Energy Storage Materials 55 (2023) 364–387

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Energy Storage Materials

journal homepage: www.elsevier.com/locate/ensm

Search for stable host materials as low-voltage anodes for lithium-ion

batteries: A mini-review
Yun Zhang a, Jun Huang a, Nagahiro Saito b, Zhengxi Zhang a, c, *, Li Yang a, c, d, *,
Shin-ichi Hirano d
a
School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules, Shanghai Jiao Tong University, Shanghai 200240, China
b
Department of Chemical Systems Engineering, Graduate School of Engineering, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8603, Japan
c
Shanghai Electrochemical Energy Devices Research Center, Shanghai 200240, China
d
Hirano Institute for Materials Innovation, Shanghai Jiao Tong University, Shanghai 200240, China

A R T I C L E I N F O A B S T R A C T

Keywords: The explosive demand for lithium-ion batteries (LIBs) in electric vehicles, portable electronics, and smart grids
Anodes has spurred extensive research in recent years. The key to essential advances in LIBs depends on the search for
Lithium-ion batteries stable host electrode materials with desirable energy and power densities. In the development of emerging stable
Low-voltage
host anode materials, the operating potential is an overlooked but crucial parameter because it deeply influences
Stable host
the energy, power, and safety of batteries. The ideal potential should not be too close to the lithium deposition
potential like graphite (0.1 V vs. Li+/Li) which would trigger the formation of lithium dendrites under high rates,
nor should be too high like spinel Li4Ti5O12 (> 1.5 V vs. Li+/Li) which compromises the batteries’ power and
energy density. This mini-review firstly gives an account of several types of titanium-based and vanadium-based
compounds as stable host anodes with the average operating potentials around or below 1 V vs. Li+/Li. The
mechanisms for stable lithium storage and the origins of the low operating potentials are discussed by combining
various characterization technologies. The key barriers and corresponding approaches are summarized for
progressive electrochemical performance. Furthermore, several concise perspectives and challenges aiming at
further theoretical prediction and practical application are provided.

1. Introduction ever-increasing market [12,13].

To reduce carbon emissions and tackle global climate change, the
transition from fossil energy to renewable and clean energy is the most
urgent theme of today’s society [1–4]. The development of energy
storage devices plays a crucial role in the preservation of clean energy
such as solar and wind and the popularization of zero-emission electric
vehicles (EVs) [5–7]. Since the first commercialization by Sony corpo­
ration in 1991, lithium-ion batteries (LIBs) have occupied the leading
position in the energy storage market due to the combination of high
energy and power density, durable cycling stability, and environmental
benignity [2,8-11]. The electrochemical performance of LIBs signifi­
cantly depends on the upgrade of cell architecture and the selection of
electrode materials. As for cathode materials, LiFePO4, known for its
better safety and structural toleration, and layered oxides (e.g.,
LiNi0.8Co0.15Al0.05O2 and Li(Ni,Mn,Co)O2) with high power and energy
density, have been promoted to meet the diversified situations in the
As for anodes, graphite still dominates the mainstream material
market. Graphite theoretically offers a specific gravimetric capacity of
372 mAh g− 1. The intercalation-based mechanism enables graphite to
maintain its structural integrity and undergo small volume changes
during repeated Li+ insertion and extraction [14,15], and the solid
electrolyte interface (SEI) formed at low potentials can effectively pro­
tect the graphite from being exfoliated by the carbonate electrolyte [16,
17]. In addition, the low and flat working potential (0.1 V vs. Li+/Li)
could guarantee the maximum output voltage of the full battery. How­
ever, given the sluggish Li+ kinetic for graphite, this potential
approaching the lithium plating also means a high risk for lithium
dendrites [18,19], which seriously threatens the battery’s safety.
Alloying-type [20–22]. (Si, Sn, Ge, P, etc.) and most conversion-type
[23,24]. (Fe3O4, MnO2, MoO3, CoO, etc.) can provide high theoretical
capacity, while the drastic volume vibration, high irreversible capacity,
and poor kinetics of these anodes cause unstoppable capacity decay,

* Corresponding authors.
E-mail addresses: zhengxizhang@sjtu.edu.cn (Z. Zhang), liyangce@sjtu.edu.cn (L. Yang).

https://doi.org/10.1016/j.ensm.2022.11.030
Received 15 May 2022; Received in revised form 10 September 2022; Accepted 14 November 2022
Available online 23 November 2022
2405-8297/© 2022 Published by Elsevier B.V.
Y. Zhang et al.
severe polarization, and lead to rapid battery failure. To relieve the is­
sues, alloying-type materials need to be composite with a large amount
of carbon additive or designed into elaborate nano-sized structures,
which would in turn greatly decrease the packing density as well as
exacerbate the interfacial side reactions and increase the manufacturing
cost. Lithium metal is the optimal choice for the anode in terms of energy
density [25,26]. However, the concerns of dendrites and poor cycling
stability still hinder it from practical application.
In comparison with alloying-type and lithium metal, intercalation-
type anode materials can offer appropriate empty sites to accommo­
date Li+ with the smaller lattice volume expansion, hence possessing
excellent cycling stability [27,28]. Besides graphite, Li4Ti5O12 (LTO), as
an intercalation-type anode, also attracted considerable attention in
recent years due to its superior safety, zero-strain character, relatively
high volumetric capacity, and improved low-temperature operation (e.
g., 0 to -30 ◦ C) [29,30]. Nevertheless, the relatively low theoretical ca­
pacity (175 mAh g− 1) and too high operating potential (1.55 V vs.
Li+/Li) impede the full energy application of LTO. Thus, continued ef­
forts are needed to search for suitable host frameworks for Li+ storage
with dual characters of high capacity and safe potential.
A series of intercalation-type titanium(Ti)-based and niobium(Nb)-
based materials with outstanding electrochemical performance have
been developed to replace LTO. For instance, TiNb2O7 with a Wadsley-
Roth shear structure delivers a high reversible capacity of over 300 mAh
g− 1, which greatly exceeds that of LTO [31,32]. T-Nb2O5 (ortho­
rhombic) with layered structure offers much high electric conductivity
(3.4 × 10− 6 S cm− 1 vs. 10− 8 to 10− 13 S cm− 1 for LTO at 300 K) and
higher theoretical capacity (200 mAh g− 1) [33]. Niobium tungsten ox­
ides Nb16W5O55 and Nb18W16O93 could achieve unprecedented bulk
rate capacity because of the rapid Li+ diffusion in the crystallographic
shear and bronze-like structures [34]. However, most of them exhibit
similar high operating potentials (> 1.5 V) to LTO with the variation of
the redox couples of Ti4+/Ti3+, Nb5+/Nb4+, Nb4+/Nb3+, and W6+/W5+.
Such high potentials compromise the operating voltage after incorpo­
rating the cathode. In general, without considering the mass of inactive
components (such as conductive carbon black and binders), electrolytes,
separators, and battery casings, the energy density of the unit cell can be
calculated as follows [35]:
ΔV = Vc − Va (1)
Cc × Ca
E= × ΔV (2)
Cc + Ca
where ΔV is the operating voltage of a full cell; Vc and Va are the working
potential of cathode and anode, respectively; E is the energy density; Cc
and Ca are the specific capacity of cathode and anode, respectively. The
increase of Vc could reduce the value of ΔV, which decreases the energy
density exponentially, e.g., the T-Nb2O5/LiNi0.8Co0.1Mn0.1O2 full cell
only output the average voltage of 2.12 V [33]. Such low operating
potentials make LIBs lose their justification in comparison with the
aqueous batteries. Therefore, searching for stable host frameworks with
operating potential below 1 V has significant meaning for the anodes’
application. Most transition metal oxides and sulfides undergo drastic
phase transformation with great volume expansion at the low potential
range (0 - 1 V vs. Li+/Li).
Most transition metal oxides and sulfides undergo drastic phase
transformation with great volume expansion at the low potential range
(0 - 1 V vs. Li+/Li). Up to date, only a few anode materials have been
found for stable lithium storage under a low-voltage range. Fig. 1 firstly
summarizes these stable host anode materials with average potentials
around or below 1 V. Among these anodes, some have relatively flat
voltage plots (e.g., LiEuTiO4, Li1+xVO2), while others display sloping
voltage curves (e.g., Li0.5La0.5TiO3, SrVO3). The specific voltage-
capacity plot of each anode will be discussed in the following sections.
These materials can be generally divided into two categories according
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Energy Storage Materials 55 (2023) 364–387
Fig. 1. Schematic illustration of stable host anodes for low-voltage
lithium storage.
to their elemental composition: titanium(Ti) based and vanadium(V)
based materials. When based on the lithium storage mechanism, these
anodes can be divided into intercalation-type and conversion-type. It is
worth noting here that the conversion-type materials discussed in this
review refer to those which can provide stable lithium storage properties
with a relatively small volume change, unlike most conversion-type
materials with huge volume change during lithium insertion/extraction.
The current manuscrip firstly unifies these rigid anodes into the
scope of low-voltage materials. we highlight the breakthrough and key
progress along the timeline in Fig. 2 for these low-voltage stable host
anodes. Owing to the disparate structure and properties of these anodes,
we will separately discuss the structural features, electrochemical
properties, and lithium insertion mechanism. On this basis, the modifi­
cation methods will be summarized.
2. Titanium-based materials
Titanium-based materials such as Li4Ti5O12, TiO2, and TiNb2O7 have
been extensively investigated as high-safety anode materials due to their
high operating potential above 1 V vs. Li+/Li. Here we will focus on the
unusual titanium-based materials with operating potential below 1 V.
These anodes can be divided into three categories: Li2TiSiO5 and its
derivatives, Rare earth titanates, and Li(V1-xTix)S2 sulfides. We will
discuss the reasons for low-voltage characteristics, lithium storage
mechanism, and modification strategies of these three types of materials
in the following sections.
2.1. Li2TiSiO5 and its derivatives
2.1.1. Discovery and mechanism of LTSO for low-voltage lithium storage
Polyanionic silicate materials initially attracted attention in the field
of cathodes. Li2MSiO4 (M = Fe, Co, Mn) compounds [36–40] were
investigated as promising cathodes owing to their excellent safety,
absence of raw materials, and environmental friendliness. The SiO4
tetrahedra stabilize the Li2MSiO4 framework and induce the elevated
potential [41] of M3+/M2+, as the effect of polyanion PO4 in LiFePO4
[42]. As a member of polyanion silicates, Li2TiSiO5(LTSO) was initially
studied as a cathode material by Masquelier et al. in 2002 [43]. The
crystalline structure of Li2TiSiO5 consists of infinite interconnected
corner-shared SiO4 tetrahedra and TiO5 square pyramids where lithium
ions are located at the octahedral sites of the three-dimensional tunnels,
as shown in Fig. 3a. From the view of the b-axis, the slabs of TiSiO2− 5
slabs are separated by lithium-ion layers perpendicular to the [001]
direction. However, LTSO can only insert 0.15 lithium ions per struc­
tural formula under the discharge cut-off voltage of 1.0 V versus Li+/Li
(Fig. 3b), corresponding to the specific capacity of only 23 mA h g− 1,
making it difficult for practical application.
Y. Zhang et al.
Fig. 2. Key discovery and progress for stable host frameworks as low-voltage anodes.
No research on LTSO for anode was reported until 2017. Yongyao
Xia’s group first reported LTSO as a low-voltage anode material for LIBs
[44]. LTSO can deliver a high specific capacity of 308 mA h g− 1 at a
current density of 0.02 A g− 1 when discharged to 0 V, as shown in
Fig. 3c. The discharge-charge profile of LTSO shows that an obvious
voltage plateau is around 0.28 V, which is significantly lower than that
of LTO. In addition, the carbon-coated LTSO particles with irregular
shape and submicron size exhibit excellent cycling stability of almost no
capacity fading occurring after 1000 cycles and ~ 70 % capacity
retention at a current density of 1 A g− 1 (Fig. 3d).
To clarify the mechanism of LTSO, operando synchrotron X-ray
diffraction (XRD) and ex situ XRD were carried out (Fig. 3e). When
discharged from 3 V to 0.28 V, the corresponding XRD patterns shift
little, indicating the solid-solution process with slight structural change.
As further discharged from 0.28 to 0.1 V, the appearance and disap­
pearance of new peaks corresponding to TiO and Li4SiO4 indicate a
conversion transition occurring. Hence, they proposed a mechanism of
solid-solution process combination with conversion reaction accompa­
nied by two-electron(T4+/Ti2+) transfer. The lithiation/de-lithiation
process can be described as follow:
Li4d 4d 4e
2 TiSiO5 + xLi ↔ Li2 Lix TiSiO5 (x ≤ 0.5) (3)
Li4d 4e
2 Lix TiSiO5 + (2 − x)Li ↔ Li4 SiO4 + TiO (4)
Xia’s group further systematically probed into the fundamental
origin of the reduced redox potential of Ti4+/Ti3+ in LTSO compared to
LTO by combining X-ray Absorption Fine Structure (XAFS), 7Li magic
angle spinning NMR (7Li MAS NMR), and DFT calculations [45]. Against
the inductive effect of PO3+ 3+
4 to raise the redox potential of Fe /Fe
2+
in
LiFePO4, they considered that the SiO4 tetrahedra adjacent to the TiO5
square pyramids in LTSO framework function a reversely inducive ef­
fect, which reduces the redox potential of Ti4+/Ti3+ upon the electro­
chemical process. Such reversed inducive effect is possibly related to the
coordination of Ti from the square pyramid TiO5 to distorted octahedral
coordination upon lithium intercalation (Fig. 3f), and hence results in
the low operating potential of LTSO.
LTSO started to receive continued attention due to the following
merits: (1) LTSO has a high specific capacity (308 mA h g− 1),
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Energy Storage Materials 55 (2023) 364–387
significantly surpassing that of LTO; (2) The main operating potential
range of LTSO is between graphite and Li4Ti5O12 can prevent the lithium
dendrites while avoiding the excessive loss of output voltage; (3)
Although a conversion reaction occurs during lithium insertion, the
cycling stability of LTSO is better than most conversion-type anode
materials; (4) The low-cost constituent elements such as Si and Ti
facilitate the mass production. Based on the above advantages, LTSO
become a promising candidate for next-generation anode materials.
However, such two electron conversion between TiO and Li4SiO4 during
lithiation/de-lithiation inevitably induces phase separation and grain
distortion [46] and accompanies the unstable SEI formation [47],
leading to slow-changing but still fatal particles crack and pulverization
during long-term cycling. Moreover, LTSO also suffers from intrinsic low
electron conductivity, and the phase transformation could block the ion
transport channel, resulting in poor rate performance.
2.1.2. Modification strategies for performance improvement
Up to now, several modification strategies were applied to further
improve the electrochemical properties of LTSO. The first one is LTSO
composite with carbon materials. This strategy has been proved as an
effective strategy to enhance electronic conductivity and restrict the
volume expansion of conversion materials [48–50]. For instance, a
nanocomposite anode of LTSO and expanded graphite (EG) was facilely
synthesized via a sol-gel method. The rate performance of the
as-prepared LTSO-EG anode is greatly improved with the 60 % capacity
remaining at a high current density of 4 A g− 1 [51]. Zheng et al. pro­
posed a dual-modified carbon strategy consisting of graphitized carbon
nanotubes (CNT) and amorphous carbon to form a 3D carbon network
for more sufficient encapsulation of LTSO [52], as shown in Fig. 4a. As a
result, the C@LTSO@CNT anode exhibits the excellent high-rate capa­
bility of over 125 mAh g− 1 at over 10 C (3.15 A g− 1) and durable cycling
performance of 1500 cycles without any decay (Fig. 4b). After pairing a
LiFePO4 (LFP) cathode, the full cell displays the output voltage of over 3
V and high-rate capacity of 165.8 mAh g− 1 at 7.5 C and 113.0 mAh g− 1
at 10 C (Fig. 4c), respectively, demonstrating a superior power perfor­
mance. To reduce synthesis costs, Xutang Tao and co-workers employed
a one-pot method by utilizing pitch as carbon source to synthesize soft
carbon-combined LTSO composites [53]. The anode exhibits a reversible
Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

Fig. 3. (a) Crystal structure of LTSO along the c axis. (b) Potential-composition curves of LTSO vs. Li+/Li. (a-b) Reproduced with permission [43]. Copyright 2014,
American Chemical Society. (c) Voltage-capacity curves of LTSO for the first 2 cycles at the cut-off potential of 0 V. (d) long-term cycling performance at 0.5 A g− 1
and rate capability of LTSO. (e) Ex situ XRD patterns of LTSO electrode at different states of charges, each XRD pattern shown by Log(intensity) vs. 2θ plots, the
discharge products Li4SiO4 and TiO labeled by azure circles and orange triangles, respectively. (c-e) Reproduced with permission [44]. Copyright 2017, Royal Society
of Chemistry. (f) Reversed inductive effect of LTSO with the coordination change of the TiO5 square pyramid during lithiation. Reproduced with permission [45].
Copyright 2021, American Chemical Society.

capacity of 127 mAh g− 1 at 3.2 A g− 1 and remains 273 mAh g− 1 at 0.5 A
g− 1 after 1500 cycles. However, these anodes with high-content carbon
nanocomposites via the conventional slurry coating method would
generate abundant micropores inside the electrode, significantly lowing
the tap density of the electrodes and reducing the volume energy den­
sity. Hence, Hersam et al. presented a dense graphene-functionalized
LTSO (G-LTSO) electrode through thermal processing of pyrolyzing
the ethyl cellulose to compact the electrode. The electrode packing
density reaches exceptional 80 %, exceeding most reported anode ma­
terials (e.g., Nb16W5O55, Nb2O5/G, T-Nb2O5, LTO/C, and graphite), as
shown in Fig. 4d. When the dense electrode density is combined with the
low-voltage characteristics of Li2TiSiO5, the G-LTSO behaves extremely
high volumetric energy densities at extended current densities ranges
compared to other intercalation-type anode materials (Fig. 4e).
Morphology modification is another effective way to regulate the ion
diffusion route, increase the electrolyte penetration, and buffer the
volume expansion of the LTSO anode. For the Li2O-TiO2-SiO2 triple
phases system, the conventional hydrothermal reaction is hard to
directly synthesize the specific morphology because of the high phase
formation temperature of LTSO (> 800 ◦ C). Instead, recently-emerging

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Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

Fig. 4. (a) Schematic illustration of dual-carbon network for LTSO. (b) The long-term cycling performance of C@LTSO@CNT. (c) The rate capability of the
C@LTSO@CNT full cell with LiFePO4 as a cathode. (a-c) Reproduced with permission [52]. Copyright 2019, Wiley. (d) Electrode packing percentage of G-LTSO and
other reported anode materials. (e) Volumetric energy density as a function of current density vs. a 4 V cathode for G-LTSO and other reported non-alloying anode
materials. (d-e) Reproduced with permission [46]. Copyright 2020, Elsevier.

methods including electrostatic spinning [54–57], chemical vapor
deposition (CVD) [58], and atomic layer deposition (ALD) [59] were
applied to control the morphology. Li Liu et al. synthesized
nitrogen-doped carbon encapsulated LTSO (LTSO-NDC) nanofibers via
an electrospinning method [54]. As shown in Fig. 5a, organic in­
gredients of LTSO, carbon source, and nitrogen source were mixed and
fill into the medical syringe. Under the pressure of the pump, the pre­
cursor fibers were collected and calcined under Ar atmosphere to obtain
the LTSO/C nanofibers. The nanofibers with a diameter of 200 nm
(Fig. 5b) perform a reversible capacity of over 250 mAh g− 1 at 1 A g− 1
with a working platform of 0.28 V. However, the capacity decay starts to
emerge after 750 cycling at 0.5 A g− 1, as shown in Fig. 5c. Xianluo Hu
and co-workers obtained LTSO fibers coated by an in-situ grown Li-Ti-O
layer by combining the electrospinning and ALD methods, [59] as
shown in Fig. 5d. The electrochemical performance of several samples
with different coating thickness was compared with the pristine LTSO
fibers. The ALD-300 sample referring to the one which was treated by
ALD for 300 cycles exhibits the highest specific capacity of 229 mAh g− 1
at 0.5 A g− 1 after 400 cycles (Fig. 5e) and the best rate capacity of 154
mAh g− 1 at 5 A g− 1 (Fig. 5f), which is 30 mAh g− 1 higher than that of
pristine LTSO fibers. The Nyquist plots suggest that ALD-300 endows the
smallest charge transfer resistance compared to other samples (Fig. 5g),
indicating the coating layers enable the fast Li+ transfer kinetics. How­
ever, these methods mentioned above need complicated synthetic pro­
cesses, and are difficult to achieve the mass-produce for LTSO. To this
end, Yu et al. developed a crystalline-platelet LTSO with (001)
plane-preferred exposure via a facile molten-salt strategy [60]. The
obtained LTSO platelets were followed to be treated by hydrothermal
reaction and calcination process to in-situ form a “photo-frame” like
TiO2 nanocrystal and carbon coating layers. The introduction of TiO2

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Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

Fig. 5. (a) Illustration of the synthesis of LTSO-NDC nanofibers. (b) Successive discharge/charge curves of LTSO-NDC nanofibers at 1 A g− 1. (c) Long-term per­
formance of LTSO-NDC nanofibers at 0.5 A g− 1. (a-c) Reproduced with permission [54]. Copyright 2020, Royal Society of Chemistry. (d) Illustration of the synthesis
of LTSO fibers with Li-Ti-O layers via electrospinning and atomic layer deposition. (e) The comparison of cycling performance between pristine LTSO fibers and LTSO
fibers with different thicknesses of Li-Ti-O layers at 0.5 A g− 1. (f) the corresponding comparison of rate performance. (g) The corresponding comparison of Nyquist
plots. (d-g) Reproduced with permission [59]. Copyright 2020, Elsevier. (h) The long-term cycling performance of TiO2 layer-modified LTSO platelets. Reproduced
with permission [60]. Copyright 2020, Wiley.

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Y. Zhang et al.
nanocrystal could accelerate the Li+ diffusion, and restrain the volume
expansion. The TiO2 layer-modified LTSO with certain crystal facets
exposure delivers a capacity of 196 mA h g− 1 at 500 mA g− 1 after 500
cycles with the capacity retention of 99.4 % (Fig. 5h inset). Even after
10000 cycles at 2000 mA g− 1, the capacity retention still reaches 66 %
(Fig. 5h), demonstrating excellent stability of the as-prepared anode.
The ex-situ TEM and corresponding SAED patterns were applied to
directly observe the microstructural evolution of LTSO at various dis­
charge/charge states. The LTSO lattice exhibit no obvious distortion or
transformation except for the reversible phase transition of surficial
TiO2 to LiTiO2 during lithiation/de-lithiation, demonstrating the high
stability of the double layer coated LTSO anode.
2.1.3. Derivatives from LTSO
Na2TiSiO5(NTSO), as a derivative of LTSO, was also investigated as a
low-voltage anode for LIBs because of the abundant Na source compared
to the Li source [61,62]. Na2TiSiO5 possesses three polymorphs. The
T-NTSO named natisite has a similar layer structure to that of Li2TiSiO5,
which has a tetragonal structure (P4/nmm) with infinite layers
comprising corner-shared TiO5 square pyramids and SiO4 tetrahedra
and Na+ in the interlayer, as shown in Fig. 6a. The lithium storage
properties of Na2TiSiO5 were first investigated by Yu et al. as an anode
for LIBs. T-NTSO obtained by a facile hydrothermal reaction delivers the
second discharge capacity of almost 320 mAh g− 1 at 100 mA g− 1 with an
average operating voltage of 0.9 V (Fig. 6b). Similar to LTSO, the cycling
performance of T-NTSO is quite stable, which exhibits 94 % capacity
retention at 500 mA g− 1 after 100 cycles. Our group further enhanced
the electrochemical properties of T-NTSO through the one-pot
Fig. 6. (a) Crystal structure of T-NTSO. (b) Charge/discharge curves of T-NTSO in the 2nd and 3rd cycles at 0.1 A g− 1. (a-b) Reproduced with permission [65].
Copyright 2019, Royal Society of Chemistry. (c) Long-term cycling performance of O-NTSO nanowires at 0.5 A g− 1. Inset: the selected discharge/charge curves at 0.5
A g− 1. Reproduced with permission [64]. Copyright 2022, Wiley.
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Energy Storage Materials 55 (2023) 364–387
hydrothermal synthesis of porous assemblies of Na2TiSiO5 nanotubes
[63]. The anode could achieve a high capacity of over 400 mAh g− 1 at
100 mA g− 1 and remain 77 % capacity retention after 3000 cycles.
Recently, Haijun Yu and his co-workers further studied orthorhombic
Na2TiSiO5 (O-NTSO) as a low-voltage anode for LIBs [64]. O-NTSO
nanowires synthesized by the electrospinning method could provide a
reversible discharge capacity of 246 mAh g− 1 in 2nd cycle at 50 mA g− 1
(Fig. 6c inset). The discharge-charge profile displays no obvious voltage
plateau but sloping curves with the average potential of 1.1 V. The ca­
pacity remains 53 % when the current density is increased from 0.5 to
4.0 A g− 1, demonstrating considerable rate performance. After being
activated for five cycles at 50 mA g− 1, the O-NTSO anode has been
cycled for 1000 cycles at 500 mA g− 1 with a high capacity retention of
97.8 % (Fig. 6c). In addition, kinetic analysis employed by cyclic vol­
tammetry (CV) indicate that both capacitive and diffusion behavior
control the specific capacity of O-NTSO.
Apart from Na2TiSiO5, Li2TiGeO5, as another derivative anode ma­
terial from LTSO, was investigated by Xia et al. with an operational
potential of 0.5 V vs. Li/Li+. Li2TiGeO5 has a similar structure to LTSO,
which consists of corner-linked TiO5 square pyramids and GeO4 tetra­
hedra and lithium ions located in the interlayer [66]. Carbon-coated
Li2TiGeO5 exhibits a high initial discharge capacity of 1021 mAh g− 1,
and initial charge capacity remains 691 mAh g− 1 with a low initial CE of
68 %. The high initial discharge capacity can be attributed to a con­
version reaction and subsequent Li-Ge alloying process. Like other
conversion anodes, part of the produced Li2O from the structural
transformation cannot participate in the de-alloying process durithe ng
charge process, leading to the low initial CE. However, unlike most
Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

conversion or alloying anodes whose capacities decay rapidly, carbon Li2TiSiO5 with (001) plane exposure exhibits ultralong cycling perfor­
coated Li2TiGeO5 with irregular submicron sizes displays stable cycling mance of 66 % capacity retention after 10000 cycles [60]. The Table 1
performance, achieving a discharge capacity of 406 mAh g− 1 after 600 summarizes the synthetic methods, initial capacity, rate performance,
cycles at 1 A g− 1, corresponding to 91 % capacity retention. The and cycling performance of the modified anodes. As recently-emerging
decomposition products including amorphous TiO and Li2O probably new anodes, LTSO and its derivatives have potential for
act as buffers to release the volume change from Li-Ge alloying/deal­ next-generation anodes. To this end, several issues need to be resolved:
loying during cycles. Recently, similar electrochemical properties can be (1) the low initial coulombic efficiency (< 75 %) induced by phase
found in similar structure of Na2TiGeO5 [67] and LiNbGeO5 [68], which transformation and SEI formation at low voltage range during first
presents better cycling stability without obvious capacity decay after lithiation; (2) severe polarization of the dense electrode at high rate; (3)
4000 cycles of Na2TiGeO5 and 5000 cycles of LiNbGeO5, respectively. inferior electrochemical properties of the thick electrode. More
The synergistic effects from multicomponent provide a new way to advanced technologies and strategies need to be applied to tap the po­
improve the performance of conversion-type materials instead of the tential of LTSO and NTSO as low-voltage anodes.
morphology modification strategy.
In summary, Li2TiSiO5 and its derivatives including Na2TiSiO5,
2.2. Rare earth titanates
Li2TiGeO5, Na2TiGeO5, and LiNbGeO5 exhibits operating potential
below 1 V with conversion reaction occurring during lithiation/de-
Rare earth (RE) elements are designated as a group of VI elements
lithiation process. The excellent cycling stability has been achieved in
from lanthanum to lutetium, and generally yttrium and scandium are
these anodes without exquisite nanostructing or high-content carbon
also considered as RE elements because they are often found in minerals
additives, suggesting that such conversion processes do not experience
along with RE. In the field of LIBs, RE are usually used as trace elements
drastic volume changes like other transition metal oxides (e.g., Fe3O4,
to dope into the active materials or coating on the surface to improve the
MoO3, CoO, NiO). In addition, the in-situ formation of amorphous
electrochemical properties of anodes. For example, Dy3+ doped
products during conversion reactions evenly disperses around the active
Li4Ti5O12 exhibits a specific capacity of 165 mAh g− 1 under the current
grains, further buffering the volume change. For pristine Li2TiSiO5
density of 100 C [71]. There are few reports regarding compounds with
anode, the main operating voltage ranges between 0.2 and 1 V along
RE as the main constituent elements for anode materials, among which
with a two-electron (T4+/Ti2+ redox couples) conversion process be­
two series of titanium-based perovskite oxides display the low-voltage
tween TiO and Li4SiO4. The discharge voltage plateau lies at 0.28 V and
character.
charge voltage plateau lies at 0.7 V at a current density of 0.02 A g− 1.
Over 0.4 V voltage difference at 0.02 A g− 1 shows severe voltage po­
2.2.1. Lithium lanthanum titanates
larization even at small current density, indicating the poor Li+ diffusion
Perovskite-type lithium lanthanum titanate Li3xLa(2/3)-xTiO3 (0 < x <
kinetics. Several modification strategies including morphology adjust­
0.16) have been attracted a considerable attention as Li-ion conductors
ment, coating, and ion doping were applied to enhance the electro­
due to their high bulk conductivities (10− 3 S cm− 1) at room temperature
chemical properties and achieved some progress, e.g., graphene-
and broad electrochemical stability window (8 V vs. Li/Li+) [72,73].
functionalized Li2TiSiO5 electrode with high packing density (2.122 g
They are derived from the perovskite-type ATiO3 structure where cation
cm− 3) displays exceptional volumetric energy density over a wide spe­
A are partially replaced by both Li and La atoms and hence provide a
cific current range between 101 and 104 mA g− 1; [46]. TiO2 coated
large number of vacant sites for Li+ transport, as shown in Fig. 7a.

Table 1
Summarization of synthesis methods, average discharge voltage, 1st charge capacity, rate capability, and cycling performance of various LTSO and its derivatives.
Material Synthesis method Average 1st charge capacity Rate capability Cycling performance
discharge
voltage
Current Capacity Current Capacity Current Cycling Capacity
density (A (mAh g− 1) density (A (mAh density (A number (mAh g− 1)
g− 1) g− 1) g− 1) g− 1)

Li2TiSiO5@C [44] Sol-gel 0.28 V 0.02 308 1 169 0.5 1000 172
Li2TiSiO5/EG [51] Sol-gel 0.43 V 0.2 200 4 140 0.2 100 190
C@ Li2TiSiO5/CNT Sol-gel 0.28 V 0.16 430 3.2 124 0.8 1500 410
[52]
C@TiO2@ Li2TiSiO5 Molten-salt 0.5 V 0.1 325 1 150 2 10000 79
[60] Hydrothermal
Li-Ti-O@ Li2TiSiO5 Atomic layer 0.28 V 0.2 230 5 154 0.5 400 228
fibers [59] deposition
G/ Li2TiSiO5 [46] Sol-gel 0.3 V 0.03 250 9 50 0.3 50 240
Li2TiSiO5 glass Heating-treating 0.28 V 0.2 116 5 180 5 5000 180
ceramic [69]
Na+ doped Li2TiSiO5 Sol-gel 0.7 V 0.5 158 5 100 0.5 150 130
[70]
Li2TiSiO5/NDC Electrostatic 0.75 V 0.05 333 4 108 0.5 500 240
nanofibers [54] spinning
Nb5+ doped Electrostatic 0.3 V 0.05 247 5 125 2 500 129
Li2TiSiO5 fibers spinning
Li2TiSiO5/C [53] Sol-gel 0.3 V 0.1 320 3.2 127 0.5 1500 250
Na+ doped Electrostatic 0.75 V 0.5 400 7 100 5 1500 200
Li2TiSiO5/C fibers spinning
[56]
Na2TiSiO5 [65] Hydrothermal 0.8 V 0.1 325 0.5 200 0.5 100 188
O- Na2TiSiO5 fibers Electrostatic 1V 0.05 246 4 87 0.5 1000 163
[64] spinning
Li2TiGeO5 [66] Solid-state 0.5 V 0.02 691 5 287 1 600 406
Na2TiGeO5 [67] Hydrothermal 0.5 V 0.05 410 2 130 0.5 4000 309

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Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

Fig. 7. (a) Crystal structure of Li0.5La0.5TiO3. (b) Rietveld refinement based on powder XRD. (c) Comparison of discharge/charge curves between Li0.5La0.5TiO3 and
LTO. (d) Comparison of rate capability for bulk Li0.5La0.5TiO3, bulk LTO and nano LTO. (e) Long-term cycling performance of Li0.5La0.5TiO3 at 10 C. (a-e) Reproduced
with permission [77]. Copyright 2020, Nature Publishing Group. (f) Representation of the crystal structure of NaYTiO4. (g) Comparison of the discharge/charge
profiles between LiYTiO4 and LiEuTiO4 after four cycles at 0.2 C. (f-g) Reproduced with permission [78]. Copyright 2013, American Chemical Society. (h) The
comparison between LiFePO4/LTO and LiFePO4/LiYTiO4 full cell in terms of operating potential and discharge capacity. Reproduced with permission [79].
Copyright 2022, Wiley.

Nakamura et al. firstly investigated the lithium insertion properties of
Li0.37La0.5Ti2.90 as a cathode material for LIBs. They pointed out that
lithium ions could occupy the A-site vacancies and 3c-site, providing the
ideal capacity of 160 mAh g− 1 with the potential below 1.5 V vs. Li+/Li
[74]. Wakihara and co-workers deeply investigated the electronic
structural change upon lithium intercalation of Li3xLa(2/3-x)TiO3 [75].
They found that a transition from insulator to metal occurred accom­
panied by the reduction from Ti4+ to Ti3+. These results indicate lithium
lanthanum titanate has the potential for low-voltage and high-rate
anode materials for LIBs. Wang et al. synthesized Li0.27La0.54TiO2.945
through a sol-gel method and studied the electrochemical properties
between 0.01 and 2 V. The reversible charge capacity delivers 145 mAh
g− 1 with slopping operating potential around 1 V [76]. Recently, Du
et al. increased the lithium content and decreased the content of
lanthanum to synthesize lithium-rich La0.5Li0.5TiO3 as a high-rate anode
material with moderate operating potential. The refinement of XRD
patterns of La0.5Li0.5TiO3 suggests that La0.5Li0.5TiO3 belong to tetrag­
onal phase with space group of P4/mmm (Fig. 7b). The anode delivers a
reversible capacity of 229 mAh g− 1 with an average potential around 1 V
capability and long-term stability. The La0.5Li0.5TiO3 electrode exhibits
the reversible capacity of nearly 100 mAh g− 1 at 10 C and 79 % capacity
retention after 3000 cycles (Fig. 7e). In situ synchrotron X-ray diffrac­
tion patterns during charge/discharge process indicates a highly
reversible solid-solution transition occurring with a two-phase transition
from pseudo-cubic to tetragonal structure to accommodate more lithium
ions.
2.2.2. ALnTiO4 (A = Na or Li, Ln = rare earth)
Apart from lithium lanthanum titanate, Goodenough et al. reported
another perovskite-type layered oxides ALnTiO4 (A = Na or Li, Ln = rare
earth) for reversible lithium insertion/extraction [78]. The structure of
NaLnTiO4 is originated from the structure of orthorhombic La2CuO4 by
substituting alkali ions for Ln3+ and Ti4+ for Cu2+ sites, which contains
two rock salt layers of NaO and LnO alternating with corner-shared TiO6
octahedra layers, as shown in Fig. 7f. LiLnTiO4 possesses similar struc­
ture with orthorhombic structure to NaLnTiO4 except for the smaller
lithium ions forming the antifluorite layers. The internal electric field
generated by positive (LnO)2+ 2−
2 layer and negative (NaO)2 or (Li2O2)
2−

under the current density of 0.1 C (1 C = 200 mA g− 1). In comparison
with commercial Li4Ti5O12 anode, the dual merits of higher capacity and
lower potential render La0.5Li0.5TiO3 a promising candidate in the
practical application (Fig. 7c). In addition, bulk La0.5Li0.5TiO3 displays
better rate capability than nano and bulk LTO owing to the rapid lithium
diffusion kinetics (Fig. 7d). The anode also demonstrates excellent rate
layer is perpendicular to the bilayers and leads the displacement of TiO6
octahedra from the center site. Electrochemical tests were carried out to
both NaLnTiO4 and LiLnTiO4 under the voltage range from 0.01 to 2.5 V
vs. Li+/Li, and the charge/discharge profile of LiYTiO4 and LiEuTiO4 at a
rate of 0.2 C is shown in Fig. 7g. LiYTiO4 displays two plateaus near 0.1
V and 0.3 V, while LiEuTiO4 shows a plateau of 0.8 V vs Li+/Li. Other Ln

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compounds have similar voltage plateaus to LiYTiO4. Based on the fact
that the position and of the platforms are almost the same other than the
difference of the Ln elements, the platforms of are probably attributed to
the Ti4+/Ti3+ redox except for LiEuTiO4 and NaEuTiO4 which show 0.8
V voltage platform due to the Eu3+/Eu2+ redox. The almost 1 V voltage
reduction of these layered perovskites compared to spinel Li4Ti5O12 may
due to that the parallel-plate condense-like internal electric field raises
the energy of Ti4+/Ti3+ redox. The strategy of tuning the redox energy
by internal electric field is attractive. However, no further research has
been carried out so far. In 2017, our group conducted further research
on the electrochemical properties of LiEuTiO4 as a 0.8 V
intercalation-type anode [80]. Through a facile sol-gel method followed
by ion-exchange reaction, LiEuTiO4 anode delivers 219 mAh g− 1 (the
2nd discharge) with an operating potential of 0.8 V. The anode reveals
superior rate capability and cycling stability due to the rapid Li+ diffu­
sion kinetics in the layered perovskite framework. When the current
density ranges from 1 A g− 1 to 4 A g− 1, the capacity of 117 mAh g− 1 can
be retained with the CE of 98.2 %. In comparison of valance states of Eu
in the pristine sample, the valance states of Eu after discharged to 0.01 V
can be observed to change by X-ray photoelectron spectroscopy (XPS)
analysis, while the valence state of Ti has not changed after discharged
to 0.01 V. Recently, we further deeply investigated the electrochemical
properties and lithium storage mechanism of layered perovskite LiYTiO4
[79]. LiYTiO4 anode could present an average potential of 0.3 V vs.
Li+/Li and deliver a reversible capacity of 236 mAh g− 1. Moreover, the
anode also demonstrates outstanding rate performance, which achieves
112 and 87 mAh g− 1 at 60 C and 100 C (1 C = 200 mA g− 1), respectively.
As a result, the full cell of LiFePO4/LiYTiO4 exhibits higher discharge
capacity and higher operating potential than those of LiFePO4/LTO, and
is 2.4 times that of LiFePO4/LTO in terms of energy density (Fig. 7h). In
situ XRD analysis and DFT calculations reveal that a reversible
three-phase solid solution reaction with rapid Li+ migration along the
2D channels in LiYTiO4 occurs during discharge and charge.
Fig. 8. (a-b) The comparison of 1st discharge-charge curves between LiVS2, LiV0.5Ti0.5S2, and LiV0.6Ti0.4S2. (c-d) The comparison of cycling performance between
LiTiS2, LiV0.5Ti0.5S2, and LiV0.6Ti0.4S2. a-d) Reproduced with permission [81]. Copyright 2016, Nature Publishing Group.
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Energy Storage Materials 55 (2023) 364–387
2.3. Li(V1-xTix)S2 Sulfides
Binary transition metal sulfides MS (M = Ti, V, Cr, Fe, and Co) occur
conversion reaction with the production of M and Li2S as Li+ insert into
at low potentials [82]. Goodenough et al. investigated the electro­
chemical insertion of Li+ into the lithium transition metal sulfides LiMS2
(M = Ti, V, and Cr) [83,84]. They confirmed that the voltage plateau
corresponding to Ti3+/Ti2+ redox couple in LiTiS2 lies in 0.5 V vs.
Li+/Li, while the V3+/V2+ level in LiVS2 is at 1.0 V vs. Li+/Li. The
low-voltage character from Ti3+/Ti2+ and V3+/V2+ redox couples in
LiTiS2 and LiVS2 is attractive. However, for LiVS2, although the
discharge voltage platform is at 1.0 V, the subsequent charge process
with Li+ extraction occurs at 1.4 V even at a low current density of 20
mA g− 1, resulting in severe polarization. For LiTiS2, it encounters
massive irreversible capacity loss (180 mAh g− 1) at initial cycle and
rapid capacity decay during cycling, in which the capacity reduces to
120 mAh g− 1 after only five cycles [83]. To enhance the cycling stability
and reduce the polarization, Bruce et al. proposed to adjust the
solid-solution ratio of Ti/V to optimize the electrochemical properties of
Li(V1-xTix)S2 [81]. LiV0.5Ti0.5S2 displays the higher reversible capacity
at 1st cycle and better cycling performance after 100 cycles in compar­
ison with LiV0.6Ti0.4S2 (Fig. 8a and 8c). The comparison of
discharge-charge profile between LiV0.5Ti0.5S2 and LiVS2 demonstrates
the obvious decrease of voltage plateau and smaller voltage polarization
of LiV0.5T0.5S2 (Fig. 8b). In addition, the cycling performance of
LiV0.5T0.5S2 is significantly better than that of LiTiS2, as shown in
Fig. 8d. Such dual merits render LiV0.5T0.5S2 as a promising candidate
for low-voltage anode. However, still 11 % of the first capacity loss and
continuous capacity decay exist with the normal electrolyte (1 M LiPF6
in ethylene carbonate–dimethyl carbonate 1:1), which means unremit­
ting interfacial reactions occur during the cycles. Further work needs to
be done to form robust SEI and decrease the side reactions. However, no
relevant studies have been reported so far.
Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

3. Vanadium-based materials
Vanadium-based compounds have been intensively researched for
many years in the field of energy storage [85]. Vanadium, as a transition
metal element of the VB group, has several valence states varying from
+2 to +5, which means multiple electrons transfer process may occur
during ion insertion/extraction and a high specific capacity can be
achieved. In addition, since the flexible valance change of vanadium,
vanadium-based family consists of a large number of compounds with
different compositions, crystal structure and electrochemical properties
[86]. Based on the several valence states of vanadium and diverse crystal
structures, continual and enormous research were conducted on
vanadium-based materials for metal-ion batteries beyond lithium in
recent years [87]. In the field of anode materials for LIBs, various types
of vanadium-based materials have been developed for many years, but
most of them including MxVyOz (M = Co, Cu, Mn, Fe, Zn, Ni) belong to
the conversion-type materials with drastic volume change and phase
transformation [88–92], which are not within the scope of this review.
In this review, we retrospect the important advances on several stable
vanadium-based frameworks with emphasis on the low-voltage
property.
3.1. Li3VO4
3.1.1. Fundamental understanding of LVO as a low-voltage insertion anode
Since first proposed in 2013 by Haoshen Zhou’s group as an
insertion-type anode, Li3VO4(LVO) has received tremendous attentions
and dozens of papers were published to report the progress in the aspect
of lithium storage properties. It has been favored due to: (1) an
intercalation/de-intercalation mechanism, leading the small volume

Fig. 9. (a) The comparison of LVO with

LTO and graphite in terms of operating
potential, specific capacity and, energy
density. (b) XRD pattern of the as-
prepared LVO by solid-state reaction;
the inset shows the crystal structures of
β-form LVO where oxygen atoms are
marked by blue balls, the LiO4 and VO4
tetrahedra are denoted by green and red
color, respectively. (c) The first three
galvanostatic discharge-charge curves
of LVO at a current density of 20 mA
g− 1 between 0.2-3 V vs. Li+/Li. (d)
Cycling performance of LVO at a current
density of 20 mA g− 1 between 0.2-3 V
vs. Li+/Li. (e) Ex-situ XRD of the LVO
electrode at different state of charge
during first discharge/charge process.
Reproduced with permission [93].
Copyright 2013, Wiley.

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change and highly structural stability when suffering long-term lithium
ions insertion and extraction compared with other alloying or conver­
sion type materials [94–97]; (2) the main operating voltage ranging
between 0.5 and 1 V (Fig. 9a), effectively avoiding the tendency of
lithium dendrites compared with graphite [98,99] and halving output
voltage compared with LTO [100,101]; (3) relatively higher specific
capacity than LTO (394 mAh g− 1 vs. 175 mAh g− 1); (4) low cost because
of the abundant V resource and facile synthetic method. Such merits can
be owing to the unique structure of LVO and the lithium storage
mechanism.
LVO for lithium storage belongs to β-Li3VO4 which is stable at rela­
tively low temperature (< 700 ◦ C), while another polymorph γ-Li3VO4
can be transferred to β-Li3VO4 when temperature reduces [102,103].
Unless otherwise specified, the LVO mentioned below refers to β-Li3VO4.
As the isostructural oxide to Li3PO4, LVO possesses orthorhombic
structure, and the XRD patterns can be indexed by the standard PDF card
(JCPDS No. 38-1247), as shown in Fig. 9b. LVO is composed of
corner-connected LiO4 and VO4 tetrahedrons which form the hollow
lantern-like 3D framework (Fig. 9b inset). The hollow 3D structure may
provide many empty sites and lithium migration channels. Haoshen
Zhou and co-workers first discovered that LVO could deliver a charge
capacity of 302 mAh g− 1 at 1st cycle with the average discharge voltage
below 1 V (Fig. 9c). In addition, when cycled at 20 mA g− 1 between
0.2-3 V, 87 % capacity retention can be achieved after 25 cycles
(Fig. 9d). The preliminary electrochemical tests indicate that Li3VO4 has
great potential as low-voltage anode material. To figure out the mech­
anism, they further employed ex XRD to determine the structural evo­
lution during charge/discharge process. As shown in Fig. 9e, three new
peaks at around 17.5◦ , 33.5◦ and 49◦ appear and enhance until discharge
to 0.2 V, indicating the second phase generated. Upon charging, the
appeared new peaks weaken and finally vanish when charge back to 3V,
leaving only the original XRD patterns of LVO, demonstrating a
reversible insertion mechanism. However, which phase these peaks
belong to needs further investigation. In addition, the structural change
under deep discharge (< 0.2 V) needs to be clarified.
Jeong et al. found that V2+ exists in the lithiated LVO when dis­
charged down to 0.1 V by ex XPS analysis, indicating the possible
variation from V5+ to V2+ [104]. The progressive understanding was
proposed by Zhao et al. through combining the first-principles calcula­
tion and in-situ XRD [105]. As shown in Fig. 10a, two possible

Fig. 10. (a) Schematic description of graphite-like LVO upon full Li insertion. (b) In-situ XRD patterns of LVO/C anode during 1st discharge-charge process. (c) The
second cycle open-circuit voltage curves of LVO/C sample. (a-c) Reproduced with permission [105]. Copyright 2015, Elsevier. d) In-situ XRD patterns of the LVO
anode in the first cycle. Reproduced with permission [106]. Copyright 2016, American Chemical Society. (e) Calculated voltage-composition curve at 0 K for LVO
according to the convex hull. Reproduced with permission [94]. Copyright 2016, American Chemical Society. (f) DFT calculations of LVO projected along c-axis and
a-axis and the diffusion energy barrier before and after lithiation. VO4 and LiO4 tetrahedron are plotted in yellow and blue, respectively. V: Cray; Li: Blue; O: Red.
Reproduced with permission [107]. Copyright 2017, Wiley. (g) Selected regions of in-situ SXRD patterns of LVO hollow nanospheres at representative
discharge-charge states during the first cycle at a current density of 0.1 A g− 1. Reproduced with permission [108]. Copyright 2021, Wiley.

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Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

Li-insertion sites (2a and 4b sites) are calculated to stably accommodate
three lithium ions per unit LVO. Three lithium ions inserted means the
higher reversible specific capacity can be achieved when discharged to
0.1 V. Further in-situ XRD results (Fig. 10b) reveal that the whole pro­
cess of lithium insertion can be divided into three stages (Fig. 10c). The
first stage belongs to the solid-solution process until discharge to 0.8 V,
in which all the typical peaks of LVO slightly shifts to low angle field and
no new peak appears, indicating the increase of interplanar spacing and
integrity of the original structure. The second stage is the process of
two-phase transition, corresponding to several new peaks appearance.
When deep discharged to 0.1 V, all the formed peaks weaken, except two
peaks appear at 17.4◦ and 37.5◦ , indicating another new phase forma­
tion (stage three).
However, the intensity of the peaks is relatively weak, and the rough
background covers up some important XRD information during charge/
discharge. In addition, which phases the newly formed typical peaks
belong to need to be figured out. Therefore, Sun et al. performed in-situ
XRD once again to study the phase transition and some new insights
were disclosed [106]. The fact that two new phases appear and one of
them does not vanish in the end of the initial cycle proves that an irre­
versible phase transformation exists at the end of discharge (Fig. 10d).
Moreover, the formation of SEI during first cycles was also verified by
in-situ EIS. The SEI and irreversible phase transformation leads to
capacity loss (30 %), and hence lower the ICE. Amador et al. investigated
the lithium insertion mechanism and various Li3+xVO4 configurations
by density functional theory [94]. Based on the optimized structure, the
original LVO has hexagonal package structure, which is noted as H1
structure (Fig. 10e). Upon lithium insertion, a stable intermediate phase
H2-Li5VO4 is formed at 0.7 V. The simulated XRD patterns are consistent
with the experimental findings. The close structural relationship be­
tween H1 and H2 render a moderate structural transition with a low
volume expansion of 4 %. However, with the third lithium insertion, the
H2 structure would be reconstructively transformed to an
antifluorite-type C structure of Li6VO4 with 20 % volume expansion. The
transformation of H to C occurring in low predicted voltage range (0.14
V vs. Li+/Li) make unlikely the reversible insertion of the third lithium
ion. The result partially explains the initial capacity loss. However,
whether three lithium ions inserted into Li3VO4 are still controversial
because most reported capacity values are between 1.5-2.5 Li per unit
LVO. Although the LVO@C [109,110] or nanosized LVO [110] obtained
from some solution-based methods deliver capacity of over 500 mAh
g− 1, the high capacity may not all be from the V5+/V2+ redox but from
the existence of carbon and large specific surface area of nanostructure
which may induce great capacity contribution via surface or pseudo­
capacitive lithium storage [111–113]. In addition, Yu et al. further
calculated the energy barriers of two Li+ inserted sites (2a and 4b)

Fig. 11. (a) Charge− discharge curves (from 1st to 20th cycle) of pristine-LVO/MWCNT (60/40) composite half-cell at 0.25 C (1 C = 394 mA h g− 1). Inset: voltage
hysteresis (ΔV) vs cycle number. (b) Plots of Li diffusion coefficients and corresponding galvanostatic intermittent titration technique (GITT) lithiation curves for
activated and nonactivated pristine LVO/MWCNT. (c) Overall redox mechanism of LVO without (left) and with (right) activation process. Without activation, the
accommodation of the reversible 5+/4+ vanadium valence state is ensured by a shift out of the center of the Td environment. With activation the reduction down to
V3+ induce irreversible migration of V to Oh sites and further de-lithiation/lithiation proceed mainly via local distortion. Reproduced with permission [116].
Copyright 2018, American Chemical Society.

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Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

[107], as shown in Fig. 10f. The calculation results display that the
energy barrier of 2a sites and 4b sites in pristine LVO are 0.49 eV and
0.66 eV, respectively, which are comparable with high-rate inter­
calation-type anode materials [114,115], indicating the rapid lithium
diffusion kinetics. Sun et al. employed in-situ synchrotron X-ray
diffraction (SR-XRD) to identify the real-time structural variation of LVO
during charge/discharge process [108]. The new peaks which corre­
spond to the XRD patterns of Li3+xVO4 and Li3+yVO4 appear successively
during discharge and vanish during charge, proving a reversible inser­
tion/extraction mechanism for LVO (Fig. 10g).
The above mechanism studies have focused on the structural changes
of LVO during the first two charge/discharge process. Naoi and co-
workers further elucidated the structural and electrochemical signa­
ture changes during cycling by combining in situ/operando X-ray
diffraction and X-ray absorption fine structure (XAFNS) analyses [116].
As shown in Fig. 11a, obvious decrease of the polarization (ΔV)
accompanied by the continuous change of the galvanostatic profiles
from the first to tenth cycle is observed in the first twenty 20 cycling
plots of LVO anode. The electrochemical signature indicates that LVO
undergoes an activated process during repeated lithium insertion and
extraction, which is also proved by the increase of lithium diffusion
coefficients in 2 orders of magnitude between pristine LVO and the one

Fig. 12. (a) Illustration of the formation for mesoporous LVO/C hollow spheres. (b) SEM and TEM images of LVO/C hollow spheres. (a, b) Reproduced with
permission [117]. Copyright 2016, Royal Society of Chemistry. (c) Schematic illustration for the synthesis procedure of mesoporous LVO/C submicron-ellipsoids with
reduced graphene oxides. (d) Corresponding SEM and TEM images. (c, d) Reproduced with permission [118]. Copyright 2015, Wiley. (e) Schematic mechanism of the
synthesis procedure of the LVO/C core–shell composite. Reproduced with permission [119]. Copyright 2015, Wiley. (f) Schematic illustration of the formation
procedure of LVO/C spheres. (g) SEM and TEM images of LVO/C spheres. (f, g) Reproduced with permission [120]. Copyright 2017, Wiley.

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Y. Zhang et al.
after activation (Fig. 11b). In comparison with the structural evolution
between pristine β-LVO and the one after 20 cycles via in-situ X-ray and
XAFNS, a cation-disorder mechanism is proposed (Fig. 11c). As the
repeated insertion and extraction of two Li, gradual and irreversible
migration of Li and V ions from tetrahedral to octahedral sites occur,
rendering cation-disordered LVO formed during cycles. As a result, the
formed cation-disordered LVO anode during cycles can more smoothly
and reversibly accommodate two Li+ with reduced polarization and
improve the Li+ transport capability compared to the pristine LVO
anode. The new insights provide more opportunities of LVO for
high-rate energy storage.
3.1.2. Modification strategies of LVO for performance improvement
While the mechanism is being recognized, some intrinsic drawbacks
of LVO still need to be resolved, as follow, (1) the poor electronic con­
ductivity [119,121,122] results in the large resistance polarization and
poor rate performance; (2) the great capacity loss (30%) related to SEI
formation and irreversible phase transformation [106,123] during first
lithiation leads to low initial coulombic efficiency; (3) hydrophilic
character needs dry environment for storage. Lots of efforts have been
employed against the demerits of L3VO4. In addition, rapid improve­
ment in its performance have been achieved. various morphology
modification including nanostructure engineering [122,124-127],
composition [128–130], and surface coating [117-119, 126,131-133]
have been extensively promoted To handle the issue of poor electron
conductivity and enhance the activity of LVO. These strategies were
always combined with each other to achieve the best effects on LVO
anodes. For instance, Wu et al. proposed a hollow structured LVO
microbox wrapped with graphene nanosheets via facile one-pot hydro­
thermal reaction for lithium storage. The anode delivers a higher
reversible capacity of 223 mAh g− 1 at 20 C (1 C = 400 mA g− 1) than that
(87 mAh g− 1) of the one without graphene layers [121]. Cao et al.
prepared highly graphitized carbon-wrapped LVO nanoparticles with
porous structure via a green freeze-drying method combined with in situ
carbonizing [122]. A capacity of 381 mAh g− 1 at 0.2 A g− 1 with almost
no decay after 300 cycles has been achieved. And even at a high rate of 4
A g− 1, the anode still retains 275 mAh g− 1 after 500 cycles. To improve
the long-term cycling stability, Zhao et al. employed a facile spray
drying route to construct mesoporous LVO/C hollow spheres [117]. As
shown in Fig. 12a, the aerosol droplets produced by two-fluid nozzle
contain Li2CO3, V2O5 and glucose, and undergo evaporation and fol­
lowed heating treatment in an Ar atmosphere at 550 ◦ C to form the
LVO/C hollow sphere (Fig. 12b). The anode achieves 97 % capacity
retention (275 mAh g− 1) after 3000 cycles at 10 C, demonstrating the
excellent stability of the microstructure. Mai et al. further greatly
enhanced the rate capability and long-term cycling performance by
developing the mesoporous LVO/C submicron-ellipsoids with reduced
graphene oxides [118]. The synthetic route is facile and scalable, as
shown in Fig. 12c. A solution reaction occurs between LiOH and
NH4VO3 and leads to the formation of LVO nanoclusters with ethylene
glycol (EG) absorbed on the surface, which can further self-assemble
into submicron-ellipsoids (Fig. 12d). After annealing the obtained pre­
cursor in Ar, mesoporous LVO/C are left with the decomposition and
carbonization of EG. The anode exhibits outstanding rate capacity of 230
mAh g− 1 at 125 C and prolonged cycling stability of 82.5 % capacity
retention after 5000 cycles at 10 C. However, although these hollow
structures mentioned above significantly enhance the electrochemical
properties of LVO, the large hollow pores and voids severely reduce the
tap density and lead inferior volume energy density [134,135]. A
carbon-encapsulated LVO was designed by Cao et al. via directly
annealing organic vanadium source VO(C5H7O2)2 and LiOH in Ar at­
mosphere [119], as shown in Fig. 12e. The anode presents excellent rate
performance of 106 mAh g− 1 at extremely high rate of 10 C. Yu et al.
firstly synthesized the precursor of mesoporous V2O5 by controlling the
hydrolysis of vanadium alkoxide [120]. As shown in Fig. 12f, the ob­
tained V2O5 spherical colloids are sintered with lithium source in inert
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Energy Storage Materials 55 (2023) 364–387
atmosphere to form homogenous core-shell LVO@C spheres (Fig. 12g).
The submicron LVO@C spheres exhibit 66 % capacity retention (257
mAh g− 1) when the current rate is increased from 0.2 to 30 C, demon­
strating rapid Li+ diffusion in the core-shell structure. Besides the
spherical morphology, other types such as nanoflakes [136], nanofibers
[137], nanowires [107,138,139] and nanosheets [140] were fabricated
to reduce the interface resistance, accelerate the electronic and ionic
transport and release the internal strain for LVO during cycling.
Compared with carbon composition or surface modification, ion-
doping can directly adjust the inherent electronic structure, introduce
lattice defects and even change the configuration to influence the elec­
trochemical properties of active materials [142–144]. Up to date,
diverse elements such as Ni [145], Mg [127], Ca [146,147], Mo [148],
Ti [149], Nb [150], Si [141,151], Na [152], Cu [153], Fe [154] and F
[155] were selected to promote the electronic and ion transport in LVO.
Dong et al. has reported that Mo6+ doped LVO possesses higher elec­
tronic conductivity because Mo6+ alter the electronic bond structure of
LVO as n-type semiconductor and cause the Fermi level shift towards
conductive band due to the excess electrons [148]. The partial intro­
duction of Ti4+ induces additional interstitial Li+ in the octahedral sites
and enhance the Li+ diffusion kinetics. In addition, partial substitution
of lithium ions in LVO by alkali or alkaline earth metal ions could
enlarge the lattice expansion and accelerate the electronic transport. For
instance, the electronic conductivity Mg-doped LVO exhibits two orders
of magnitude higher than the pristine LVO [127]. Notably, ion doping
may trigger the phase transition, which can completely alter the lithium
storage properties. Li et al. successfully mediated the stabilization of
γ-LVO in room temperature by controlling the content of Si-doping and
studied the electrochemical properties [141]. γ-LVO generally only ex­
ists at high temperature and would transform to β phase as the tem­
perature cools down. The structural difference between β-LVO and
γ-LVO lies in the orientations of the LiO4 tetrahedrons and VO4 tetra­
hedrons. As shown in Fig. 13a, half of the tetrahedrons face opposite to
the other half in γ-LVO structure, while tetrahedrons in β-LVO face the
same orientation. As a result, the formation energy of pure γ-LVO is
higher than that of β-LVO at room temperature. The introducing of Si4+
to replace V5+ would bring in additional Li+ in interstitial sites to bal­
ance charge neutralization. As a result, calculations’ results indicate that
the Si-doped γ-LVO associated with interstitial Li is energetically more
favorable than that of β-LVO at room temperature, which is consistent
with the experimental results (Fig. 13b). As an anode, γ-LVO also ex­
hibits average operating potential of around 1 V, but the dQ/dV curves
display only a single couple of peaks, which are different from that of
β-LVO (two couples of peaks), indicating only one single redox variation
during charge/discharge (Fig. 13c). Moreover, the dQ/dV curve after 20
cycles almost overlaps the first dQ/dV curve in γ-LVO, while the in­
tensity and position in dQ/dV curves for β-LVO continuously changes
with the cycle number, indicating the more stable lithium storage in
Si-doped γ-LVO. Recently, Che et al. further enhanced the electro­
chemical performance of γ-LVO by co-doping Cr3+ and Si4+ [151]. The
obtained Li3.08Cr0.02Si0.09V0.9O4 nanowires exhibits 251.2 mAh g− 1 at
10 C and 95 % capacity retention after 2000 cycles, providing a prom­
ising candidate for future application.
3.2. Li1+xV1-xO2
Before lithium vanadate Li3VO4 was used as anode material, another
stoichiometric ratio of lithium vanadate Li1+xV1-xO2 had been investi­
gated as an intercalation-type anode material. Li1+xV1-xO2 is derived
from LiVO2 which possesses similar layered structure to LiCoO2. The
research of LiVO2 dates back to the 1960s, investigating the electric and
magnetic properties [158]. LiVO2 was first used as cathode to study the
lithium insertion property [159,160]. Choi et al. firstly studied the
electrochemical properties of layered structure Li1.1V0.9O2 as
insertion-type anode material [156]. The capacity can deliver 350 mAh
g− 1 with two obvious voltage plateaus of 0.4 and 0.15 V when discharge
Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

Fig. 13. (a) the cell volume and phase composition versus x of compounds Li3+xV1− xSixO4 and corresponding crystal structure of β- and γ-Li3VO4. (b) The calculated
structures and energies of Si-doped β and γ phases Li3+xV1− xSixO4 (x = 0.125) under interstitial Li mechanism. (c) dQ/dV curves of β-Li3VO4 (x = 0) and
γ-Li3.1V0.9Si0.1O4 (x = 0.1). Reproduced with permission [141]. Copyright 2018, Wiley.

to 0.01 V, as shown in Fig. 14a. Kim et al. optimized the Li/V ratio of
Li1+xVO2 and control the grain size via spray pyrolysis to improve the
electrochemical performance [161]. However, the optimum anode still
displays poor coulombic efficiency and inferior cycling stability. The
lithium storage mechanism of Li1+xV1-xO2 is attractive because no other
intercalation-type oxides has yet been found to endow such a low
lithium insertion potential (0.1 V vs. Li+/Li) except graphite. Bruce et al.
compared the charge-discharge curves of several Li1+xV1-xO2 with
different Li/V ratio, [157] as shown in Fig. 14b. Surprisingly, the 0.1 V
voltage plateaus only exist in the Li-rich Li1+xVO2 (x > 0), while pure
LiVO2 demonstrates no obvious lithium insertion behavior, which could
be also verified by X-ray and neutron diffraction analysis. To figure out
the effect of non-stoichiometry on intercalation, the powder neutron
diffraction patterns were collected at various states of charge to reveal
the structural evolution of Li1.07V0.93O2 (Fig. 14c). A two-phase transi­
tion between the original phase and Li2VO2 occurs at the 0.1 V discharge
voltage range. Li2VO2 is isostructural with the layered Li2NiO2, Li2MnO2
and Li2Mn0.5Ni0.5O2, which are also produced from the corresponding
layered LiMO2 phase [162–164]. For Li-rich Li1.07V0.93O2, partial Li
substitute V into the octahedral transition metal layers, which render the
tetrahedral sites in the Li layer more energetically accessible by Li
compared to LiVO2, as shown in Fig. 14d. As lithium insertion, the
resultant Li+-Li+ repulsions induce the shearing from the ion layers of
cubic close-packed structure to hexagonal close-packed structure. The
understanding of the non-stoichiometry provides new insight for
developing low-voltage anode materials.
3.3. Disordered rock-salt Li3+xV2O5
Lithium-rich disordered rock-salt (DRS) oxides are promising cath­
ode materials due to enhanced structural stability and faster Li diffusion
through percolating network than the layered counterparts [166,167].

379
Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

Fig. 14. (a) Charge and discharge curves of Li1.1V0.9O2 electrodes at the first cycle. Reproduced with permission [156]. Copyright 2009, Elsevier. (b) Variation of
potential (vs. Li+/Li) with state of charge for Li1+xV1− xO2 at a current density of 10 mA g− 1. Inset shows variation of capacity with cycle number for x = 0.07. (c)
Expanded regions of the powder neutron diffraction patterns collected at various states of charge for Li1.07V0.93O2. (d) Calculated local structures around an inserted
Li+ ion in LiVO2 and Li1.07V0.93O2. b-d) Reproduced with permission [157]. Copyright 2011, Nature Publishing Group.

However, there is little research on lithium intercalation of DRS oxides
in anode field. Delmas et al. found that layered V2O5 would irreversibly
be transformed to rock-salt Li3V2O5 when inserted to three lithium [168,
169]. Recently, Liu and co-workers applied such disordered rock-salt
Li3+xV2O5 as a fast-charging anode for LIBs [165]. Rock-salt Li3+xV2O5
is obtained from electrochemical lithiation of layered V2O5. As shown in
Fig. 15a, Li3+xV2O5 can be reversibly cycled at the voltage range be­
tween 0.01 V and 2 V with an average discharging voltage of 0.6 V and
delivers a specific capacity of 266 mAh g− 1 at 0.1 A g− 1. The Rietveld
refinement of neutron diffraction and X-ray diffraction confirm that
Li3+xV2O5 possesses a disordered rock-salt structure which octahedral
4b sites are disordered occupied by Li and V ions and other small amount

380
Y. Zhang et al. Energy Storage Materials 55 (2023) 364–387

Fig. 15. (a) The experimental voltage

profiles of graphite, Li4Ti5O12 and
disordered rock-salt Li3+xV2O5 under a
current density of 0.1 A g− 1. (b) The
crystal structure of disordered rock-salt
Li3V2O5. The red balls represent O, the
blue tetrahedron represents Li in tetra­
hedral sites, and the green octahedron
represents the Li/V shared octahedral
sites. (c) Neutron diffraction patterns of
disordered rock-salt Li3V2O5 and lithi­
ated disordered rock-salt Li3+xV2O5. (d)
Illustration of 0-TM and 1-TM mecha­
nism for rapid lithium diffusion in rock-
salt Li3+xV2O5. (e) The electrochemical
performance of disordered rock-salt
Li3V2O5. (a-e) Reproduced with
permission [165]. Copyright 2020, Na­
ture Publishing Group.

of Li ions (4 %) fill into tetrahedral sites in the cubic lattice composed of
O ions (Fig. 15b). In situ XRD and neutron diffraction at different states
of charges proved an intercalation-type mechanism of Li3+xV2O5 for
lithium storage (Fig. 15c). The DFT calculations reveal that the Li ions
firstly tend to insert into the empty tetrahedral sites that are surrounded
by LiO6 octahedra without adjacent VO6 octahedra, as shown in
Fig. 15d. This 0-transition metal (0-TM) surrounding configuration is
energetically favorable for lithium insertion in comparison with the
1-TM (one transition metal surrounding) configuration. The result is
consistent with the previous researches on disordered rock-salt cathode
which provide rapid lithium diffusion channels due to the 0-TM
configuration [166]. As a result, disordered rock-salt Li3+xV2O5 not
only display long-term stability of negligible capacity decay after 1000
cycles, but also extraordinary rate performance (Fig. 15e), e.g., at
extremely high current density of 20 A g− 1, 41 % (109 mAh g− 1) of the
capacity at 0.1 A g− 1 achieved. After pairing with LiNi0.8Mn0.1Co0.1O2 as
the cathode, the full battery can still release the specific capacity of 153
mAh g− 1 at 0.5 A g− 1 with an average voltage of 3.15 V and maintain
86.9 % capacity after 1000 cycles.
3.4. Other types of vanadates
In addition to the three types lithium vanadates, other vanadates
were also developed as stable host anodes for low-voltage lithium
storage. Metallic SrVO3 possesses a ABO3 perovskite structure, where
the large Sr cation occupy the center site and corner-shared VO6 form
the 3D tunnel structure which enables rapid lithium migration. SrVO3
was first reported by Chen et al. as a cathode material which could
deliver a reversible capacity of less than 100 mAh g− 1 with the working
potential of 1 V vs. Li+/Li [170]. Due to the both high electronic (3.5 ×
104 S cm− 1) [171] and ionic conductivity (10− 8 S cm− 1) [170] associ­
ated with low-voltage character, recently Liu and co-workers reported
the perovskite-type SrVO3 as an high-rate and low-voltage anode ma­
terial [172]. Conductive additive-free SrVO3 anode delivers a specific
capacity of 324 mAh g− 1 with an average voltage of 0.9 V. Notably, a
high areal capacity of ~5.4 mAh cm− 2 is achieved by using an ultrathick
(120 µm) electrode.
Besides the intercalation-type vanadates, Mai et al. reported that
calcium vanadate CaV4O9 based on conversion reaction could simulta­
neously achieve high capacity and near-zero volume change [173,174].
CaV4O9 has a tetragonal structure, where Ca2+ are uniformly distributed
in the layers. CaV4O9 was first studied as a stable anode for sodium ion

381
Y. Zhang et al.
batteries [175]. As anode for LIBs, CaV4O9 shows a high capacity of
more than 600 mAh g− 1 with average discharge voltage of 0.8 V. Such a
high capacity means a multi-electron conversion reaction occurring
upon lithium insertion, which generally results in severe volume
expansion. However, CaV4O9 exhibits a near-zero volume change
character during lithium intercalation/de-intercalation process and
excellent cycling stability at a high mass loading of 6.6 mg cm− 2. This
may be due to the amorphous Li-V-O compound produced from the
lithiation process acts as buffering matrix to release the internal stress
from conversion reaction. Such self-confined character help to broad the
scope for searching new rigid hosts as low-voltage anodes.
4. Perspectives and challenges
In this mini-review, we firstly showcase the thread of the various
stable host anodes with low-voltage character for LIBs. These emerging
anodes presents main operating potential around or below 1 V vs. Li+/
Li, which are significantly lower than that of high-potential anodes (>
1.5 V vs. Li+/Li). According to the elements composition, these stable
host frameworks are classified two categories: one is titanium-based
compounds which embrace Li2TiSiO5 and its derivatives, rare earth ti­
tanates, and Li(V1-xTix)S2 sulfides; another is vanadium-based oxides
which include three types of lithium vanadates (Li3VO4, Li1+xV1-xO2,
and rock-salt Li3V2O5), SrVO3 and CaV4O9. Such stable host frameworks
as low-voltage anodes broaden the range of candidates for next-
generation LIBs.
4.1. Perspectives for theoretical prediction of low-voltage anode materials
These novel stable materials for low-voltage anodes were exclusively
discovered by trial and error, which often relied on the researchers’
experience and intuition. Such an experimental approach is time-
consuming, low-throughput, and high degree of uncertainty. In recent
years, with the rapid development of computational materials science,
theory calculations can be utilized to explain the structure-properties
mechanism, guide the experimental design, retrieve the deviated route
of synthesis, and even predict the promising candidates. For instance,
the atomistic models with a few physical parameters obtained by first-
principle calculations (DFT) [176] or molecular dynamics (MD) [177]
can be used as input data for high-throughput screening (HT) [178] or
machine-learning (ML) [179] to filter out the upcoming electrode ma­
terials in the Materials Project database, after that the selected candidate
can be conducted by the validation experiment in a feedback loop. The
screening for stable low-voltage anodes is a complex process constrained
by multiple physical parameters. The constraint factors not only include
the cell potential interval (e.g., 0.25 V vs. Li+/Li < cell potential < 1 V
vs. Li+/Li) and maximum volume expansion (e.g., 20 %), but also
involve crystalline stability, safety, toxicity, mass, and volumetric ca­
pacity, discharging and charging rates and cost.
Although there is no relevant research dedicated to the screening of
stable low-voltage anode materials, the search process can be divided
into three steps. First, it starts with the establishment of the chemical
compositions which include the active metal redox, inactive cationic
components, and coordinated anions (oxides, sulfides, phosphides, ni­
trides, carbides). For intercalation-type anodes, the crystal structures
have a crucial effect on the electrochemical properties. DFT calculations
are then carried out to identify the crystallographic structural stability of
each candidate. The structural information and parametrization of the
thermodynamic stability by DFT calculations consist of a dataset that
contains the chemical formula, space group, vacancy sites, formation
energy, energy above hull, volume of the unit cell, density, and band
gap. For the selected thermodynamically stable candidates, such a
dataset can also act as the feature vectors or descriptors to derive more
crystal systems by data mining or machine training.
Second, to juggle the energy density and safety, the average poten­
tials for low-voltage anodes can be prescribed in the range of 0.25-1 V
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Energy Storage Materials 55 (2023) 364–387
vs. Li+/Li to further filter out the candidates. The equilibrium cell
voltage between anodes and lithium metal is related to the difference in
the Gibbs free-energy between lithiation products at different states of
charge [180]. Without considering the entropic contribution, the reac­
tion free-energy can be approximately equal to the internal energy.
However, standard DFT functionals based on either the local density
approximation (LDA) [181] or the generalized gradient approximation
(GGA) [182] may produce a large systematic error to predict the cell
potential due to ignoring the strongly correlated electrons around the
metal center [183]. Some less expensive methods including DFT+U
correction [184,185] and hybrid functionals [186] can be applied for
extensive screening of low-voltage anode materials in voltage predic­
tion, which has been proved validity to reduce the self-interaction error
of LDA/GGA for the voltage prediction of cathode materials [187,188].
In addition, to achieve stable and reversible lithium
intercalation/de-intercalation, host structures with layers or tunnels for
Li+ migration can be preferred, where the lattice distortion is as small as
possible during lithium insertion.
Third, after the screening for electrode potential and cycling stabil­
ity, the remaining candidates can be further filtered by the ion con­
ductivity which determines the charge and discharge rate of electrode
materials. However, either the ab initio calculations or the nudged elastic
band (NEB) methods to evaluate the energy barriers of Li+ diffusion are
notoriously complicated and expensive and difficult for high-throughput
screening. To reduce the computational difficulty and ensure the pre­
diction accuracy, newly developing theoretical simulations based on
high-throughput and machine learning should be combined with the
experimental observations to propose reasonable models and feature
descriptors to assess the ion mobility of low-voltage candidates.
4.2. Challenges for practical applications
Searching for novel stable low-voltage host anodes opens up new
scenarios for next-generation LIBs development. However, several
challenges should be subtly taken into consideration for practical
applications.
(1) The electrochemical evaluation of these anode materials in half-
cells is sometimes misleading. Half-cell refers to that the anode
materials are regarded as cathode while the metallic lithium is
employed as a counter electrode in the standard two-electrode
cell. The discharge/charge process for anode materials is oppo­
site to that in the full cell. When a full cell is used, the discharge
capacity depends on the de-lithiation of the anode and the lith­
iation of the cathode, which means the de-lithiation of the anode
is vital for practical application. The de-lithiation corresponds to
the charging process of anodes in a half-cell. Therefore, the
charging potential of anodes in half-cells should receive more
attention. For the newborn low-voltage candidates, intrinsic poor
electronic conductivity and sluggish Li+ diffusion kinetics may
induce severe polarization and voltage hysteresis, leading to the
separation between discharging and charging profiles. Several
modification strategies including ion doping, particle size con­
trolling, carbon compositing, and surface and interface engi­
neering should be adopted to enhance both the electronic and ion
conductivity to reduce the voltage hysteresis.
(2) The influence of the voltage window on recording the specific
capacity of anodes should be carefully considered. The main­
stream studies on anodes set the voltage window to 0-3 V vs. Li+/
Li to determine the capacity. Different from cathode whose ca­
pacity is mostly delivered at a narrow voltage range with flat
voltage plateaus, a large number of anodes usually exhibit sloping
capacity-voltage curves and pseudocapacitive behavior, leading
the capacity being proportional to the range of potential window.
The capacity in the upper voltage range (2-3 V vs. Li+/Li) prob­
ably accounts for a large portion of the overall capacity.
Y. Zhang et al.
However, in practical LIBs, the anode can hardly reach higher
than 2 V vs. Li+/Li. In addition, the cutoff voltage is also crucial to
impacting the performance of anodes. Some anodes may generate
irreversible phase transition under an extremely low-voltage
range. For instance, according to the theoretical calculations
[94], unit Li3VO4 can accommodate two lithium ions with little
volume expansion of 4 % above 0.2 V vs. Li+/Li, while further
lithiation towards 0 V vs. Li+/Li would induce the third Li
insertion with phase transformation and volume expansion of 20
%. Therefore, the selection of voltage window should be more
cautious when testing the low-voltage anodes.
(3) The initial CE should be given more emphasis when judging the
application prospect. These new emerging low-voltage anodes
generally present inferior initial CE without targeted optimiza­
tion. The inevitable side reaction induces the formation of SEI
films on the electrode surface under low operating potentials
after utilizing carbonates electrolytes, decreasing the initial CE of
the anodes. Moreover, for the conversion-type anodes, the phase
transformation itself could consume partial Li during the first
lithiation. And the resulting unstable interface would further
aggravate the side reactions, leading to poor initial CE. Some
modification strategies such as nanosizing may result in more
exposed surfaces to form more SEI films, further lowering the
initial CE. Prelithiation has been widely investigated to
compensate for the irreversible lithium loss and improve the
initial CE. Direct adding extra active lithium such as stabilized
lithium metal powder [189] or mechanical blending with Li foil
[190] may improve the initial CE of these low-voltage anodes. In
addition, some chemical or electrochemical prelithiation based
on the solution process can be used to achieve more homoge­
neous prelithiation. The prelithiation treatments can help
low-voltage anodes possess higher reversible charging capacity
and hence elevate the initial CE.
(4) For low-voltage anodes, although most literature reports the
electrochemical performance solely in terms of reversible ca­
pacity, the energy density is a more crucial parameter for prac­
tical application rather than reversible capacity, and it is a
product of capacity and voltage. However, the estimation of en­
ergy density for low-voltage anodes in half-cells is difficult
because the average potentials of anodes are inversely propor­
tional to the energy density. It may be feasible to set a universal
cathode reference potential [191] to forecast the energy density
of these anodes in the half-cell set-up, or directly pair with
mainstream cathodes to calculate the energy density.
(5) The cost of these anode materials needs to be carefully considered
when promoting to be large-scale production. These low-voltage
anodes listed above are rare-earth-based compounds or contain
rare elements, e.g., for LiEuTiO4 and SrVO3, reviewing their costs
before the promotion is necessary. Another consideration is the
cost of synthesis. For instance, Li1+xVO2 has to be synthesized
under the reductive atmosphere (H2/Ar gas), greatly pushing up
the manufacturing cost.
In general, gaining the uniform identification of these stable host
low-voltage anodes is quite difficult because each type owns its distinct
lithium storage properties. For each promising candidate, multi-level
and interdisciplinary characterizations combined with theoretical
calculation are required to clarify the structural evolution, lithium
insertion mechanism, and origin of the potential plateau. On this basis,
some targeted modification strategies are expected to be proposed to
enhance the performance.
Declaration of Competing Interest
We declared that there is no conflict of interest in this manuscript
and all the listed authors fully agree with publishing the manuscript.
383
Energy Storage Materials 55 (2023) 364–387
Meanwhile, the manuscript has not been published previously, and not
under consideration for publication elsewhere.
Acknowledgments
The authors gratefully acknowledge funding supported by the Na­
tional Key Research and Development Program (Grant No.
2017YFE0127100), and the National Natural Science Foundation of
China (Grant No. 51772188 and 21878185).
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