LLZTO
interface stabilized by the porous hard carbon layer [135]. (c) Schematic illustration of the role of the
interface stabilized by the
Ag-C nanocomposite porous
layer on thehard carbon
current layerto[135].
collector (c) the
stabilize Schematic illustration
Li coating of the role
during charging and of the
Ag-Cdischarging [136]. (d)layer
nanocomposite Comparison
on the of the interfacial
current collectorbehavior of LLZTO
to stabilize with
the Li pure Liduring
coating and Li-C [137]. and
charging
(e) Schematic
discharging illustration
[136]. of the deposition
(d) Comparison process onbehavior
of the interfacial Li metal and 3D composite
of LLZTO anode
with pure Li in
andanLi-C
all- [137].
solid-state Li metal battery [138].
(e) Schematic illustration of the deposition process on Li metal and 3D composite anode in an
all-solid-state Li metal battery [138].
The main problem in organic polymer electrolytes is their low electrical conductivity.
Adding fillers can effectively reduce the crystallinity of the electrolyte and improve the
In addition, graphite–lithium metal composite electrodes can also be designed using
conductivity. Materials such as graphene [139,140] and carbon quantum dots [141] as fill-
theers
lithiophilic properties
added to polymer of graphite
electrolytes can in solid-state batteries.
simultaneously improve the Duan et al. [137]
mechanical cast a mixed
properties
slurry of lithium metal and graphite into
and electrical conductivity of the electrolytes. a pole piece and applied it in an LLZO electrolyte
battery (Figure 11d). The graphite–lithium metal composite electrode can effectively
4. Summary
improve and Outlook
the affinity with the solid electrolyte and reduce the interfacial impedance.
Comparedgraphite
Integrating with otherdirectly
materials,
intocarbon materials
solid-state are unique can
electrolytes in the field of
utilize theenergy
interstitial
storage
spaces due to their
between low cost,
graphite andcontrollable microstructure,
ceramic particles tunable
to store electrical
lithium conductivity,
metal. Furthermore,
theand modifiablenegative
lithium-free surface structure.
electrodeDiverse
designcarbon materials
can also obtainhavehighplayed a huge
specific role inbatter-
energy
ies.lithium
Ping Liu metal batteries.
et al. Lithium
[138] mixed metal batteries
graphite into theusing carbon
sulfide solidmaterials as current
electrolyte, and the collec-
resulting
tors can effectively
composite anode could reduce the current
effectively density the
alleviate and infiltration
disperse heat.ofFor the modified
lithium metal in carbon
the lattice
gapmaterial, it will short
and prevent also have the effect
circuits of regulating
(Figure 11e). Thethe nucleation
critical current anddensity
growthof of the
lithium
electrode
metal. In particular, graphitized carbon
increases and the interface resistance decreases. materials can be used as a deposition substrate to
effectively improve the coulombic efficiency of the anode. The use of carbon materials as
The main problem in organic polymer electrolytes is their low electrical conductivity.
additives or artificial SEI in lithium metal batteries can achieve the role of stabilizing the
Adding fillers can effectively reduce the crystallinity of the electrolyte and improve the
interface layer. In solid-state batteries, carbon materials as interface layers can improve
conductivity.
the wettabilityMaterials such
of lithium as graphene
metal [139,140]
and electrolyte and carbon
and increase quantum
the ultimate dots [141]
exchange as fillers
current
added
density. We summarize the application and research of carbon materials in lithium metal and
to polymer electrolytes can simultaneously improve the mechanical properties
electrical
batteries conductivity
in recent years.of the electrolytes.
These works explore the possibilities of carbon materials from
various angles. Combined with our reflections on current research, we make some empir-
ical recommendations:
Batteries 2022, 8, 246 18 of 24

4. Summary and Outlook

Compared with other materials, carbon materials are unique in the field of energy
storage due to their low cost, controllable microstructure, tunable electrical conductivity,
and modifiable surface structure. Diverse carbon materials have played a huge role in
lithium metal batteries. Lithium metal batteries using carbon materials as current collectors
can effectively reduce the current density and disperse heat. For the modified carbon
material, it will also have the effect of regulating the nucleation and growth of lithium
metal. In particular, graphitized carbon materials can be used as a deposition substrate to
effectively improve the coulombic efficiency of the anode. The use of carbon materials as
additives or artificial SEI in lithium metal batteries can achieve the role of stabilizing the
interface layer. In solid-state batteries, carbon materials as interface layers can improve
the wettability of lithium metal and electrolyte and increase the ultimate exchange cur-
rent density. We summarize the application and research of carbon materials in lithium
metal batteries in recent years. These works explore the possibilities of carbon materials
from various angles. Combined with our reflections on current research, we make some
empirical recommendations:
1. When introducing carbon materials into the design of lithium metal batteries, the neg-
ative effects of carbon materials, such as chemical/electrochemical stability, structural
stability, etc., should be considered at the same time.
2. When designing carbon-based three-dimensional current collectors, the effects of
porosity and specific surface area should be considered at the same time. The size of
porosity directly affects the mass transfer process of lithium ions: too large porosity
will weaken the advantages brought by the 3D structure, while too small porosity
will affect the mass transfer process of lithium ions in it. A large specific surface area
can achieve more uniform deposition by dispersing the local current density, but at
the same time, it will also increase the SEI film area and reduce the first effect and
Coulomb efficiency of the battery.
3. The lithium metal foil used in the laboratory test is generally thick. The excessive
lithium metal and electrolyte greatly prolong the failure time of the battery. When con-
ducting battery tests, the experimental conditions should be scientifically controlled
in order to truly reflect the role of materials in the battery.
4. Pay attention to the overall specific capacity of the battery. Excess lithium metal will
reduce the actual specific capacity of the battery. The use of carbon materials can
improve the cycle stability and battery life of lithium metal batteries to a certain extent.
However, the mass and volume of carbon materials themselves are often overlooked.
Controlling the lithium–carbon ratio is particularly important to ensure the specific
capacity of the battery.
5. The experiment is established on the basis of the full cell, and its feasibility is verified
with a pouch cell or a cylindrical cell.
With the advancement of materials science and the development of nanotechnology,
carbon materials are increasingly incorporated into various battery systems and are success-
fully applied. With the unremitting efforts of mankind, carbon materials will also provide
a strong boost to the development of lithium metal batteries.

Author Contributions: Z.W (Zeyu Wu) drafted the majority of this review paper. K.S. and Z.W.
(Zhenhua Wang) were involved in the editing and literature-screening efforts. All authors participated
in writing the manuscript and discussing the contents to be included in this review. All authors have
read and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: The data presented in this study are available on request from the
corresponding authors.
Conflicts of Interest: The authors declare no conflict of interest.
Batteries 2022, 8, 246 19 of 24

References
1. Gür, T.M. Review of electrical energy storage technologies, materials and systems: Challenges and prospects for large-scale grid
storage. Energy Environ. Sci. 2018, 11, 2696–2767. [CrossRef]
2. Goodenough, J.B.; Kim, Y. Challenges for Rechargeable Li Batteries. Chem. Mater. 2010, 22, 587–603. [CrossRef]
3. Dunn, B.; Kamath, H.; Tarascon, J.M. Electrical Energy Storage for the Grid: A Battery of Choices. Science 2011, 334, 928–935.
[CrossRef] [PubMed]
4. Winter, M.; Barnett, B.; Xu, K. Before Li Ion Batteries. Chem. Rev. 2018, 118, 11433–11456. [CrossRef] [PubMed]
5. Li, M.; Lu, J.; Chen, Z.; Amine, K. 30 Years of Lithium-Ion Batteries. Adv. Mater. 2018, 30, 1800561. [CrossRef]
6. Armand, M.; Tarascon, J.M. Building better batteries. Nature 2008, 451, 652–657. [CrossRef]
7. Tarascon, J.M.; Armand, M. Issues and challenges facing rechargeable lithium batteries. Nature 2001, 414, 359–367. [CrossRef]
8. Liu, W.; Oh, P.; Liu, X.; Lee, M.J.; Cho, W.; Chae, S.; Kim, Y.; Cho, J. Nickel-rich layered lithium transition-metal oxide for
high-energy lithium-ion batteries. Angew. Chem. Int. Ed. 2015, 54, 4440–4457. [CrossRef]
9. Choi, J.W.; Aurbach, D. Promise and reality of post-lithium-ion batteries with high energy densities. Nat. Rev. Mater. 2016,
1, 16013. [CrossRef]
10. Zhang, W.-J. A review of the electrochemical performance of alloy anodes for lithium-ion batteries. J. Power Sources 2011, 196,
13–24. [CrossRef]
11. Lin, D.; Liu, Y.; Cui, Y. Reviving the lithium metal anode for high-energy batteries. Nat. Nanotechnol. 2017, 12, 194–206. [CrossRef]
[PubMed]
12. Guo, Y.; Li, H.; Zhai, T. Reviving Lithium-Metal Anodes for Next-Generation High-Energy Batteries. Adv. Mater. 2017, 29, 1700007.
[CrossRef] [PubMed]
13. Zu, C.-X.; Li, H. Thermodynamic analysis on energy densities of batteries. Energy Environ. Sci. 2011, 4, 2614–2624. [CrossRef]
14. Albertus, P.; Babinec, S.; Litzelman, S.; Newman, A. Status and challenges in enabling the lithium metal electrode for high-energy
and low-cost rechargeable batteries. Nat. Energy 2018, 3, 16–21. [CrossRef]
15. Zhang, H.; Eshetu, G.G.; Judez, X.; Li, C.M.; Rodriguez-Martinez, L.M.; Armand, M. Electrolyte Additives for Lithium Metal
Anodes and Rechargeable Lithium Metal Batteries: Progress and Perspectives. Angew. Chem. Int. Ed. 2018, 57, 15002–15027.
[CrossRef]
16. Chen, S.R.; Zheng, J.M.; Mei, D.H.; Han, K.S.; Engelhard, M.H.; Zhao, W.G.; Xu, W.; Liu, J.; Zhang, J.G. High-Voltage Lithium-
Metal Batteries Enabled by Localized High-Concentration Electrolytes. Adv. Mater. 2018, 30, 1706102. [CrossRef]
17. Ren, X.D.; Zou, L.F.; Cao, X.; Engelhard, M.H.; Liu, W.; Burton, S.D.; Lee, H.; Niu, C.J.; Matthews, B.E.; Zhu, Z.H.; et al. Enabling
High-Voltage Lithium-Metal Batteries under Practical Conditions. Joule 2019, 3, 1662–1676. [CrossRef]
18. Qian, J.F.; Henderson, W.A.; Xu, W.; Bhattacharya, P.; Engelhard, M.; Borodin, O.; Zhang, J.G. High rate and stable cycling of
lithium metal anode. Nat. Commun. 2015, 6, 6362. [CrossRef]
19. Fan, X.L.; Chen, L.; Borodin, O.; Ji, X.; Chen, J.; Hou, S.; Deng, T.; Zheng, J.; Yang, C.Y.; Liou, S.C.; et al. Non-flammable electrolyte
enables Li-metal batteries with aggressive cathode chemistries. Nat. Nanotechnol. 2018, 13, 715–722. [CrossRef]
20. Suo, L.M.; Xue, W.J.; Gobet, M.; Greenbaum, S.G.; Wang, C.; Chen, Y.M.; Yang, W.L.; Li, Y.X.; Li, J. Fluorine-donating electrolytes
enable highly reversible 5-V-class Li metal batteries. Proc. Natl. Acad. Sci. USA 2018, 115, 1156–1161. [CrossRef]
21. Ding, F.; Xu, W.; Graff, G.L.; Zhang, J.; Sushko, M.L.; Chen, X.L.; Shao, Y.Y.; Engelhard, M.H.; Nie, Z.M.; Xiao, J.; et al.
Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism. J. Am. Chem. Soc. 2013, 135, 4450–4456.
[CrossRef]
22. Zhang, S.; Cheng, B.; Fang, Y.; Dang, D.; Shen, X.; Li, Z.; Wu, M.; Hong, Y.; Liu, Q. Inhibition of lithium dendrites and dead
lithium by an ionic liquid additive toward safe and stable lithium metal anodes. Chin. Chem. Lett. 2022, 33, 3951–3954. [CrossRef]
23. Zhang, W.D.; Tu, Z.Y.; Qian, J.W.; Choudhury, S.; Archer, L.A.; Lu, Y.Y. Design Principles of Functional Polymer Separators for
High-Energy, Metal-Based Batteries. Small 2018, 14, 1703001. [CrossRef] [PubMed]
24. Hao, X.M.; Zhu, J.; Jiang, X.; Wu, H.T.; Qiao, J.S.; Sun, W.; Wang, Z.H.; Sun, K.N. Ultrastrong Polyoxyzole Nanofiber Membranes
for Dendrite-Proof and Heat-Resistant Battery Separators. Nano Lett. 2016, 16, 2981–2987. [CrossRef] [PubMed]
25. Li, C.F.; Liu, S.H.; Shi, C.G.; Liang, G.H.; Lu, Z.T.; Fu, R.W.; Wu, D.C. Two-dimensional molecular brush-functionalized porous
bilayer composite separators toward ultrastable high-current density lithium metal anodes. Nat. Commun. 2019, 10, 1363.
[CrossRef] [PubMed]
26. Jin, R.; Fu, L.X.; Zhou, H.L.; Wang, Z.Y.; Qiu, Z.F.; Shi, L.Y.; Zhu, J.F.; Yuan, S. High Li+ Ionic Flux Separator Enhancing Cycling
Stability of Lithium Metal Anode. ACS Sustain. Chem. Eng. 2018, 6, 2961–2968. [CrossRef]
27. Woo, S.G.; Hwang, E.K.; Kang, H.K.; Lee, H.; Lee, J.N.; Kim, H.S.; Jeong, G.; Yoo, D.J.; Lee, J.; Kim, S.; et al. High transference
number enabled by sulfated zirconia superacid for lithium metal batteries with carbonate electrolytes. Energy Environ. Sci. 2021,
14, 1420–1428. [CrossRef]
28. Liu, Y.J.; Tao, X.Y.; Wang, Y.; Jiang, C.; Ma, C.; Sheng, O.W.; Lu, G.X.; Lou, X.W. Self-assembled monolayers direct a LiF-rich
interphase toward long-life lithium metal batteries. Science 2022, 375, 739–745. [CrossRef] [PubMed]
29. Yang, Y.; Yao, S.Y.; Liang, Z.W.; Wen, Y.C.; Liu, Z.B.; Wu, Y.W.; Liu, J.; Zhu, M. A Self-Supporting Covalent Organic Framework
Separator with Desolvation Effect for High Energy Density Lithium Metal Batteries. ACS Energy Lett. 2022, 7, 885–896. [CrossRef]
30. Wu, H.; Jia, H.; Wang, C.; Zhang, J.G.; Xu, W. Recent Progress in Understanding Solid Electrolyte Interphase on Lithium Metal
Anodes. Adv. Energy Mater. 2020, 11, 2003092. [CrossRef]
Batteries 2022, 8, 246 20 of 24

31. Meyerson, M.L.; Papa, P.E.; Heller, A.; Mullins, C.B. Recent Developments in Dendrite-Free Lithium-Metal Deposition through
Tailoring of Micro- and Nanoscale Artificial Coatings. ACS Nano 2021, 15, 29–46. [CrossRef] [PubMed]
32. Fedorov, R.G.; Maletti, S.; Heubner, C.; Michaelis, A.; Ein-Eli, Y. Molecular Engineering Approaches to Fabricate Artificial
Solid-Electrolyte Interphases on Anodes for Li-Ion Batteries: A Critical Review. Adv. Energy Mater. 2021, 11, 2101173. [CrossRef]
33. Liu, K.; Pei, A.; Lee, H.R.; Kong, B.; Liu, N.; Lin, D.C.; Liu, Y.Y.; Liu, C.; Hsu, P.C.; Bao, Z.A.; et al. Lithium Metal Anodes with an
Adaptive "Solid-Liquid" Interfacial Protective Layer. J. Am. Chem. Soc. 2017, 139, 4815–4820. [CrossRef] [PubMed]
34. Tu, Z.Y.; Choudhury, S.; Zachman, M.J.; Wei, S.Y.; Zhang, K.H.; Kourkoutis, L.F.; Archer, L.A. Designing Artificial Solid-Electrolyte
Interphases for Single-Ion and High-Efficiency Transport in Batteries. Joule 2017, 1, 394–406. [CrossRef]
35. Gao, Y.; Yan, Z.F.; Gray, J.L.; He, X.; Wang, D.W.; Chen, T.H.; Huang, Q.Q.; Li, Y.G.C.; Wang, H.Y.; Kim, S.H.; et al. Polymer-
inorganic solid-electrolyte interphase for stable lithium metal batteries under lean electrolyte conditions. Nat. Mater. 2019, 18,
384–389. [CrossRef]
36. Cha, E.; Patel, M.D.; Park, J.; Hwang, J.; Prasad, V.; Cho, K.; Choi, W. 2D MoS2 as an efficient protective layer for lithium metal
anodes in high-performance Li-S batteries. Nat. Nanotechnol. 2018, 13, 337–344. [CrossRef]
37. Zheng, G.; Lee, S.W.; Liang, Z.; Lee, H.-W.; Yan, K.; Yao, H.; Wang, H.; Li, W.; Chu, S.; Cui, Y. Interconnected hollow carbon
nanospheres for stable lithium metal anodes. Nat. Nanotechnol. 2014, 9, 618–623. [CrossRef]
38. Lin, Z.; Ma, Y.; Wang, W.; He, Y.; Wang, M.; Tang, J.; Fan, C.; Sun, K. A homogeneous and mechanically stable artificial diffusion
layer using rigid-flexible hybrid polymer for high-performance lithium metal batteries. J. Energy Chem. 2022, 76, 631–638.
[CrossRef]
39. Han, Y.H.; Jie, Y.L.; Huang, F.Y.; Chen, Y.W.; Lei, Z.W.; Zhang, G.Q.; Ren, X.D.; Qin, L.J.; Cao, R.G.; Jiao, S.H. Enabling Stable
Lithium Metal Anode through Electrochemical Kinetics Manipulation. Adv. Funct. Mater. 2019, 29, 1904629. [CrossRef]
40. Zhou, B.X.; Bonakdarpour, A.; Stosevski, I.; Fang, B.Z.; Wilkinson, D.P. Modification of Cu current collectors for lithium metal
batteries-A review. Prog. Mater. Sci. 2022, 130, 100996. [CrossRef]
41. Zhao, H.; Lei, D.N.; He, Y.B.; Yuan, Y.F.; Yun, Q.B.; Ni, B.; Lv, W.; Li, B.H.; Yang, Q.H.; Kang, F.Y.; et al. Compact 3D Copper with
Uniform Porous Structure Derived by Electrochemical Dealloying as Dendrite-Free Lithium Metal Anode Current Collector.
Adv. Energy Mater. 2018, 8, 1800266. [CrossRef]
42. Ke, X.; Liang, Y.H.; Ou, L.H.; Liu, H.D.; Chen, Y.M.; Wu, W.L.; Cheng, Y.F.; Guo, Z.P.; Lai, Y.Q.; Liu, P.; et al. Surface engineering
of commercial Ni foams for stable Li metal anodes. Energy Stor. Mater. 2019, 23, 547–555. [CrossRef]
43. Fan, L.; Wei, S.Y.; Li, S.Y.; Li, Q.; Lu, Y.Y. Recent Progress of the Solid-State Electrolytes for High-Energy Metal-Based Batteries.
Adv. Energy Mater. 2018, 8, 1702657. [CrossRef]
44. Yang, C.P.; Fu, K.; Zhang, Y.; Hitz, E.; Hu, L.B. Protected Lithium-Metal Anodes in Batteries: From Liquid to Solid. Adv. Mater.
2017, 29, 1701169. [CrossRef]
45. Zhou, D.; Shanmukaraj, D.; Tkacheva, A.; Armand, M.; Wang, G.X. Polymer Electrolytes for Lithium-Based Batteries: Advances
and Prospects. Chem 2019, 5, 2326–2352. [CrossRef]
46. Chen, R.S.; Li, Q.H.; Yu, X.Q.; Chen, L.Q.; Li, H. Approaching Practically Accessible Solid-State Batteries: Stability Issues Related
to Solid Electrolytes and Interfaces. Chem. Rev. 2020, 120, 6820–6877. [CrossRef]
47. Yu, Q.J.; Jiang, K.C.; Yu, C.L.; Chen, X.J.; Zhang, C.J.; Yao, Y.; Jiang, B.; Long, H.J. Recent progress of composite solid polymer
electrolytes for all-solid-state lithium metal batteries. Chin. Chem. Lett. 2021, 32, 2659–2678. [CrossRef]
48. Zhao, B.L.; Ma, L.X.; Wu, K.; Cao, M.X.; Xu, M.G.; Zhang, X.X.; Liu, W.; Chen, J.T. Asymmetric double-layer composite electrolyte
with enhanced ionic conductivity and interface stability for all-solid-state lithium metal batteries. Chin. Chem. Lett. 2021, 32,
125–131. [CrossRef]
49. Liu, H.; Cheng, X.B.; Huang, J.Q.; Yuan, H.; Lu, Y.; Yan, C.; Zhu, G.L.; Xu, R.; Zhao, C.Z.; Hou, L.P.; et al. Controlling Dendrite
Growth in Solid-State Electrolytes. ACS Energy Lett. 2020, 5, 833–843. [CrossRef]
50. Sun, M.H.; Liu, T.F.; Yuan, Y.F.; Ling, M.; Xu, N.; Liu, Y.Y.; Yan, L.J.; Li, H.; Liu, C.Y.; Lu, Y.Y.; et al. Visualizing Lithium Dendrite
Formation within Solid-State Electrolytes. ACS Energy Lett. 2021, 6, 451–458. [CrossRef]
51. Raj, V.; Venturi, V.; Kankanallu, V.R.; Kuiri, B.; Viswanathan, V.; Aetukuri, N.P.B. Direct correlation between void formation and
lithium dendrite growth in solid-state electrolytes with interlayers. Nat. Mater. 2022, 21, 1050–1056. [CrossRef] [PubMed]
52. Yan, K.; Lu, Z.; Lee, H.-W.; Xiong, F.; Hsu, P.-C.; Li, Y.; Zhao, J.; Chu, S.; Cui, Y. Selective deposition and stable encapsulation of
lithium through heterogeneous seeded growth. Nat. Energy 2016, 1, 16010. [CrossRef]
53. Pei, A.; Zheng, G.Y.; Shi, F.F.; Li, Y.Z.; Cui, Y. Nanoscale Nucleation and Growth of Electrodeposited Lithium Metal. Nano Lett.
2017, 17, 1132–1139. [CrossRef]
54. Jaeckle, M.; Gross, A. Microscopic properties of lithium, sodium, and magnesium battery anode materials related to possible
dendrite growth. J. Chem. Phys. 2014, 141, 174710. [CrossRef]
55. Xiao, J. How lithium dendrites form in liquid batteries. Science 2019, 366, 426–427. [CrossRef] [PubMed]
56. Cheng, X.B.; Zhang, R.; Zhao, C.Z.; Zhang, Q. Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review. Chem. Rev.
2017, 117, 10403–10473. [CrossRef] [PubMed]
57. Fleury, V.; Chazalviel, J.N.; Rosso, M.; Sapoval, B. The role of the anions in the growth speed of fractal electrodeposits. J. Electroanal.
Chem. Interfacial Electrochem. 1990, 290, 249–255. [CrossRef]
58. Chazalviel, J. Electrochemical aspects of the generation of ramified metallic electrodeposits. Phys. Rev. A 1990, 42, 7355–7367.
[CrossRef]
Batteries 2022, 8, 246 21 of 24

59. Seong, I.W.; Hong, C.H.; Kim, B.K.; Yoon, W.Y. The effects of current density and amount of discharge on dendrite formation in
the lithium powder anode electrode. J. Power Sources 2008, 178, 769–773. [CrossRef]
60. Monroe, C.; Newman, J. The impact of elastic deformation on deposition kinetics at lithium/polymer interfaces. J. Electrochem.
Soc. 2005, 152, A396–A404. [CrossRef]
61. Ota, H.; Shima, K.; Ue, M.; Yamaki, J. Effect of vinylene carbonate as additive to electrolyte for lithium metal anode. Electrochim.
Acta 2004, 49, 565–572. [CrossRef]
62. Fang, C.C.; Li, J.X.; Zhang, M.H.; Zhang, Y.H.; Yang, F.; Lee, J.Z.; Lee, M.H.; Alvarado, J.; Schroeder, M.A.; Yang, Y.Y.C.; et al.
Quantifying inactive lithium in lithium metal batteries. Nature 2019, 572, 511–515. [CrossRef] [PubMed]
63. Xiang, Y.; Tao, M.; Zhong, G.; Liang, Z.; Zheng, G.; Huang, X.; Liu, X.; Jin, Y.; Xu, N.; Armand, M.; et al. Quantitatively analyzing
the failure processes of rechargeable Li metal batteries. Sci. Adv. 2021, 7, eabj3423. [CrossRef] [PubMed]
64. Cheng, X.B.; Zhang, R.; Zhao, C.Z.; Wei, F.; Zhang, J.G.; Zhang, Q. A Review of Solid Electrolyte Interphases on Lithium Metal
Anode. Adv. Sci. 2016, 3, 1500213. [CrossRef]
65. Xu, K. Electrolytes and Interphases in Li-Ion Batteries and Beyond. Chem. Rev. 2014, 114, 11503–11618. [CrossRef]
66. Cohen, Y.S.; Cohen, Y.; Aurbach, D. Micromorphological studies of lithium electrodes in alkyl carbonate solutions using in situ
atomic force microscopy. J. Phys. Chem. B 2000, 104, 12282–12291. [CrossRef]
67. An, S.J.; Li, J.; Daniel, C.; Mohanty, D.; Nagpure, S.; Wood, D.L., III. The state of understanding of the lithium-ion-battery graphite
solid electrolyte interphase (SEI) and its relationship to formation cycling. Carbon 2016, 105, 52–76. [CrossRef]
68. Aurbach, D.; Daroux, M.L.; Faguy, P.W.; Yeager, E. IDENTIFICATION OF SURFACE-FILMS FORMED ON LITHIUM IN
PROPYLENE CARBONATE SOLUTIONS. J. Electrochem. Soc. 1987, 134, 1611–1620. [CrossRef]
69. Aurbach, D.; Zaban, A.; Ein-Eli, Y.; Weissman, I.; Chusid, O.; Markovsky, B.; Levi, M.; Levi, E.; Schechter, A.; Granot, E. Recent
studies on the correlation between surface chemistry, morphology, three-dimensional structures and performance of Li and Li-C
intercalation anodes in several important electrolyte systems. J. Power Sources 1997, 68, 91–98. [CrossRef]
70. Aurbach, D.; Zaban, A.; Gofer, Y.; Ely, Y.E.; Weissman, I.; Chusid, O.; Abramson, O. Recent studies of the lithium liquid electrolyte
interface-electrochemical, morphological and spectral studies of a few important systems. J. Power Sources 1995, 54, 76–84.
[CrossRef]
71. Aurbach, D. Review of selected electrode-solution interactions which determine the performance of Li and Li ion batteries.
J. Power Sources 2000, 89, 206–218. [CrossRef]
72. Peled, E.; Ardel, G. Advanced Model for Solid Electrolyte Interphase Electrodes in Liquid and Polymer Electrolytes. J. Electrochem.
Soc. 1997, 144, L208–L210. [CrossRef]
73. Li, Y.; Li, Y.; Pei, A.; Yan, K.; Sun, Y.; Wu, C.-L.; Joubert, L.-M.; Chin, R.; Koh, A.L.; Yu, Y.; et al. Atomic structure of sensitive
battery materials and Interfaces revealed by cryo-electron microscopy. Science 2017, 358, 506–510. [CrossRef] [PubMed]
74. Ramasubramanian, A.; Yurkiv, V.; Foroozan, T.; Ragone, M.; Shahbazian-Yassar, R.; Mashayek, F.l. Lithium Diffusion Mechanism
through Solid-Electrolyte Interphase in Rechargeable Lithium Batteries. J. Phys. Chem. C 2019, 123, 10237–10245. [CrossRef]
75. Zhang, X.Q.; Cheng, X.B.; Chen, X.; Yan, C.; Zhang, Q. Fluoroethylene Carbonate Additives to Render Uniform Li Deposits in
Lithium Metal Batteries. Adv. Funct. Mater. 2017, 27, 1605989. [CrossRef]
76. Mogi, R.; Inaba, M.; Jeong, S.K.; Iriyama, Y.; Abe, T.; Ogumi, Z. Effects of some organic additives on lithium deposition in
propylene carbonate. J. Electrochem. Soc. 2002, 149, A1578–A1583. [CrossRef]
77. Mukra, T.; Peled, E. Elucidation of the Losses in Cycling Lithium-Metal Anodes in Carbonate-Based Electrolytes. J. Electrochem.
Soc. 2020, 167, 100520. [CrossRef]
78. Zhang, M.S.; Liu, R.J.; Wang, Z.K.; Xing, X.Y.; Liu, Y.G.; Deng, B.B.; Yang, T. Electrolyte additive maintains high performance for
dendrite-free lithium metal anode. Chin. Chem. Lett. 2020, 31, 1217–1220. [CrossRef]
79. Cheng, X.B.; Zhao, M.Q.; Chen, C.; Pentecost, A.; Maleski, K.; Mathis, T.; Zhang, X.Q.; Zhang, Q.; Jiang, J.J.; Gogotsi, Y.
Nanodiamonds suppress the growth of lithium dendrites. Nat. Commun. 2017, 8, 336. [CrossRef]
80. Hu, Y.; Chen, W.; Lei, T.; Jiao, Y.; Wang, H.; Wang, X.; Rao, G.; Wang, X.; Chen, B.; Xiong, J. Graphene Quantum Dots as the
Nucleation Sites and Interfacial Regulator to Suppress Lithium Dendrites for High-Loading Lithium-Sulfur Battery. Nano Energy
2019, 68, 104373. [CrossRef]
81. Xu, S.; Zhao, T.; Ye, Y.; Yang, T.; Luo, R.; Li, L.; Wu, F.; Chen, R. A Designed Lithiophilic Carbon Channel on Separator to Regulate
Lithium Deposition Behavior. Small 2022, 18, 2104390. [CrossRef] [PubMed]
82. Li, Z.; Peng, M.; Zhou, X.; Shin, K.; Tunmee, S.; Zhang, X.; Xie, C.; Saitoh, H.; Zheng, Y.; Zhou, Z.; et al. In Situ Chemical Lithiation
Transforms Diamond-Like Carbon into an Ultrastrong Ion Conductor for Dendrite-Free Lithium-Metal Anodes. Adv. Mater. 2021,
33, 2100793. [CrossRef] [PubMed]
83. Wang, Z.H.; Wang, X.D.; Sun, W.; Sun, K.N. Dendrite-Free Lithium Metal Anodes in High Performance Lithium-Sulfur Batteries
with Bifunctional Carbon Nanofiber Interlayers. Electrochim. Acta 2017, 252, 127–137. [CrossRef]
84. Liu, Y.; Liu, Q.; Xin, L.; Liu, Y.; Yang, F.; Stach, E.A.; Xie, J. Making Li-metal electrodes rechargeable by controlling the dendrite
growth direction. Nat. Energy 2017, 2, 17083. [CrossRef]
85. Wondimkun, Z.T.; Beyene, T.T.; Weret, M.A.; Sahalie, N.A.; Huang, C.-J.; Thirumalraj, B.; Jote, B.A.; Wang, D.; Su, W.-N.;
Wang, C.-H.; et al. Binder-free ultra-thin graphene oxide as an artificial solid electrolyte interphase for anode-free rechargeable
lithium metal batteries. J. Power Sources 2020, 450, 227589. [CrossRef]
Batteries 2022, 8, 246 22 of 24

86. Liu, W.; Xia, Y.; Wang, W.; Wang, Y.; Jin, J.; Chen, Y.; Paek, E.; Mitlin, D. Pristine or Highly Defective? Understanding the Role of
Graphene Structure for Stable Lithium Metal Plating. Adv. Energy Mater. 2019, 9, 1802918. [CrossRef]
87. Ma, Y.; Qi, P.; Ma, J.; Wei, L.; Zhao, L.; Cheng, J.; Su, Y.; Gu, Y.; Lian, Y.; Peng, Y.; et al. Wax-Transferred Hydrophobic CVD
Graphene Enables Water-Resistant and Dendrite-Free Lithium Anode toward Long Cycle Li-Air Battery. Adv. Sci. 2021, 8, 2100488.
[CrossRef] [PubMed]
88. Zhou, Y.; Zhang, X.; Ding, Y.; Zhang, L.; Yu, G. Reversible Deposition of Lithium Particles Enabled by Ultraconformal and
Stretchable Graphene Film for Lithium Metal Batteries. Adv. Mater. 2020, 32, 2005763. [CrossRef]
89. Xie, K.; Wei, W.; Yuan, K.; Lu, W.; Guo, M.; Li, Z.; Song, Q.; Liu, X.; Wang, J.-G.; Shen, C. Toward Dendrite-Free Lithium Deposition
via Structural and Interfacial Synergistic Effects of 3D Graphene@Ni Scaffold. ACS Appl. Mater. Interfaces 2016, 8, 26091–26097.
[CrossRef]
90. Fan, L.; Sun, B.; Yan, K.; Xiong, P.; Guo, X.; Guo, Z.; Zhang, N.; Feng, Y.; Sun, K.; Wang, G. A Dual-Protective Artificial Interface
for Stable Lithium Metal Anodes. Adv. Energy Mater. 2021, 11, 2102242. [CrossRef]
91. Zhu, J.; Li, P.; Chen, X.; Legut, D.; Fan, Y.; Zhang, R.; Lu, Y.; Cheng, X.; Zhang, Q. Rational design of graphitic-inorganic Bi-layer
artificial SEI for stable lithium metal anode. Energy Stor. Mater. 2019, 16, 426–433. [CrossRef]
92. Tang, K.; Xiao, J.; Li, X.; Wang, D.; Long, M.; Chen, J.; Gao, H.; Chen, W.; Liu, C.; Liu, H. Advances of Carbon-Based Materials for
Lithium Metal Anodes. Front. Chem. 2020, 8, 595972. [CrossRef] [PubMed]
93. Pomerantseva, E.; Bonaccorso, F.; Feng, X.; Cui, Y.; Gogotsi, Y. Energy storage: The future enabled by nanomaterials. Science 2019,
366, 969–980. [CrossRef] [PubMed]
94. Cao, W.; Chen, W.; Lu, M.; Zhang, C.; Tian, D.; Wang, L.; Yu, F. In situ generation of Li3N concentration gradient in 3D
carbon-based lithium anodes towards highly-stable lithium metal batteries. J. Energy Chem. 2022, 76, 648–656. [CrossRef]
95. Liu, J.; Ma, H.; Wen, Z.; Li, H.; Yang, J.; Pei, N.; Zhang, P.; Zhao, J. Layered Ag-graphene films synthesized by Gamma ray
irradiation for stable lithium metal anodes in carbonate-based electrolytes. J. Energy Chem. 2022, 64, 354–363. [CrossRef]
96. Chen, H.; Li, M.; Li, C.; Li, X.; Wu, Y.; Chen, X.; Wu, J.; Li, X.; Chen, Y. Electrospun carbon nanofibers for lithium metal anodes:
Progress and perspectives. Chin. Chem. Lett. 2022, 33, 141–152. [CrossRef]
97. Zhang, Z.; Zhu, P.; Li, C.; Yu, J.; Cai, J.; Yang, Z. Needle-like cobalt phosphide arrays grown on carbon fiber cloth as a binder-free
electrode with enhanced lithium storage performance. Chin. Chem. Lett. 2021, 32, 154–157. [CrossRef]
98. Liu, H.; Zhang, J.; Liu, Y.; Wei, Y.; Ren, S.; Pan, L.; Su, Y.; Xiao, J.; Fan, H.; Lin, Y.; et al. A flexible artificial solid-electrolyte
interlayer supported by compactness-tailored carbon nanotube network for dendrite-free lithium metal anode. J. Energy Chem.
2022, 69, 421–427. [CrossRef]
99. Zhang, F.; Liu, X.Y.; Yang, M.H.; Cao, X.Q.; Huang, X.Y.; Tian, Y.; Zhang, F.; Li, H.X. Novel S-doped ordered mesoporous carbon
nanospheres toward advanced lithium metal anodes. Nano Energy 2020, 69, 104443. [CrossRef]
100. Qi, J.; Li, Y.; Wei, G.; Li, J.; Sun, X.; Shen, J.; Han, W.; Wang, L. Nitrogen doped porous hollow carbon spheres for enhanced
benzene removal. Sep. Purif. Technol. 2017, 188, 112–118. [CrossRef]
101. Jiang, H.; Zhou, Y.; Zhu, H.; Qin, F.; Han, Z.; Bai, M.; Yang, J.; Li, J.; Hong, B.; Lai, Y. Interconnected stacked hollow carbon spheres
uniformly embedded with Ni2P nanoparticles as scalable host for practical Li metal anode. Chem. Eng. J. 2022, 428, 132648.
[CrossRef]
102. Chen, W.; Hong, Y.; Zhao, Z.; Zhang, Y.; Pan, L.; Wan, J.; Nazir, M.; Wang, J.; He, H. Directing the deposition of lithium metal
to the inner concave surface of graphitic carbon tubes to enable lithium-metal batteries. J. Mater. Chem. A 2021, 9, 16936–16942.
[CrossRef]
103. Liu, L.; Yin, Y.-X.; Li, J.-Y.; Li, N.-W.; Zeng, X.-X.; Ye, H.; Guo, Y.-G.; Wan, L.-J. Free-Standing Hollow Carbon Fibers as
High-Capacity Containers for Stable Lithium Metal Anodes. Joule 2017, 1, 563–575. [CrossRef]
104. Chen, C.; Guan, J.; Li, N.W.; Lu, Y.; Luan, D.; Zhang, C.H.; Cheng, G.; Yu, L.; Lou, X.W.D. Lotus-Root-Like Carbon Fibers
Embedded with Ni-Co Nanoparticles for Dendrite-Free Lithium Metal Anodes. Adv. Mater. 2021, 33, 2100608. [CrossRef]
105. Wang, Z.Y.; Lu, Z.X.; Guo, W.; Luo, Q.; Yin, Y.H.; Liu, X.B.; Li, Y.S.; Xia, B.Y.; Wu, Z.P. A Dendrite-Free Lithium/Carbon Nanotube
Hybrid for Lithium-Metal Batteries. Adv. Mater. 2021, 33, 2006702. [CrossRef]
106. Niu, C.J.; Pan, H.L.; Xu, W.; Xiao, J.; Zhang, J.G.; Luo, L.L.; Wang, C.M.; Mei, D.H.; Meng, J.S.; Wang, X.P.; et al. Self-smoothing
anode for achieving high-energy lithium metal batteries under realistic conditions. Nat. Nanotechnol. 2019, 14, 594–601. [CrossRef]
107. Liu, K.; Li, Z.; Xie, W.; Li, J.; Rao, D.; Shao, M.; Zhang, B.; Wei, M. Oxygen-rich carbon nanotube networks for enhanced lithium
metal anode. Energy Stor. Mater. 2018, 15, 308–314. [CrossRef]
108. Lin, D.; Liu, Y.; Liang, Z.; Lee, H.-W.; Sun, J.; Wang, H.; Yan, K.; Xie, J.; Cui, Y. Layered reduced graphene oxide with nanoscale
interlayer gaps as a stable host for lithium metal anodes. Nat. Nanotechnol. 2016, 11, 626–632. [CrossRef]
109. Xu, Z.; Xu, L.; Xu, Z.; Deng, Z.; Wang, X. N, O-Codoped Carbon Nanosheet Array Enabling Stable Lithium Metal Anode.
Adv. Funct. Mater. 2021, 31, 2102354. [CrossRef]
110. Wang, T.; Zhai, P.; Legut, D.; Wang, L.; Liu, X.; Li, B.; Dong, C.; Fan, Y.; Gong, Y.; Zhang, Q. S-Doped Graphene-Regional
Nucleation Mechanism for Dendrite-Free Lithium Metal Anodes. Adv. Energy Mater. 2019, 9, 1804000. [CrossRef]
111. Li, Z.; Li, X.; Zhou, L.; Xiao, Z.; Zhou, S.; Zhang, X.; Li, L.; Zhi, L. A synergistic strategy for stable lithium metal anodes using 3D
fluorine-doped graphene shuttle-implanted porous carbon networks. Nano Energy 2018, 49, 179–185. [CrossRef]
112. Fang, Y.; Zeng, Y.; Jin, Q.; Lu, X.F.; Luan, D.; Zhang, X.; Lou, X.W.D. Nitrogen-Doped Amorphous Zn-Carbon Multichannel Fibers
for Stable Lithium Metal Anodes. Angew. Chem. Int. Ed. 2021, 60, 8515–8520. [CrossRef] [PubMed]
Batteries 2022, 8, 246 23 of 24

113. Yang, T.; Li, L.; Wu, F.; Chen, R. A Soft Lithiophilic Graphene Aerogel for Stable Lithium Metal Anode. Adv. Funct. Mater. 2020,
30, 2002013. [CrossRef]
114. Zhao, C.; Yu, C.; Li, S.; Guo, W.; Zhao, Y.; Dong, Q.; Lin, X.; Song, Z.; Tan, X.; Wang, C.; et al. Ultrahigh-Capacity and Long-
Life Lithium-Metal Batteries Enabled by Engineering Carbon Nanofiber-Stabilized Graphene Aerogel Film Host. Small 2018,
14, 1803310. [CrossRef]
115. Li, Y.; Li, Y.; Zhang, L.; Tao, H.; Li, Q.; Zhang, J.; Yang, X. Lithiophilicity: The key to efficient lithium metal anodes for lithium
batteries. J. Energy Chem. 2022, in press. [CrossRef]
116. Zhang, F.; Liu, P.; Tian, Y.; Wu, J.; Wang, X.; Li, H.; Liu, X. Uniform lithium nucleation/deposition regulated by N/S co-doped
carbon nanospheres towards ultra-stable lithium metal anodes. J. Mater. Chem. A 2022, 10, 1463–1472. [CrossRef]
117. Zhao, C.Y.; Yin, X.J.; Guo, Z.K.; Zhao, D.; Yang, G.Y.; Chen, A.S.; Fan, L.S.; Zhang, Y.; Zhang, N.Q. High lithiophilic nitrogen-doped
carbon nanotube arrays prepared by in-situ catalyze for lithium metal anode. Chin. Chem. Lett. 2021, 32, 2254–2258. [CrossRef]
118. Chu, Y.T.; Xi, B.J.; Xiong, S.L. One-step construction of MoO2 uniform nanoparticles on graphene with enhanced lithium storage.
Chin. Chem. Lett. 2021, 32, 1983–1987. [CrossRef]
119. Li, D.; Gao, Y.; Xie, C.; Zheng, Z. Au-coated carbon fabric as Janus current collector for dendrite-free flexible lithium metal anode
and battery. Appl. Phys. Rev. 2022, 9, 011424. [CrossRef]
120. Tian, R.; Wan, S.L.; Guan, L.; Duan, H.N.; Guo, Y.P.; Li, H.; Liu, H.Z. Oriented growth of Li metal for stable Li/carbon composite
negative electrode. Electrochim. Acta 2018, 292, 227–233. [CrossRef]
121. Gao, Y.; Wang, D.; Shin, Y.K.; Yan, Z.; Han, Z.; Wang, K.; Hossain, M.J.; Shen, S.; AlZahrani, A.; van Duin, A.C.T.; et al. Stable
metal anodes enabled by a labile organic molecule bonded to a reduced graphene oxide aerogel. Proc. Natl. Acad. Sci. USA 2020,
117, 30135–30141. [CrossRef]
122. Martin, C.; Genovese, M.; Louli, A.J.; Weber, R.; Dahn, J.R. Cycling Lithium Metal on Graphite to Form Hybrid Lithium-
Ion/Lithium Metal Cells. Joule 2020, 4, 1296–1310. [CrossRef]
123. Duan, J.; Zheng, Y.; Luo, W.; Wu, W.; Wang, T.; Xie, Y.; Li, S.; Li, J.; Huang, Y. Is graphite lithiophobic or lithiophilic? Natl. Sci. Rev.
2020, 7, 1208–1217. [CrossRef] [PubMed]
124. Yang, G.; Zhang, S.; Weng, S.; Li, X.; Wang, X.; Wang, Z.; Chen, L. Anionic Effect on Enhancing the Stability of a Solid Electrolyte
Interphase Film for Lithium Deposition on Graphite. Nano Lett. 2021, 21, 5316–5323. [CrossRef] [PubMed]
125. Ye, H.; Xin, S.; Yin, Y.-X.; Li, J.-Y.; Guo, Y.-G.; Wan, L.-J. Stable Li Plating/Stripping Electrochemistry Realized by a Hybrid Li
Reservoir in Spherical Carbon Granules with 3D Conducting Skeletons. J. Am. Chem. Soc. 2017, 139, 5916–5922. [CrossRef]
126. Sun, Y.; Zheng, G.; Seh, Z.W.; Liu, N.; Wang, S.; Sun, J.; Lee, H.R.; Cui, Y. Graphite-Encapsulated Li-Metal Hybrid Anodes for
High-Capacity Li Batteries. Chem 2016, 1, 287–297. [CrossRef]
127. Zuo, T.T.; Wu, X.W.; Yang, C.P.; Yin, Y.X.; Ye, H.; Li, N.W.; Guo, Y.G. Graphitized Carbon Fibers as Multifunctional 3D Current
Collectors for High Areal Capacity Li Anodes. Adv. Mater. 2017, 29, 1700389. [CrossRef]
128. Cai, W.; Yan, C.; Yao, Y.X.; Xu, L.; Chen, X.R.; Huang, J.Q.; Zhang, Q. The Boundary of Lithium Plating in Graphite Electrode for
Safe Lithium-Ion Batteries. Angew. Chem. Int. Ed. 2021, 60, 13007–13012. [CrossRef]
129. Yang, G.; Zhang, S.; Tong, Y.; Li, X.; Wang, Z.; Chen, L. Minimizing carbon particle size to improve lithium deposition on natural
graphite. Carbon 2019, 155, 9–15. [CrossRef]
130. Ho, A.S.; Parkinson, D.Y.; Finegan, D.P.; Trask, S.E.; Jansen, A.N.; Tong, W.; Balsara, N.P. 3D Detection of Lithiation and Lithium
Plating in Graphite Anodes during Fast Charging. ACS Nano 2021, 15, 10480–10487. [CrossRef]
131. Luo, J.; Wu, C.E.; Su, L.Y.; Huang, S.S.; Fang, C.C.; Wu, Y.S.; Chou, J.; Wu, N.L. A proof-of-concept graphite anode with a lithium
dendrite suppressing polymer coating. J. Power Sources 2018, 406, 63–69. [CrossRef]
132. Cui, C.; Yang, C.; Eidson, N.; Chen, J.; Han, F.; Chen, L.; Luo, C.; Wang, P.F.; Fan, X.; Wang, C. A Highly Reversible, Dendrite-Free
Lithium Metal Anode Enabled by a Lithium-Fluoride-Enriched Interphase. Adv. Mater. 2020, 32, 1906427. [CrossRef] [PubMed]
133. Wang, S.; Liu, D.; Cai, X.; Zhang, L.; Liu, Y.; Qin, X.; Zhao, R.; Zeng, X.; Han, C.; Zhan, C.; et al. Promoting the reversibility
of lithium ion/lithium metal hybrid graphite anode by regulating solid electrolyte interface. Nano Energy 2021, 90, 106510.
[CrossRef]
134. Feng, W.; Dong, X.; Zhang, X.; Lai, Z.; Li, P.; Wang, C.; Wang, Y.; Xia, Y. Li/Garnet Interface Stabilization by Thermal-
Decomposition Vapor Deposition of an Amorphous Carbon Layer. Angew. Chem. Int. Ed. 2020, 59, 5346–5349. [CrossRef]
[PubMed]
135. Chen, L.; Zhang, J.; Tong, R.A.; Zhang, J.; Wang, H.; Shao, G.; Wang, C.A. Excellent Li/Garnet Interface Wettability Achieved by
Porous Hard Carbon Layer for Solid State Li Metal Battery. Small 2022, 18, 2106142. [CrossRef] [PubMed]
136. Lee, Y.G.; Fujiki, S.; Jung, C.; Suzuki, N.; Yashiro, N.; Omoda, R.; Ko, D.S.; Shiratsuchi, T.; Sugimoto, T.; Ryu, S.; et al. High-energy
long-cycling all-solid-state lithium metal batteries enabled by silver-carbon composite anodes. Nat. Energy 2020, 5, 299–308.
[CrossRef]
137. Duan, J.; Wu, W.Y.; Nolan, A.M.; Wang, T.R.; Wen, J.Y.; Hu, C.C.; Mo, Y.F.; Luo, W.; Huang, Y.H. Lithium-Graphite Paste: An
Interface Compatible Anode for Solid-State Batteries. Adv. Mater. 2019, 31, 1807243. [CrossRef]
138. Xing, X.; Li, Y.; Wang, S.; Liu, H.; Wu, Z.; Yu, S.; Holoubek, J.; Zhou, H.; Liu, P. YY Graphite-Based Lithium-Free 3D Hybrid
Anodes for High Energy Density All-Solid-State Batteries. ACS Energy Lett. 2021, 6, 1831–1838. [CrossRef]
Batteries 2022, 8, 246 24 of 24

139. Bao, W.; Hu, Z.Y.; Wang, Y.Y.; Jiang, J.H.; Huo, S.K.; Fan, W.Z.; Chen, W.J.; Jing, X.; Long, X.Y.; Zhang, Y.F. Poly(ionic liquid)-
functionalized graphene oxide towards ambient temperature operation of all-solid-state PEO-based polymer electrolyte lithium
metal batteries. Chem. Eng. J. 2022, 437, 135420. [CrossRef]
140. Nicotera, I.; Simari, C.; Agostini, M.; Enotiadis, A.; Brutti, S. A Novel Li+-Nafion-Sulfonated Graphene Oxide Membrane as
Single Lithium-Ion Conducting Polymer Electrolyte for Lithium Batteries. J. Phys. Chem. C 2019, 123, 27406–27416. [CrossRef]
141. Li, Z.Y.; Liu, F.; Chen, S.S.; Zhai, F.; Li, Y.; Feng, Y.Y.; Feng, W. Single Li ion conducting solid-state polymer electrolytes based on
carbon quantum dots for Li-metal batteries. Nano Energy 2021, 82, 105698. [CrossRef]