Conversion Reaction-Based Oxide Nanomaterials For Lithium Ion Battery Anodes

reviews
www.MaterialsViews.com
Anode Materials
Conversion Reaction-Based Oxide Nanomaterials for

Lithium Ion Battery Anodes
Seung-Ho Yu, Soo Hong Lee, Dong Jun Lee, Yung-Eun Sung,*
and Taeghwan Hyeon*
From the Contents
1. Introduction ........................................ 2147

Developing high-energy-density electrodes for lithium
2. Iron Oxide............................................ 2147 ion batteries (LIBs) is of primary importance to meet
the challenges in electronics and automobile industries
3. Manganese Oxide ................................ 2150
in the near future. Conversion reaction-based transition
4. Cobalt Oxide ........................................ 2153 metal oxides are attractive candidates for LIB anodes
because of their high theoretical capacities. This review
5. Copper Oxide ....................................... 2157 summarizes recent advances on the development of
6. Nickel Oxide ........................................ 2158
nanostructured transition metal oxides for use in lithium
ion battery anodes based on conversion reactions. The
7. Molybdenum Oxide ............................. 2159 oxide materials covered in this review include oxides of
iron, manganese, cobalt, copper, nickel, molybdenum,
8. Zinc Oxide ........................................... 2160
zinc, ruthenium, chromium, and tungsten, and mixed
9. Ruthenium Oxide ................................. 2160 metal oxides. Various kinds of nanostructured materials
including nanowires, nanosheets, hollow structures,
10. Chromium Oxide .................................. 2161
porous structures, and oxide/carbon nanocomposites are
11. Tungsten Oxide .................................... 2162 discussed in terms of their LIB anode applications.
12. Mixed-Transition Metal Oxides ............. 2162
13. Summary and Outlook ......................... 2164
2146 www.small-journal.com © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim small 2016, 12, No. 16, 2146–2172
1. Introduction q = nF / m = 26801( n/ m)[mAhg −1 ] (3)
Over the past two decades, rechargeable lithium ion bat- Most conversion reaction-based transition metal oxides
teries (LIBs) have become one of the most important have much higher theoretical capacities than graphite
power sources for portable electronic devices because LIBs (372 mAh g−1), and some can exceed 1000 mAh g−1. Despite
exhibit many advantageous features including long life span, the high theoretical capacity, conversion reaction-based oxide
high reaction voltage, low self-discharge, wide temperature nanomaterials should be further optimized to overcome other
window, and lack of a memory effect.[1–5] Recently, they unsatisfactory electrochemical properties including voltage
have also been incorporated into the development of hybrid hysteresis.[22,23] A difference in voltages exists between the
electric vehicles (HEVs), plug in hybrid electric vehicles discharge and charge profiles, causing huge round-trip energy
(PHEVs), and electric vehicles (EVs).[4–6] To be commer- density inefficiency. In addition, very large volume changes
cially successful in various EVs and to meet the increasing occur during charging and discharging leading to cycle fading.
energy and performance expectations in electronic devices, A low initial Coulombic efficiency and rate capability should
LIBs should have increased energy densities. The most also be improved. Exploitation of nanostructured materials
straightforward way to accomplish this objective is to can effectively alleviate the strain derived from the volume
develop high-voltage cathodes and high-capacity anodes.[7–13] change, resulting in enhanced specific capacity retention. Fur-
However, developing high-voltage cathodes (≈5.0 V) is thermore, nanostructured materials can provide large elec-
extremely challenging because conventional organic electrode–electrolyte contact areas and shorten diffusion length
trolytes are unstable at the high voltages.[7,8] Consequently, of lithium ion in the active materials, leading to a high rate
tremendous efforts have been devoted to developing high- capability.[24–29] To address these issues, various transition
capacity anode materials for LIBs.[9–13] Various nanoma- metal oxide nanostructures having many different morpholo-
terials, including Li4Ti5O12 and SnO2 nanoparticles (NPs), gies and compositions have been investigated as LIB anodes.
have been employed as anode materials, and some have In this review, we summarize recent progress on the develop-
shown superior electrochemical properties.[14–20] Among ment of conversion reaction-based nanostructured transition
them, nanostructured transition metal oxides such as iron metal oxides for LIB anodes. All potentials in this review are
oxide and manganese oxide have attracted a great deal of given versus Li+/Li.
attention due to their high theoretical capacity since the
early 2000s.[21–24] The reaction between lithium and nano-
sized transition metal oxides, the so-called “conversion reac- 2. Iron Oxide
tion,” is shown in Equation (1)
Iron oxide has received much attention as anode mate-
rials for LIBs because of its very high theoretical capacity
M xO y + 2 yLi + + 2 ye − ↔ xM 0 + yLi 2 O(M = transitionmetals) (1)
(for example, 1007 mAh g−1 for Fe2O3 and 924 mAh g−1
for Fe3O4), low cost, and environmental benignity. Conver-
Figure 1a shows a schematic illustration of the conversion reactions in iron oxide electrodes were observed first
sion reaction of transition metal oxides for LIB anodes. From in the 1980s using molten salt electrolytes.[30] After this ini-
Equation (1), 2y lithium ions can be stored per formula unit tial observation, many researchers utilized iron oxide as a
of metal oxide through a conversion reaction, causing a struc- negative electrode for LIBs. However, the electrochemical
tural change and amorphization of transition metal oxides reversibility of these electrodes was much lower than the the-
that involves large volume expansion. At the end of lithia- oretical expectation. A breakthrough occurred in the 2000s
tion, nanoscale transition metal clusters are embedded in the that improved the electrochemical reversibility when nanom-
lithium oxide (Li2O) matrix. During delithiation, these transi- eter-scale iron oxide was introduced.[21]
tion metal clusters are oxidized to form amorphous transition The α-Fe2O3 (hematite) and Fe3O4 (magnetite) phases
metal oxide. For example, 1–2 nm metallic Co NPs dispersed are the most explored iron oxides for LIB anodes. The con-
in a Li2O matrix are observed when 100–200 nm CoO version reaction involves massive structural reorganization
powder is fully lithiated (Figure 1b,c,e,f). The composition and volumetric changes (about 100% volume expansion for
changes from Co to CoO during delithiation (Figure 1d,g). Fe3O4).[31] As shown in a typical voltage profile of iron oxide,
The theoretical capacity (q) of the electrode materials can be
described as follows:
Dr. S.-H. Yu, S. H. Lee, D. J. Lee, Prof. Y.-E. Sung,
q = Qm / m
Prof. T. Hyeon
(2)
Center for Nanoparticle Research
Institute for Basic Science (IBS)
where Qm is the total quantity of charge that can be stored Seoul 151-742, South Korea
in an electrode molecule, and m is the molecular weight E-mail: ysung@snu.ac.kr; thyeon@snu.ac.kr
(g) of the electrode materials. Because Qm can be obtained Dr. S.-H. Yu, S. H. Lee, D. J. Lee, Prof. Y.-E. Sung, Prof. T. Hyeon
by multiplying the number of moles of stored electrons (n, School of Chemical and Biological Engineering
which is equal to 2y in Equation (1)) and the Faraday con- Seoul National University
Seoul 151-742, South Korea
stant (F = 96 485 C mol−1 = 26 801 mAh mol−1), Equation (2)
can be converted as follows: DOI: 10.1002/smll.201502299
small 2016, 12, No. 16, 2146–2172 © 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.small-journal.com 2147
reviews
a well-defined plateau at about 0.8 V corresponding to the

full reduction of FeOx to a Fe0/Li2O mixture occurs fol- Seung-Ho Yu received his B.S. degree (2008)
lowed by electrolyte decomposition that provides additional and PhD (2013) from the School of Chemi-
capacity and interfacial storage.[32] Moreover, the first cycle cal and Biological Engineering from Seoul
exhibits a different profile from subsequent cycles, which is National University under Prof. Y.-E. Sung.
He worked as a researcher in the Research
related to activation processes and an irreversible capacity
Institute of Advanced Materials at Seoul
loss.
National University (RIAM, 2013–2014)
Various shaped hematite nanostructures have been eval- under Prof. K. Kang and a senior researcher
uated to improve the electrochemical properties. Hollow in the Center for Nanoparticle Research
nanostructured hematite has been shown enhanced electro- in the Institute for Basic Science (IBS,
chemical performances while alleviating volume expansion 2014–2015). He is currently a postdoctoral
during cycling effectively.[33–42] Hard templates (silica[33] and researcher at Cornell University in the group
of Prof. H. D. Abruña. His research interests
soft templates (organic nanotube,[34] quasi-emulsion,[36] and
focus on developing new materials for en-
metal–organic framework (MOF)[37,38] have been utilized
ergy storage and conversion, including Li-ion
frequently followed by etching processes, such as calcina- and Li-S batteries.
tion or soaking, to create hollow interior structures. Hematite
microboxes derived from Prussian blue microcubes exhibited Yung-Eun Sung received B.S. degree
a reversible capacity of 945 mAh g−1 after 30 cycles.[38] How- (1986) and M.S. degree (1988) in Chemical
Technology from Seoul National University,
ever, hollow structures sacrifice volumetric specific capacities
and PhD in Chemistry from the University
due to low tap densities of active materials. Therefore, a thick
of Illinois at Urbana-Champaign (1996).
electrode with a high mass loading is needed, but a thick elec- He then completed postdoctoral studies at
trode makes it difficult to provide effective electrical pathway the University of Texas at Austin (1998). He
during cycling. joined the faculty in Gwangju Institute of
Another strategy for enhancing battery performance is Science and Technology in 1998 and moved
making composites with carbonaceous materials. Carbon can to the School of Chemical and Biological
Engineering in Seoul National University
provide mechanical strength against deformation generated
(2004). He is currently group leader of the
during extensive volume expansion, and supply electron- Center for Nanoparticle Research, IBS. His
transfer channels between the current collector and active research interests include electrochemical
materials. Moreover, a carbon coating on the electrode sur- energy conversion and storage devices such as fuel cells, lithium rechargeable batter-
face can prevent excessive buildup of a solid electrolyte inter- ies, and dye-sensitized solar cells.
phase (SEI) layer.[42] Many hematite compounds and carbon
Taeghwan Hyeon received his B.S. degree
structures, such as reduced graphene oxide (RGO),[43] carbon
(1987) and M.S. degree (1989) in Chemistry
nanotubes (CNTs),[44] and carbon matrices,[45,46] showed from Seoul National University. He obtained
good battery performance, including capacity retention and his PhD (1996) in Chemistry from the
rate capability. Chemically modified graphene oxide with University of Illinois at Urbana-Champaign.
hematite NPs yielded a capacity of more than 1000 mAh g−1 Since he joined the faculty of School of
after 50 cycles, which overwhelms the theoretical capacity.[43] Chemical and Biological Engineering of
Mesoporous hematite nanostructures have also been Seoul National University in 1997, he has
focused on the synthesis and applications of
employed as anode materials. Mesoporous silica NPs[47]
uniform-sized nanocrystals and nanoporous
and MOF[48] are typically used as templates. For example, materials. He is a director of the Center
mesoporous α-Fe2O3 prepared using a Fe-containing MOF for Nanoparticle Research in IBS. He is
exhibited a capacity of 911 mAh g−1 after 50 cycles at a currently serving as an Associate Editor of
0.2 C-rate.[49] The capacity of mesoporous α-Fe2O3 increased J. Am. Chem. Soc. and an editorial advisory
slowly during the initial cycles. This slow increase might be board member of Adv. Mater., Nano Today,
Nanoscale, and Small.
caused by the reversible formation of a gel-like layer upon
electrolyte decomposition at low potentials,[50] or incom-
plete deconversion reactions owing to the presence of elec- efficiency. Hence, various nanostructures have been tested
trically disconnected regions in the electrode.[22] A capacity to overcome these problems. Such nanostructures include
of 424 mAh g−1 could be achieved even when cycled at hollow structures,[52] mesoporous structures,[53] nanocompos-
10 C. Hematite nanostructures deposited on current collec- ites with graphene,[54–57] CNTs,[58,59] carbon matrixes,[60–66]
tors, such as copper[50] and nickel foil,[51] have also been eval- and nanostructures deposited on metal current collectors.[67]
uated for LIB anodes. These nanostructures maintain direct Controlling excessive SEI formation on anode surfaces has
electric contact with conductive metal substrates, allowing been considered an important issue for safe and stable bat-
omission of carbon additives in the electrode. There are still tery operation. Lee et al. reported that cycle performance
limitations in the film thickness, however, resulting in a low can be enhanced by changing the geometric configuration
volumetric specific capacity. of active materials.[54] Uniform iron oxide NPs were syn-
Magnetite has problems similar to other conversion thesized by thermal decomposition of an iron oleate-ligand
reaction-based transition metal oxides, including volume complex.[68] 10 nm sized iron oxide NPs self-assembled into
expansion, excessive SEI formation, and low Coulombic clusters using cationic surfactants as an oil-in-water emulsion
Figure 1. a) Schematic illustration of the conversion reaction of a transition metal oxide in a lithium ion battery. TEM images of b) the starting CoO
electrode, c) the fully lithiated CoO electrode, and d) a delithiated CoO electrode, and e–g) their corresponding SAED patterns. Reproduced with
permission.[21] Copyright 2000, Nature Publishing Group.
system to form 200 nm sized secondary particles (Figure 2a). removal. It remains a challenge to develop facile and scal-
After heat treatment in an inert gas, mesoporous iron oxide able syntheses of hierarchical nanostructures. A carbon-
nanoparticle clusters (MIONCs) showed uniform mesopores coated hierarchical nanoporous Fe3O4 nanocomposite has
centered at 3.5 nm, derived from interparticle spaces. By been developed by a simple one-pot reaction.[63] The syn-
comparing the electrochemical properties with those of thetic route involves simple mixing of iron chloride with
iron oxide, the MIONCs exhibited a high cyclic stability up sodium dodecyl sulfate (SDS) at 70 °C, followed by addi-
to 80 cycles, and higher Coulombic efficiency (Figure 2b). A tion of pyrrole as the carbon source without any washing
specific capacity of 867 mAh g−1 was maintained up to 100 steps (Figure 3a). The residual Fe3+ ions in the solution can
cycles, and the Coulombic efficiency increased rapidly after initiate polymerization of pyrrole, eliminating the need for
several cycles, reaching 99.7%. In addition, the MIONCs additional oxidants. After calcination in Ar, the resulting C/
showed higher reversible capacities than random aggregates Fe3O4 nanocomposite exhibited a spherical sea-urchin-like
of iron oxide nanoparticles (RAIONs) at high current densi- morphology with diameters of 200–500 nm (Figure 3b). The
ties, yielding 473 mAh g−1 at 1600 mA g−1 (Figure 2c). The inner part of the C/Fe3O4 nanocomposite was composed of
MIONCs exhibited a stable SEI layer on their surfaces and a nanoporous structure with irregular nanosized subunits
maintained their original morphology even after selective (Figure 3c). Interestingly, the specific capacity of the C/Fe3O4
etching of the SEI layer (Figure 2d). In comparison, RAIONs nanocomposite increased slowly as cycling progressed and
were buried under an excessive SEI layer. eventually stabilized, caused by the aforementioned active
Many other kinds of hierarchical porous nanostruc- processes (Figure 3d). The C/Fe3O4 nanocomposite showed
tures including assembled structures have been developed a capacity of 800–1000 mAh g−1 at a current of 100 mA g−1
using hard and soft templates. However, these materials up to 100 cycles, demonstrating high reversibility. For its
require elaborate procedures involving synthesis of spe- rate capability, the C/Fe3O4 nanocomposite delivered about
cific templates, impregnation of precursors, and template 418 mAh g−1 at a current of 2500 mA g−1 (Figure 3e).
reviews
Figure 2. a) TEM image of mesoporous iron oxide nanoparticle clusters. b) Cycle performances and c) rate properties of mesoporous iron oxide
nanoparticle clusters and random aggregates of iron oxide nanoparticles. d) Schematic illustration of SEI formation on mesoporous iron oxide
nanoparticle clusters and random aggregates of iron oxide nanoparticles. Reproduced with permission.[53] Copyright 2013, American Chemical
Society.
In addition to Fe2O3 and Fe3O4 phases, FeO has also (<0.8 V) compared with other transition metal oxides.[74]
been recently investigated as an anode for LIBs. FeO adopts Manganese oxide has a variety of crystallographic structures,
the cubic rock salt structure and contains nonstoichiometric which include cubic rock salt (MnO, 756 mAh g−1), inverse
compounds, typically exhibiting iron-deficient composi- spinel (Mn3O4, 937 mAh g−1), hexagonal corundum (Mn2O3,
tions (Fe0.84O–Fe0.95O). Two lithium ions can react with FeO, 1019 mAh g−1), and a manganese dioxide structure (MnO2,
resulting in a theoretical specific capacity of 744 mAh g−1. 1223 mAh g−1).[24] Although manganese oxide has many
However, FeO has a higher electronic conductivity than advantages for use as an anode in LIBs, fully utilization of
Fe2O3 and Fe3O4, thereby providing intimate electronic con- manganese oxide is difficult. Manganese oxide has extremely
tact between the active materials and the current collector.[69] low electrical conductivity (≈10−7–10−8 S cm−1 for Mn3O4)
Pure FeO/C electrodes were prepared through a carboth- that hampers its usage and commercialization as an electrode
ermal reduction process involving Fe2O3 and a carbon source. material.[75]
The reduction of Fe2O3 occurs in three stages (Fe2O3 → Understanding the reaction mechanism during charge/
Fe3O4 → FeO → Fe) in the presence of C, CO, and H2. The discharge cycling is very important for improving electrode
resulting FeO/C electrode was reported to exhibit a high stability as mentioned in the previous section. However, the
specific capacity of 710 mAh g−1 after 60 cycles at a current structural and chemical changes during a conversion reac-
density of 100 mA g−1.[70] However, the FeO phase is not tion make it difficult to investigate the reaction mechanism.
chemically stable and is prone to decomposition into Fe and In addition, the sensitivity of the reaction intermediates and
Fe3O4 through a two-step disproportionation process below products to ambient conditions impose limitations on ex situ
575 °C.[71] Therefore, it is not surprising that composited techniques. Therefore, various in situ techniques such as in
Fe3O4/FeO/C anode materials for LIBs have been reported situ transmission electron microscopy (TEM),[76] X-ray dif-
previously.[72,73] The Fe3O4/FeO/C composite was shown to fraction (XRD),[77] X-ray absorption spectroscopy (XAS),[78]
deliver an exceptionally high reversible capacity of approxi- and X-ray tomography,[79] have been recently adopted that
mately 1200 mAh g−1 after 100 cycles at a current density of reveal the events occurring during cycling. Lowe et al. ana-
200 mA g−1.[73] lyzed the conversion reaction in a Mn3O4 electrode using
in operando XRD and XAS techniques and proposed the
mechanism depicted in Figure 4. Zhang et al. prepared MnO
3. Manganese Oxide films with a thickness of 130 nm on Ti substrates using pulsed
laser deposition in order to quantify the mechanical prop-
Manganese oxide has been investigated because of its high erties of the SEI layer.[80] Different states of the SEI layer
theoretical specific capacity, low reaction potential (0.2–0.5 V were prepared by changing the cut-off voltage. Atomic force
during the initial discharge),[22] and low voltage hysteresis microscopy (AFM) and force spectroscopy were carried
Figure 3. a) Schematic illustration of synthetic procedure for a sea urchin-like porous C-Fe3O4 nanocomposite. TEM images of b) prepared and
c) sectioned C-Fe3O4 nanocomposite. d) Cycle performance and e) rate properties of sea urchin-like C-Fe3O4 nanocomposite. Reproduced with
permission.[62] Copyright 2012, Royal Society of Chemistry.
out in vacuum to prevent air exposure to the SEI layer. As- was formed with surface roughness varying over the range
deposited MnO films showed a granular morphology with a of 14–17 nm (Figure 5b,c). In these two samples, the SEI
surface roughness of ≈12 nm (Figure 5a). When two MnO layer responded to external mechanical forces with an initial
electrodes were discharged at 0.8 and 0.3 V, the SEI layer elastic deformation followed by plastic yield. These events
Figure 4. Schematic representation of proposed reaction mechanism of Mn3O4. Reproduced with permission.[77] Copyright 2013, Royal Society of
Chemistry.
reviews
Figure 5. AFM images of MnO electrode surface during the first cycle a) before electrochemical test, b) at 0.8 V, c) at 0.3 V, d) at 0.1 V, e) at 0.01 V
during discharge, and f) at 3 V after charge. Reproduced with permission.[80] Copyright 2012, American Chemical Society.
were confirmed by the indentation curves. Moreover, the SEI oxide nanocomposites combined with conducting materials,
layer in these samples showed a one-layer structure of 43 nm such as carbon,[81–93] CNTs,[94–96] graphene,[97–101] N-doped
thickness with a Young’s modulus of 1.1 GPa. Because this carbon,[102–106] and RGO.[107–109] Controlling the mor-
value is much higher than that of usual organic materials, a phology of manganese oxide has also been demonstrated on
thin and hard inorganic SEI layer formed, but no soft organic mesoporous[78,110–113] and hollow structures.[114,115] Interest-
SEI layer developed. Interestingly, the electrode discharge ingly, some reports showed a U-shaped capacity and cycle
at 0.3 V exhibited only a two-electron reduction process, number plots, in which the capacity decreased during the
likely due to the low conductivity of MnO. When the elec- first few cycles and then increased slowly upon additional
trode is discharged at 0.1 and 0.01 V, the surface grain size cycling.[84,102] In some cases, the capacity at the last cycle was
and roughness started to grow drastically to the range of much higher than the initial capacity.[99] This cycling behavior
65–280 nm (Figure 5d,e). The SEI layer in these samples also can be attributed to several factors including lithiation-
exhibited initial elastic deformation followed by plastic yield, induced reactivation[116] and generation of Mn4+ during the
but another set of elastic and yield regions were also clearly charge process. The latter occurs because Mn2+ was partly
observed, demonstrating a double-layer structure. A Young’s reoxidized to a higher oxidation state.[82]
modulus of 16 MPa and a thickness of 40 nm for the outer MnO/C “nanopeapods” exhibited high power and energy
layer, and a Young’s modulus of 540 MPa and a thickness of densities as well as stable cycling.[82] The MnO/C nanopeapod
70 nm for the inner layer was observed. The inner layer corre- structure with an internal void space was successfully fabri-
sponds to hard inorganic materials, and the soft outer layer is cated by using the fact that poorly crystalline MnO nanowires
likely to be composed of organic materials in a double-layer (NWs) are easily broken into NPs. In comparison, highly crys-
structure, showing that one-electron and two-electron reduc- talline MnO NWs maintain their original morphology even
tions occurred simultaneously. Finally, when the electrode during the high-temperature carbonization process. These
was charged back to 3.0 V (Figure 5f), the SEI layer shrunk two materials, poorly crystalline MnO precursor (MnO-P)
back to a thickness of approximately 9 nm with a Young’s NWs and single-crystalline MnO NWs, were used as starting
modulus >1 GPa. As a result, the unstable soft organic SEI materials for the self-polymerization of dopamine to synthe-
layer decomposed during charging while the inorganic SEI size MnO-P NW@polydopamine (PDA) and MnO NW@
layer partially remained intact. It is noteworthy that the dis- PDA core/shell nanostructures, respectively. After the high-
tribution of the SEI layer on the electrode surface was highly temperature carbonization process, the MnO-P@PDA core/
inhomogeneous. In nanosized active materials, the control of shell nanostructure was transformed into MnO NPs confined
SEI layer formation can be much more difficult owing to the in CNTs having a wall thickness of ≈15 nm (MnO/C nan-
extremely high surface-to-volume ratio. Therefore, proper opeapods, Figure 6b), while the MnO NW@PDA core/shell
strategies to achieve controllable SEI layers can be devel- nanostructure maintained its original morphology except
oped by means of different nanomaterial synthetic methods. for carbonization of the PDA shell resulting in, namely,
A variety of manganese oxide nanostructures have MnO/C core/shell NWs. The morphology and elemental dis-
been fabricated and tested in pursuit of high battery perfor- tribution of the MnO/C nanopeapods were confirmed by
mance and stable cycling. Construction strategies are similar TEM and energy dispersive spectroscopy (EDS) mapping
to those mentioned for iron oxide, including manganese (Figure 6c–f), showing a gap between two different MnO NPs
Figure 6. a) Schematic of morphological changes during lithiation in MnO nanowires, MnO/C core/shell nanowires, and MnO/C nanopeapods.
b) SEM image and c–f) TEM-EDS mapping of the MnO/C nanopeapods. Cycle performances of MnO/C nanopeapods g) at 500 mA g−1 for 100 cycles
and h) at 2000 mA g−1 for 1000 cycles. Reproduced with permission.[82] Copyright 2014, American Chemical Society.
inside a hollow carbon wire. MnO/C nanopeapods delivered (1019 mAh g−1) and a relatively low operating voltage (average
463 mAh g−1 at a very high current density of 5000 mA g−1, discharge voltage at 0.5 V and charge voltage at 1.2 V). These
which is excellent performance in comparison with other con- features can result in a higher energy density than that of other
trol groups. In addition, MnO/C nanopeapods exhibit over transition metal oxide-based anode materials. However, the
1000 mAh g−1 at a current density of 500 mA g−1 after 100 low intrinsic conductivity of Mn2O3 can cause poor capacity
cycles, demonstrating excellent cycling stability (Figure 6g). retention and low rate capability. To address this issue, var-
Impressively, a reversible capacity of 525 mAh g−1 at a cur- ious types of mesoporous Mn2O3 nanostructures have been
rent density of 2000 mA g−1 after 1000 cycles verified the explored as anode materials[117–120] because large size voids can
long-term stability of MnO/C nanopeapods. Such improved facilitate lithium ion diffusion and electrolyte access. Porous
battery performance can be attributed to (i) enhanced elec- Mn2O3 nanostructures were mainly synthesized by mor-
trical conductivity through the carbon shell, (ii) reduced phology-conserved phase transformation from Mn-containing
aggregation of MnO NPs during cycling, and (iii) accommo- precursors, such as MnCO3,[121] Mn(OH)2,[122] and Mn-glyco-
dation of the volume expansion upon lithiation (Figure 6a). late.[123] Among these nanostructures, porous Mn2O3 nano-
Mn3O4 has a much lower electrical conductivity than plates retained a capacity of 813 mAh g−1 after 50 cycles at a
Co3O4 and Fe3O4. In order to increase the electrical conduc- current density of 100 mA g−1, whereas the capacity of the bulk
tivity of Mn3O4, Mn3O4 NPs were grown on RGO using a Mn2O3 powder electrode degraded rapidly.[123] The improved
two-step solution-phase method, resulting in the formation of electrochemical performance of the porous Mn2O3 nanoplates
Mn3O4-RGO hybrid material (Figure 7a).[75] About 10–20 nm can be attributed to the thin plate morphology and porous
sized Mn3O4 NPs with high crystallinity were uniformly dis- structure. The thin plate morphology can provide abundant
tributed on the RGO sheets (≈10 wt%) (Figure 7b,c). A spe- surface sites for electrochemical reactions and thereby increase
cific capacity of about 810 mAh g−1 was delivered at a current specific capacity, while the porous structure can alleviate the
density of 40 mA g−1 after 50 cycles (Figure 7d), which can electrode polarization during the discharge–charge process and
be attributed to innate interactions between the graphene thereby enhance the rate capability and capacity retention.
substrates and Mn3O4 NPs. Moreover, good dispersion of
the Mn3O4 NPs on the RGO sheets can prevent aggregation
during cycling, which can facilitate the movement of charge 4. Cobalt Oxide
carriers from current collectors through highly conducting
3D graphene networks. CoO and Co3O4 are the main phases used as anode mate-
Mn2O3 has interesting properties for its use as an rials, in which the theoretical capacities are 715 and
anode material for LIBs, such as a high theoretical capacity 890 mAh g−1, respectively.[124,125] The overall reactions for
reviews
Figure 7. a) Schematic of preparation of Mn3O4/RGO. b,c) TEM images of Mn3O4/RGO. d) Rate properties of Mn3O4/RGO. Reproduced with
permission.[75] Copyright 2010, American Chemical Society.
these two phases during cycling are shown in Equations (4) forming Li-intercalated LixCo3O4 resulting in a small volume
and (5) as expansion (about 20%). Interestingly, this microscopic obser-
vation is consistent with Equation (6), as previous reports
Co 3O 4 + 8Li + + 8e − ↔ 3Co+ 4Li 2O (4) discovered. As more lithium ions are inserted into Co3O4,
the lattice fringe disappears, indicating the amorphization
CoO + 2Li + + 2e − ↔ Co + Li 2O (5) of Co3O4 and the conversion to small Co–Li–O clusters. In
the final phase, the Co-rich clusters are further reduced, and
These reactions induce large volume expansions of about Co metal clusters and Li2O crystals nucleate and grow simul-
100%,[126] which cause the agglomeration of active materials taneously. Co metal clusters are then interconnected and
and a deterioration of mechanical integrity leading to poor embedded into the Li2O matrix.
capacity retention. Voltage plateaus for the Co3O4 electrode For conversion reaction-based nanostructured metal
are observed at 1.3/0.8 and 2.2 V during initial discharge and oxides, a gradual increase in capacity during the first few
charge, respectively.[127] In the case of the CoO electrode, cycles is often observed. This capacity increase is more often
voltage plateaus during initial discharge and charge occur at observed in cobalt oxide. Sometimes unexpectedly high
0.7 and 2.1 V, respectively.[124] capacities exceeding the theoretical capacity were achieved
Many attempts have been made to discover the lithiation/ for oxide materials. This phenomenon seems to occur owing
delithiation pathway using a variety of methods. Larcher et to the following reasons such as formation of polymer/gel-
al. reported that there are two different pathways during ini- like films,[130] defect-induced storage of lithium ions,[131]
tial lithiation of Co3O4. These two pathways are described in improved kinetics resulting from oxidation states higher
Equations (6) and (7) as [126] than the initial state,[102] and capacitive behavior at the inter-
face between metal NPs and Li2O.[132] It has been widely
Co 3O 4 + xLi + + xe − ↔ Li xCo 3O 4 ( x ≤ 2) (6) accepted that polymer/gel-like film can participate in revers-
ible lithium storage and is a dominant factor to increase
Co 3O 4 + 2Li + + 2e − ↔ 3CoO + Li 2O (7) the capacity.[133] Such films are formed by electrochemically
driven ring-opening polymerization of electrolytes,[130] and
They demonstrated that the lithiation pathway is gov- the polymerization activity will depend on the metal spe-
erned by the morphology of the active materials and cycling cies. Thus, cobalt oxide might result in a large increase in
conditions, such as current density and cycling temperature. the capacity because of its high catalytic activity compared
During the first discharge, formation of lithium-inserted with other metal species. Although the exact mechanism for
LixCo3O4 is favored in large-sized Co3O4 (higher on-surface these events remains unclear, studies are underway seeking
current densities), while the smaller crystal sizes (lower cur- to better understand the mechanisms, which should give new
rent densities) lead to intermediate formation of CoO. Struc- insights into the fabrication of anode materials with enhanced
tural evolution and reaction pathways were also studied by in electrochemical performance.
situ TEM.[128,129] Luo et al. reported atomic resolution obser- Due to their attractive properties, various nanostructured
vation of lithiation and delithiation-induced phase conver- cobalt oxides have been developed. Wang et al. synthesized
sion of 5 nm sized Co3O4 nanocubes.[128] In the early stage of a highly ordered mesoporous Co3O4 nanostructure using
lithiation, lithium ions diffuse into the spinel crystal structure, KIT-6 mesoporous silica as a hard template. These materials
Figure 8. a) Schematic evolution of mesoporous hollow Co3O4 sphere and SEI formation on long-term cycling. SEM images of hollow Co3O4
spheres b) before cycling, c) after 90 cycles, and d) after 850 cycles at 1.12 C. The red dashed squares in e) indicate the cracks in the SEI layers.
The scale bars represent b,c) 200 and d) 100 nm. e) The entire lithiation-induced reactivation process and cycling performance. Reproduced with
permission.[116] Copyright 2014, Nature Publishing Group.
exhibited a high specific capacity of about 1200 mAh g−1 at restored to their original functionality. However, it has been
a current density of 50 and 700 mAh g−1 at 300 mA g−1 at reported that this degradation can be controlled to restruc-
100 cycles.[134] Wang et al. reported a facile synthesis of a ture the mesoporous architecture of mesoporous Co3O4
Co3O4 nanobelt array on titanium foil through thermal treat- hollow spheres, and stabilize the SEI layer by high-rate lith-
ment of cobalt carbonate hydroxide nanobelts synthesized iation-induced reactivation.[116 ] Figure 8a represents a sche-
by a hydrothermal method.[135] The resulting nanobelt array matic illustration of this reactivation process. During the first
delivered a reversible capacity greater than 700 mAh g−1 90 cycles, the materials suffer from enormous capacity fading
after 30 cycles. In addition, diverse Co3O4 nanostructures, (Figure 8e). During this stage, the SEI layer repeatedly frag-
including nanowire/fibers/rods,[136–139] nanotubes,[127] hollow ments, exfoliates, and changes its form, which makes the SEI
microspheres,[116,140–142] nanosheet/plates,[143,144] porous nano- layer thick and unstable. Figure 8c shows that SEI layers were
capsules,[145] agglomerated NPs,[146] and nanocages[147] have cracked and very thick due to repeated mechanical destruc-
been investigated as LIB anodes. tion and reformation. Surprisingly, after capacity fading,
Recently, Wang et al. reported a synthesis method for continuous lithiation at a high current density stimulated
multishelled Co3O4 hollow microspheres using polysaccha- the reactivation of the electrode materials, gradually raising
ride-based carbonaceous microspheres and the hydrated the specific capacity during the following cycles without any
cobalt ion ([Co(H2O)6]2+) as a sacrificial template and pre- significant degradation. The scanning electron microscope
cursor, respectively. These microspheres showed superior (SEM) image in Figure 8d shows that the lithiation-induced
electrochemical performance in terms of capacity.[140] The reactivation process makes the SEI layer thinner and stable
number of shells in multishelled hollow spheres are pre- leading to a smooth and completely encapsulated SEI layer
cisely controlled by varying the number of coordinated aquo after 850 cycles.
groups within the cobalt ion ([Co(H2O)x]2+, x = 3–6), which As we have discussed in previous sections, it is widely
changes the diffusion rate of the cobalt ion. Among multi- accepted that the electrochemical performance of nanostruc-
shelled hollow microspheres with a shell number range of tured metal oxides can be enhanced by making composites
1–4, triple-shelled Co3O4 microspheres showed a promising with carbonaceous materials that can accommodate volume
capacity of 1616 mAh g−1 at 30 cycles. This incredibly high changes and act as a current collector. For these reasons,
capacity resulted from a combination of porous architecture, cobalt oxide-based composites with various carbon sub-
high surface area, and the interior cavities of multishelled strates such as graphene,[148–154] CNTs,[155,156] mesoporous
microspheres. carbon,[157] and amorphous carbon,[158–160] have been devel-
When cycle number increases, the capacity of a cell oped. However, more precise control is needed to directly
monotonically decreases because electrode materials suffer synthesize cobalt oxide NP-carbon composites because
from mechanical degradation. These “dead” cells cannot be cobalt is easily reduced. Approaches to fabricate metal
reviews
Figure 9. a) Schematic illustration of preparation of CoO/graphene hybrid. b) Photograph and c) TEM image of CoO/graphene hybrid. Reversible
charge capacity of CoO/graphene hybrid electrode at 1 A g−1 d) for 5000 cycles and e) for 500 cycles at different temperature. Reproduced with
permission.[151] Copyright 2013, Wiley-VCH.
oxide-carbon nanocomposites include heat treatment of var- of the whole electrode actually decreased, however, when
ious inorganic–organic conjugated precursors. This approach this addition was done. Consequently, additive-free elec-
has been applied for other transition metal oxides.[103,161,162] trodes are highly attracted for nanostructured materials.
However, when a cobalt–organic precursor is heated in Figure 9a shows a schematic representation of the synthesis
inert gas or vacuum conditions, cobalt oxides are reduced of a binder-free CoO–graphene composite electrode.[151]
to metallic Co via a carbothermal reduction process accom- First, α-Co(OH)2 nanosheets with a thickness of ≈2.6 nm
panied by the simultaneous conversion of the organic pre- are synthesized and mixed with graphene oxide prepared
cursor to carbon. This process results in the formation of a by Hummer’s method.[164] Note that positively charged
Co–carbon nanocomposite rather than a cobalt oxide–carbon α-Co(OH)2 nanosheets electrostatically interact with nega-
composite.[158,159] Although the activation temperature for tively charged graphene oxide, producing a composite. When
carbothermal reduction of cobalt oxide is expected to be over the composites are refluxed under reducing conditions,
750 °C,[163] the high surface energy of the NPs enabled them reduction of graphene oxide and growth/transformation of
to be reduced at a temperature lower than 750 °C. After an Co(OH)2 occurs simultaneously, resulting in a β-Co(OH)2-
oxidation step, the Co–carbon composite was converted to graphene composite. Interestingly, β-Co(OH)2 is completely
the cobalt oxide–carbon composite, which could be utilized coated on graphene due to electrostatic interactions. After
as an anode material. drop-coating, drying, and sintering, binder-free CoO–gra-
When a battery electrode is fabricated, active materials phene hybrid composites are fabricated on a Cu foil. The
are mixed with conducting carbon and binder to enhance hybrid composite does not detach from the Cu foil even after
electrical conductivity and mechanical integrity, respectively. bending, indicating that it has good adhesion and structural
Normally, only a few weight percentage of these additives is stability (Figure 9b). Figure 9c shows that CoO is uniformly
typically incorporated into the micrometer sized materials. and completely coated on graphene. Binder-free CoO-
However, over 10% of additives should be added for nano- graphene hybrid composites have excellent electrochemical
materials because of their high surface area. The capacity performance, showing capacities over 600 mAh g−1 at a high
current density of 1 A g−1, even after 5000 cycles, owing to its without any Cu2O residue. However, thinner films showed a
2D architecture and stable mechanical integrity (Figure 9d). much-enhanced deconversion rate compared with the thicker
During discharge, CoO is converted to Co metallic clusters films, and this tendency was maintained up to 60 cycles. In the
that are a few nanometers in size and Li2O, and the reduced charging process, the inner layers close to the metallic cur-
metallic clusters and highly conductive graphene layer might rent collector are oxidized first. Afterward, oxidation of the
facilitate the good rate performance. As shown in Figure 9e, outer layers is hindered because of the low conductivity of
CoO–graphene hybrid composites exhibit high cycling sta- previously formed Cu2O. As a result, the complete oxidation
bility at various operating temperatures from 0 to 55 °C. of the active film could not be accomplished.
One of the major limitations of nanostructure-based elec-
trodes is the difficulty in scaling-up because of sophisticated
5. Copper Oxide synthetic processes. In view of this fact, Park et al. reported
the gram-scale synthesis of CuO hollow nanocubes by a one-
Copper oxides, Cu2 O and CuO, are p-type semiconduc- step polyol process following the oxidation step.[169] Starting
tors and have been utilized for various energy and environ- from Cu2O nanocubes as a template, CuO NPs with various
mental applications, such as CO oxidation catalysts,[165] gas structures can be synthesized by adjusting the amount of
sensors,[166] and various heterogeneous catalysts.[167] Copper ammonia solution that is used during the post-oxidation
oxides have theoretical capacities of 375 mAh g−1 for Cu2O process (Figure 10a–d). In this process, the concentration of
and 674 mAh g−1 for CuO. These values are smaller than ammonium and hydroxide ion determine the dissolution and
the capacities of other metal oxides, which range from precipitation rate of copper oxides, which is a critical factor
1223 mAh g−1 (for MnO2) to 715 mAh g−1 (for CoO).[22] for precise control of the morphology of CuO NPs. Figure 10e
The relatively low capacities of copper oxides result from shows voltage profiles of the CuO NPs at a current density
their large atomic number and low oxidation states. In spite of 150 mA g−1. Two hollow NPs show higher initial capacities
of their low capacities, copper oxides have been utilized for compared with the urchin-like NPs. The small domains of the
LIB anode materials because they are nontoxic, abundant in hollow NPs facilitate the conversion reaction. As the cycle
nature, and cost-effective. number increases, however, the hollow NPs exhibit decreasing
Bijani et al. studied the lithiation/delithiation mecha- capacity, while urchin-like CuO NPs show excellent capacity
nism in electrodeposited Cu2O thin films by XAS.[168] Irre- retention up to 50 cycles. The capacity retention for urchin-
spective of the thickness or porosity of the films, Cu2O is like CuO can be attributed to the stability of the single-
fully reduced during the first lithiation and converted to Cu crystalline grain and the structural toughness of the branches.
Figure 10. TEM images of a) Cu2O nanocubes, b) CuO hollow cubes, c) hollow spheres, and d) urchin-like particles. The scale bars are 500 nm
in (a–d). e) Initial discharge-charge curves and f) cycle performances of CuO nanoparticles at a current density of 150 mA g−1. Reproduced with
permission.[169] Copyright 2009, Wiley-VCH.
reviews
Numerous methods have been developed to fabricate [195]

respectively. Because the electrochemical performance
nanostructured copper oxides, such as the metal–organic of nanoelectrodes can be differentiated by the microstruc-
complex template method,[170–172] microwave-assisted syn- ture of active materials, efforts have focused on synthesizing
thesis,[173] ultrasonication,[174] precipitation method,[175–180] nanostructured nickel oxide with various shapes, such as
metal foil oxidation,[181–183] electrospinning,[184] impregnation nanowalls,[196] hollow spheres,[197,198] nanosheets,[199] porous
method,[185] electrochemical deposition,[186,187] and hydro- structures,[200–203] hierarchical structures,[204,205] nanofibers,[206]
thermal reactions.[188–191] and nanocones.[207] In addition to pure nickel oxide, com-
Zhang et al. synthesized microscale cog-like CuO super- posite materials containing carbonaceous materials[208–211] or
structures showing a hierarchically self-assembled mor- conducting polymers[212,213] have been developed that dramat-
phology.[192] The CuO micro-cog film exhibited outstanding ically enhance the performance of electrodes.
performance in LIB anodes, showing an initial discharge For the last several years, in situ TEM studies have been
capacity of 1052 mAh g−1 and a reversible capacity of utilized to examine the morphology changes during lithia-
810 mAh g−1 at a current density of 30 mA g−1. Moreover, tion/delithiation-induced conversion reactions regardless of
the micro-cog film maintained a capacity of 583 mAh g−1 at its complexity and accessibility.[128,129,214–216] However, these
a high current density of 2400 mA g−1. Goyal et al. reported observations have been performed in nonvolatile environ-
the formation of CNT–copper oxide–poly(vinylidene fluo- ments, such as liquid crystal-based electrolytes or electrolyte-
ride) hybrid nanocomposite acting as both an electrode and free conditions. Because of these experimental circumstances,
separator.[186] This hybrid electrode was fabricated by elec- detailed studies including surface-induced side reactions
trochemical deposition on a CNT array grown by chemical between electrode materials and electrolytes have rarely
vapor deposition, followed by a polymer infiltration process. been accomplished. Moreover, owing to geometric limita-
This hybrid electrode showed more than two times higher tions of TEM operation, even simplified electrode/electrolyte
areal capacity than that of CNT array. interfaces such as 1D or 2D contacts failed to give any infor-
mation about events that occur in a conventional battery.
Hence, another approach was required. Lin et al. reported the
6. Nickel Oxide visualization of the electrochemically driven phase transfor-
mation in NiO nanosheets in a coin cell.[217] NiO nanosheets
Nickel monoxide (NiO) has been exploited for energy storage synthesized by a solvothermal method were loaded on the
materials such as LIB anodes and pseudocapacitors.[193,194] holey-carbon-coated TEM grid, and the grid was assembled
In LIB anode materials, NiO has a theoretical capacity of and cycled in a coin cell. Because the grid was assembled in
718 mAh g−1, in which NiO is decomposed and converted a coin cell and immersed in the electrolyte, this grid-in-a-
to metallic Ni nanoclusters and Li2O. The reverse reaction coin cell method enabled direct observation of the structural
occurs at charge/discharge.[21,195] A voltage plateau during ini- evolution of the SEI at various states of charge/discharge
tial lithiation appears at 0.6 V, where reversible voltage pla- due to the galvanostatically controllable feature of a coin
teaus are positioned at 1.3 and 2.2 V for discharge and charge, cell (Figure 11). Figure 11a shows a scanning TEM (STEM)
Figure 11. STEM images of NiO nanosheets with a) before electrochemical test, b) with a 50% SOC during discharge, c) with a fully discharged
state, d) with a 50% SOC during charge, and e) with a full cycle. f) Atomic resolution HAADF-STEM image for a selected phase conversion scene.
The scale bars represent (a,e) 100 nm, (b–d) 50 nm, and (f) 5 nm. Reproduced with permission.[217] Copyright 2014, Nature Publishing Group.
image of a NiO nanosheet before electrochemical testing. conversion reaction of MoO3 can be written as shown in
The as-synthesized nanosheets have hexagonal nanoholes Equation (8)
and a thickness range of 16–32 nm. The surface consisted of
mainly a (111) lattice plane of a rock salt crystal. After 40 MoO 3 + 6Li + + 6e − ↔ Mo + 3Li 2O (8)
cycles of charge/discharge, the capacity of the nanosheets
exhibited a significantly high value of 675 mAh g−1. STEM Variously shaped MoO3 NPs, such as the yolk–shell struc-
images at 50% state of charge (SOC) during both initial lithi- ture, exfoliated nanosheets, and hexagonal nanorods have
ation and delithiation (Figure 11b,d) show a heterogeneous been employed as LIB anodes.[218–224] Ko et al. synthesized
conversion/de-conversion phenomenon. During charging, ant-cave-structured MoO3–C composites with open nano-
nanostructured networks of metallic nickel start to nucleate channels by spray pyrolysis.[225] Three different kinds of sam-
from spatially separated regions of the NiO nanosheet and ples including well-faceted structure (Figure 12a), sphere-like
spread along the nanosheet until the conversion planes meet structure (Figure 12b), and ant-cave-structured MoO3–C
each other (Figure 11c). As seen in Figure 11e, metallic net- composite (Figure 12c), were prepared by either combining
works are no longer observed and NiO nanosheets recover with carbon source or varying the post-treatment condi-
their original morphology after a complete cycle, repre- tions. A prepared ant-cave-structured MoO3–C composite
senting the reversible nature of NiO nanosheets. From an showed superior cycling performance (Figure 12d) and rate
extensive microscopy study, it can be observed that the properties (Figure 12e) resulting from synergistic effects of
nucleation of metallic Ni initiates from the grain boundaries. its porous structure and carbon component. After 300 cycles,
Figure 11f indicates that the lattice orientations of the upper the ant-cave-structured MoO3–C composite still delivered a
and lower regions do not correspond to each other, showing high discharge capacity of 733 mAh g−1, whereas well-faceted
boundary-mediated nucleation. At a fully discharged state, all crystal structured MoO3, and spherical-like MoO3 exhibit 338
nanosheets were converted to nanoporous metallic networks and 345 mAh g−1, respectively.
and were covered with SEI layers, which were formed by a MoO2 also has a very high theoretical capacity of
decomposition reaction of the electrolyte. It is noteworthy 838 mAh g−1, which is based on the conversion reaction
that homogenous conversion/deconversion rarely occurs on shown in Equation (9)
a nanostructure in real conditions. When an actual battery is
operating, any variation of the electrolyte exposure, electrical MoO 2 + 4Li + + 4e − ↔ Mo + 2Li 2 O (9)
conductance, or crystal surface energy will facilitate hetero-
geneous phase conversion. It has been reported that bulk MoO2 undergoes a lim-
ited conversion reaction due to slow kinetics. Improving the
kinetics of this conversion reaction via a better-designed
7. Molybdenum Oxide nanostructured MoO2 should deliver an enhanced specific
capacity. Ultrafine MoO2 nanorods with a diameter of about
Molybdenum trioxide (MoO3) has a very high theoretical 5 nm exhibited a much higher capacity than bulk MoO2.[226]
capacity of 1117 mAh g−1 as LIB anodes. This capacity Self-assembled porous MoO2/graphene microspheres exhib-
is the second highest in the conversion reaction-based ited a very high reversible capacity of 1296 mAh g−1 in the
transition metal oxides (MnO2 exhibits the highest). The first cycle and 1375 mAh g−1 at the 80th cycle, exceeding the
Figure 12. SEM images of a) well-faceted crystal structured MoO3, b) spherical-like MoO3, and c) ant-cave-structured MoO3–C composite. d) Cycle
performances at a constant current density of 2 A g−1 and e) rate properties of well-faceted crystal structured MoO3, spherical-like MoO3 and ant-
cave-structured MoO3–C composite. Reproduced with permission.[225] Copyright 2013, American Chemical Society.
reviews
theoretical capacity.[227]
Ku et al. have suggested an inter- milling exhibited high cycle stability during 500 cycles with an
esting approach to enhance the electrochemical properties initial reversible capacity of 783 mAh g−1. Yang et al. synthe-
of MnO2.[228] An increased reaction rate at elevated tempera- sized ZnO quantum dots embedded in porous carbon derived
tures makes it easier for MoO2 particles to undergo a conver- from a MOF (isoreticular MOF-1) (Figure 13a).[162] 3.5 nm
sion reaction. As-generated nanosized MoO2 electrodes by ZnO quantum dots are well embedded without agglomera-
activation cycling showed excellent cycle performance with tion in micrometer sized cubic carbon (Figure 13b,c). They
a high specific capacity above 800 mAh g−1 during 30 cycles. delivered a very high initial discharge capacity of about
2300 mAh g−1 (Figure 13d). The capacity decreased for the
initial few cycles and then remained unchanged until the 50th
8. Zinc Oxide cycle (Figure 13e). Recently, MOF-derived Zn@ZnO quantum
dots/C core–shell nanorod arrays grown on a flexible carbon
ZnO has been considered as an alternative anode material cloth showed excellent cycle performance during 100 cycles at
due to its high theoretical capacity (978 mAh g−1), natural a current density of 500 mA g−1.[235]
abundance, low cost, and environmental benignity. The reac-
tion mechanism of ZnO can be separated into two steps as
show in Equations (10) and (11)[229–231] 9. Ruthenium Oxide
ZnO + 2Li + + 2e − ↔ Zn + Li 2O (10) RuO2 has a high electronic conductivity similar to

Fe3O4.[31,242] There are two distinct plateaus in the first dis-
charge curves of RuO2. The first plateau at 2.1 V is associated
Zn + Li + + e − ↔ LiZn (11) with the lithium intercalation reaction with RuO2 to form
the intermediate LixRuO2 phase (x ≤ 1).[243] The second pla-
During lithiation, ZnO undergoes a conversion reaction teau at about 0.8 V is due to the conversion reaction to form
to form Li2O and nanosized metallic zinc clusters. This step is Li2O and Ru metal clusters. Theoretically, RuO2 can store up
followed by an alloying reaction between lithium and the as- to four lithium ions per formula unit (806 mAh g−1). How-
generated Zn NPs. The main drawback of ZnO electrodes is ever, it has been reported that a much higher capacity (about
capacity fading upon cycling caused by a huge volume expan- 1130 mAh g−1) was delivered during the initial discharge.[244]
sion (about 228%),[231,232] even at very low current densities. Many researchers have proposed detailed reaction mecha-
Considerable efforts have been put to develop a nanostruc- nisms for RuO2, including mechanisms for the origin of its
tured ZnO electrode to improve its cycle performance.[162,230–241] additional capacity.[242–247] For example, Balaya et al. have
In particular, ZnO–carbon composite materials, including ZnO- proposed an overall reversible reaction mechanism for RuO2
graphene composites and carbon-coated ZnO, have shown using high-resolution TEM (HRTEM), selected area electron
better electrochemical properties.[162,230–241] For example, the diffraction (SAED), XRD, and Raman spectroscopy, which
ZnO/graphene nanocomposite prepared by high-energy ball can be summarized in Equations (12)–(14)[244]
Figure 13. a) Schematic illustrations of metal–organic framework (left) and carbon-coated ZnO quantum dots derived from a metal–organic
framework (right). b) SEM image and c) TEM image of carbon-coated ZnO quantum dots. Inset of c) shows corresponding SAED pattern. d) Voltage
profiles and e) cycle performance of carbon-coated ZnO quantum dots after heat treatment at 550 °C at a current density of 75 mA g−1. Reproduced
with permission.[162] Copyright 2013, American Chemical Society.
RuO 2 + 4Li + + 4e − ↔ Ru + 2Li 2 O MWCNTs/RuO2 electrodes delivered about 1500 μAh cm−2
(12)
at the first cycle. This result dropped to about 600 μAh cm−2
Li + + e − + electrolyte ↔ SEI(Li) after 20 cycles, and then remained stable until the 100th cycle.
(13)
Li + + e − + Ru/Li 2O ↔ Li/Ru/Li 2 O
(14)
10. Chromium Oxide
Gregorczyk et al. have found that an intermediate crystal
phase for LixRuO2 formed during the first discharge. They Cr2O3 is one of the most difficult metals to reduce through
reported that the reaction between amorphous RuO2 and a conversion reaction. It reacts with lithium at a relatively
Ru/Li2O was partially reversible during the subsequent low voltage of about 0.2 V. Cr2O3 has a very high theoretical
cycles.[242] Hu et al. have proposed that formation of LiOH capacity (1058 mAh g−1), based on the conversion reaction
and its reversible reaction to form Li2O and LiH are respon- shown in Equation (15).[249–251]
sible for the additional capacity of RuO2, using solid-state
nuclear magnetic resonance (NMR) spectroscopy and in situ Cr2O 3 + 6Li + + 6e − ↔ 2Cr + 3Li 2O (15)
synchrotron-based techniques (Figure 14).[243] Recently, Mao
et al. observed a two-step process during the first lithiation Although Cr2O3 has these advantages for LIB anodes, its
of RuO2 nanowires using in situ TEM.[245] Kim et al. demon- practical application has been hampered by poor cycle per-
strated that fast lithium storage occurs in the grain boundary formance due to high volume expansion/contraction during
of newly generated nanosized Ru metal and Li2O using in lithiation/de-lithiation (about 200%), low electrical conduc-
situ synchrotron-based techniques of TEM, X-ray photo- tivity, and formation of unstable SEI films on the surface of
electron spectroscopy (XPS), and galvanostatic intermittent the Cr2O3 electrode.[249,250] Hu et al. observed a change in the
titration.[246] thickness of SEI films on bare Cr2O3 electrodes at the fully
Much research work on RuO2 has focused on deter- lithiated (about 30–90 nm) and delithiated (<10 nm) state
mining reaction mechanisms. A few nanostructured RuO2 using high-resolution TEM.[250]
materials that show enhanced electrochemical proper- Several kinds of carbon–Cr2O3 nanocomposites have
ties have been reported. Still, the long-term cycle perfor- been developed to improve the electrochemical perfor-
mance of RuO2 is not as good as other transition metal mance of Cr2O3. Carbon not only increases electrical conduc-
oxides. Gregorczyk et al. have prepared planar RuO2 films tivity but also decreases the thickness of SEI films, leading
and 3D core–shell MWCNTs/RuO2 electrodes by atomic to enhanced electrochemical performance.[250] Cr2O3–C
layer deposition (ALD).[248] Planar RuO2 films exhibited a hierarchical core/shell nanospheres prepared by a soft tem-
very high initial discharge capacity of about 1450 mAh g−1 plate-assisted method exhibited an initial reversible capacity
at C/200 and 1300 mAh g−1 at C/20, but it decreased rap- of 688 mAh g−1, and a high cycle retention of 87% during
idly to ≈400 mAh g−1 after 40 cycles at C/20. 3D core–shell 35 cycles at a 0.2 C-rate.[252] 10–20 nm sized Cr2O3 NPs
Figure 14. Schematic representations of a) reaction pathway and b) the phase distribution at each stage with voltage profile for initial discharge.
Reproduced with permission.[243] Copyright 2013, Nature Publishing Group.
reviews
dispersed in mesoporous carbon synthesized by an in situ of 889 mAh g−1 over 250 cycles at a current density of
soft-template approach delivered reversible capacities of 710 200 mA g−1.[259]
and 639 mAh g−1 at the first and 80th cycle, respectively, at a
current density of 50 mA g−1.[253] Interconnected graphene-
Cr2O3 nanosheets exhibited an enhanced rate capability and 12. Mixed-Transition Metal Oxides
cycle performance with a high capacity (about 900 mAh g−1
at a current density of 200 mA g−1).[251] Mixed-transition metal oxides containing AxB3-xO4 spinel
structured oxides such as ferrite (AFe2O4, A = Mn, Co, Ni,
Cu, Zn, Mg and Ca),[260–294] manganite (AMn2O4, A = Co, Ni,
11. Tungsten Oxide and Zn),[295–311] and cobaltites (ACo2O4, A = Fe, Mn, Cu, Ni,
Zn, etc.)[299,300,312–331] have shown interesting electrochemical
Like most transition metal oxides, tungsten trioxide (WO3) properties as LIB anodes. Although they have multiple tran-
can react with lithium reversibly through a conversion reac- sition metal cations, they exhibit one plateau during initial
tion as shown in Equation (16) lithiation, whereas composites of different transition metal
oxides show multiple initial plateaus. For example, Kim
WO 3 + 6Li + + 6e − ↔ W + 3Li 2 O (16) et al. have shown that three distinct plateaus were observed
in the initial discharge curve of a simple mixture of Mn3O4,
The theoretical capacity of WO3 is 693 mAh g−1, but it Fe3O4, and Co3O4 (Figure 15a), whereas only one plateau
usually suffers from high volume changes, leading to poor was observed in a solid solution of MnFeCoO4 with a higher
cycle performance.[254,255] In order to overcome this problem, specific capacity (Figure 15b).[332] This phenomenon is more
various WO3-based nanostructures have been developed clearly observed in differential capacity curves (Figure 15c).
such as WO3 hollow nanospheres,[256] WO3-carbon composite In addition, potentials of this plateau can be varied by con-
nanofibers,[257] and cauliflower-like WO3.[258] WO3 nanoplate/ trolling the transition metal cations and their composition.
graphene nanosheet composites showed improved cycle As can be seen in Figure 15d, the potential shifts to higher
performance during 50 cycles, and exhibited 688.8 mAh g−1 values as the content of cobalt increases in Mn–Co mixed
at the 50th cycle.[255] Yoon et al. observed intercalation and metal oxides.[333] It has been demonstrated that the poten-
conversion reactions of cauliflower-like WO3 using in situ tial of the plateau changed as the composition of the mixed-
XRD.[258] Recently, Zhang et al. have developed a W18O49@ transition metal oxides change.[260] Hollow nanostructured
carbon nanowire web that exhibits a high reversible capacity metal oxides with tunable pore structures and compositions
Figure 15. Charge/discharge profiles of a) a simple mixture of Mn3O4, Fe3O4, and Co3O4, and b) MnFeCoO4. c) Differential capacity curves of a simple
mixture of Mn3O4, Fe3O4, and Co3O4, and MnFeCoO4 during initial discharge. Reproduced with permission.[332] Copyright 2012, American Chemical
Society. d) The first discharge curves of Mn2O3, Mn2CoO4, Mn1.5Co1.5O4, and MnCo2O4. Reproduced with permission.[333] Copyright 2007, Elsevier.
Figure 16. a) HRTEM image of a single Mn3O4 nanocrystal. b–f) HRTEM images of the hollow nanostructures synthesized by the reaction of Mn3O4
nanocrystals with 1 mL of aqueous solutions of iron (II) perchlorate having different concentrations: (b) 0.4 M, (c) 0.6 M, (d) 1.0 M, (e) 1.6 M, and
(f) 2.0 M. The insets of (a–f) show the corresponding Fourier transform patterns. g) First discharge curves and corresponding differential capacities,
and h) cycle performances of carbon-coated hollow Mn3-xFexO4. Reproduced with permission.[260] Copyright 2013, American Association for the
Advancement of Science.
can be prepared by galvanic replacement reaction. Figure 16a 2B + xLi 2O ↔ B 2O x + 2xLi + + 2xe −
shows TEM images of the as-prepared Mn3O4 nanocrystals ( x = 2 or 3 for ferrite, x = 2 or 8/3 for manganite and cobaltite) (20)
with a side dimension of ≈20 nm and height of 10 nm. Various
hollow nanoboxes with different ratios of Mn3O4/γ-Fe2O3
(Figure 16b–e) and γ-Fe2O3 nanocages (Figure 16f) were syn- If A = Zn, then further alloying reactions occur revers-
thesized by the galvanic replacement reaction with Mn3O4 ibly. If A = Mg or Ca, then MgO and CaO are formed after
nanocrystals and 1 ml of aqueous solutions of iron perchlo- the first lithiation, and the generated MgO and CaO do not
rate having different concentrations. For battery applications, participate in further reversible reactions. Two single-transi-
they were coated with polypyrrole in situ in the reaction mix- tion metal oxides have been reported in the delithiated state
ture and carbonized at 500 °C. These prepared carbon-coated in many previous reports, which strongly supports the Type
hollow Mn3-xFexO4 nanoboxes and nanocages had different 2 mechanism (namely, a displacive redox mechanism). ZnO/
reaction voltages during initial discharge. The reaction volt- Mn3O4[311] and ZnO/Fe2O3[279] domains were observed in
ages shifted from 0.400 to 0.818 V, proportional to the con- ZnMn2O4 and ZnFe2O4 electrodes, respectively, at a charged
tent of Fe in Mn3-xFexO4 (Figure 16g), indicating that the state after 1 cycle by ex situ TEM. Similarly, ZnO/Co3O4[334]
working voltage can be easily tailored. In addition, they all and FeO/Co3O4[335] were found in ZnCo2O4 and FeCo2O4,
exhibited excellent cycle performance during 50 cycles with a respectively, at a charged state after 50 cycles by ex situ TEM.
high specific capacity of about 1000 mAh g−1. Liu et al. have shown the reversible conversion between poly-
Several overall reaction mechanisms for mixed-tran- crystalline MnO/Fe3O4 and Li2O/Mn/Fe after lithiation of
sition metal oxides (AB2O4, A = Mn, Co, Ni, Cu, Zn, etc., MnFe2O4 on graphene using in situ TEM.[264] Other proposed
and B = Fe, Mn, and Co, A ≠ B) have been proposed, and mechanisms have been introduced as well. For example, Kim
they can be generally divided into two types as shown in et al. suggested a reaction mechanism for the MnFeCoO4
Equations (17)–(20). electrode based on ex situ TEM, XRD, and first principle cal-
culations, which is summarized in Equation (21)[332]
AB 2 O 4 + 8Li + + 8e − ↔ A + 2B + 4Li 2O (17)
MnFeCoO 4 + 8Li + + 8e − ↔ 3Mn 1/3 Fe 1/3Co 1/3 (metal alloy)
AB 2 O 4 + 8Li + + 8e − ↔ A + 2B + 4Li 2 O(1stlithiation) + 4Li 2 O (21)

(18)
Similar to many single-transition metal oxides,

A + Li 2O ↔ AO + 2Li + + 2e − (19) well-designed nanostructured materials can enhance
reviews
Figure 17. a) Schematic representation of preparation of ferrite/carbon nanosheets. b,c) TEM images of ferrite/carbon nanosheets. The inset of
(c) indicates highly crystalline nature of the nanosheets. d,e) TEM images of ferrite/carbon nanosheets after 10 cycles. f) Cycle performance and
g) rate properties of ferrite/carbon nanosheets. Reproduced with permission.[261] Copyright 2012, American Chemical Society.
electrochemical properties. Recently, self-assembled iron 81.5% of the original capacity was maintained for manganese-
oxide/carbon hybrid nanosheets with a 2D structure were ferrite/carbon nanosheets, attributable to the encapsulation
developed by using a one-step preparation method using of the conductive carbon nanosheets with highly ordered
an iron-oleate complex and salt particles as a precursor and 2D structures (Figure 17g). Even after 10 charge/discharge
a template, respectively (Figure 17a).[261] The overall syn- cycles, the ferrite NPs retained their original size and mor-
thetic procedure includes mixing the iron-oleate complex phology, and the 2D structure was maintained without defor-
and Na2SO4 salt, followed by heat treatment in Ar, and mation (Figure 17d,e). As a result, various metal oxide/carbon
washing with water. As shown in the SEM and TEM images, nanosheets can be synthesized by simple, inexpensive, and
the resulting nanosheets contained uniform-sized iron oxide scalable methods. Apart from these nanosheets, many other
NPs embedded in a carbon matrix and maintaining a highly nanostructured mixed-transition metal oxides have been
ordered 2D-structure (Figure 17b,c). The size and composi- developed recently as anode materials for LIBs to overcome
tion of the hybrid nanosheets can be easily controlled by problems related to conversion reaction-based materials, such
changing the relative amount of the iron-oleate precursor as cycle fading resulting from huge volume changes and low
and other metal-oleate precursor, such as a manganese-oleate rate-capability. These materials are summarized in Table 1.
complex. As a result, manganese-ferrite (MnxFe3-xO4)/carbon
nanosheets with different sizes and compositions were syn-
thesized without changing morphology or structure. This 13. Summary and Outlook
method is quite simple and can be easily scaled up to mul-
tigram quantity. In the electrochemical testing of the ferrite/ Various nanostructured transition metal oxides react with
carbon nanosheets, a reversible capacity of 600 mAh g−1 after lithium through a conversion reaction to form transition
50 cycles at a current density of 100 mA g−1 was observed metal nanoclusters and Li2O matrixes. These conversion
(Figure 17f). Furthermore, at a very high rate of 5000 mA g−1, reaction-based oxides are considered as promising anode
Table 1. Electrochemical properties of nanostructured mixed transition metal oxides.
Materials The first discharge/ Capacity [mAh g−1] / Capacity [mAh g−1] / Ref.
charge capacities [mAh g−1] number of cycles current density [mA g−1]
C-coated hollow Mn3–xFexO4 nanocages 1339/984 1001/50th cycle 302/1600 [260]
MnFe2O4/carbon hybrid nanosheets 1410a)/820a) 600a)/50th cycle 670a)/5000 [261]
MnFe2O4/graphene composites 1585/949 1017/90th cycle 315/12 000 [262]
MnFe2O4/graphene composites 1257/794 581/200th cycle 555/2000 [263]
MnFe2O4/graphene composites 1493/870 706/100th cycle 373/1600 [264]
Porous MnFe2O4 microrods 1336/937 630/1000th cycle 420/4000 [265]
CoFe2O4/graphene composite 2045/904 300a)/1400th cycle 330a)/4500 [266]
CoFe2O4/MWCNTs composite 1016/740 823/50th cycle 359/1800 [267]
Hollow CoFe2O4 nanospheres 2264/1230a) 1185/50th cycle 1030a)/900 [268]
Porous CoFe2O4 nanosheets 1619/1139 806/200th cycle 303/10 000 [269]
Hollow porous CoFe2O4 nanocubes 1352/1190 1115/200th cycle 815/20 C rate [270]
CoFe2O4 mesoporous platelets 2040/1425 1720/500th cycle 654/10 000 [271]
CoFe2O4 nanotubes 1417/1036 988/100th cycle 654/5000 [272]
NiFe2O4/graphene composites 1363/960 812/50th cycle 445/1000 [273]
Graphene/NiFe2O4/carbon composites 1990a)/1040a) 1195/200th cycle 520/1000 [274]
NiFe2O4 nanofibers 1450/1000 1000/100th cycle – [275]
NiFe2O4/onion-like carbon nanocapsules 1198/931 914/500th cycle 665/3660 [276]
C-coated hollow CuFe2O4 spheres 880a)/770a) 550a)/100th cycle 140/1600 [277]
Cu–CuFe2O4/graphene composites 1510/955 672/200th cycle 498/2000 [278]
ZnFe2O4 nano-octahedrons 1350/1036 910/80th cycle 575/960 [279]
ZnFe2O4 nanoparticles 1322/933 829/100th cycle 600/1560 [280]
ZnFe2O4 octahedra 1006/661 450/50th cycle 341/600 [281]
ZnFe2O4/C hollow spheres 1254/910a) 841/30th cycle 450/700 [282]
ZnFe2O4@polydopamine-derived carbon 1356/843 895/100th cycle 200/20 000 [283]
C-coated ZnFe2O4 nanowires 1285/1055 1292/100th cycle 753/3200 [284]
ZnFe2O4@C/graphene composites 1059/709 713/50th cycle 404/4640 [285]
ZnFe2O4/graphene composites 1446/1003 721/75th cycle 352/4002 [286]
ZnFe2O4/graphene hybrid films 1249/888 881/200th cycle 510/3200 [287]
ZnFe2O4/C@N-doped carbon nanotubes 2192/1121 844/100th cycle 747/1000 [288]
MgFe2O4 nanoparticles 1001/658 500/50th cycle 410/900 [289]
C-coated MgFe2O4 nanoparticles 700/451 744/160th cycle 217/6400 [290]
Mn0.5Co0.5Fe2O4 hollow spheres 847/526 498/500th cycle 115/2000 [291]
Mesoporous Mn0.5Co0.5Fe2O4 on graphene 1365/829 886/200th cycle 266/5000 [292]
Ni0.33Mn0.33Co0.33Fe2O4 mesoporous nanospheres 955/686 490a)/60th cycle – [293]
Ni0.33Mn0.33Co0.33Fe2O4 on oxidized carbon nanotubes 1092/692 674/100th cycle 300a)/1000 [294]
Carbon nanofiber@CoMn2O4 nanocable 1600/1170a) 650/300th cycle 160/3600 [295]
Double-shelled CoMn2O4 hollow cubes 1282/806 624/50th cycle 670a)/800 [296]
CoMn2O4 nano/submicrorods 1650/960a) 510/100th cycle 420/1000 [297]
CoMn2O4 hierarchical microspheres assembled 1442/937 894/65th cycle 241/9000 [298]
with porous nanosheets
CoMn2O4 nanowire arrays on stainless steel 1560/900 450/30th cycle 215/7000 [299]
Mesoporous hollow CoMn2O4 fibers 1213/882 798/50th cycle 575/5000 [300]
Porous NiMn2O4/C hierarchical tremella-like 1617/1015 1773/1500th cycle 671/5000 [301]
nanostructures
ZnMn2O4 ball-in-ball hollow microspheres 945/662 750/120th cycle 396/1200 [302]
ZnMn2O4/graphene nanosheets – 650/1500th cycle 568/3200 [303]
Flower-like ZnMn2O4 1350/763 626/50th cycle – [304]
reviews
Table 1. Continued.
Materials The first discharge/ Capacity [mAh g−1] / Capacity [mAh g−1] / Ref.
charge capacities [mAh g−1] number of cycles current density [mA g−1]
ZnMn2O4 tubular arrays on Ti foil 1198/713 784/100th cycle 244/3200 [305]
Quasi-mesocrystal ZnMn2O4 twin microsphere 1106/732 1084/190th cycle 329/5000 [306]
Loaf-like ZnMn2O4 nanorods 1357/839 517/100th cycle 457/1000 [307]
Nanocrystalline ZnMn2O4 1302/766 569/50th cycle – [308]
ZnMn2O4/graphene composite 1099/765 926/100th cycle 561/1200 [309]
ZnMn2O4 nanoparticles 1276/817 610/100th cycle 683/784 [310]
ZnMn2O4 nanowires 1400/880a) 660a)/40th cycle 350/1000 [311]
FeCo2O4 nanoflakes on Ni foam 2445/1870 905/170th cycle 1222/800 [312]
Hollow FeCo2O4 nanospheres 1359/1074 1060/50th cycle 823/1000 [313]
MnCo2O4 nanosheet arrays on stainless steel 1490a)/770a) 460/30th cycle 270/7000 [299]
Mesoporous hollow MnCo2O2 fibers 1402/1029 997/50th cycle 696/5000 [300]
MnCo2O2 yolk–shell submicrospheres 1425/1119 810a)/100th cycle – [314]
Mesoporous flak-like MnCo2O2 1460/1020a) 952/100th cycle 629/2000 [315]
MnCo2O4 nanowires on Ni foam 1289/966 596/50th cycle 345/1000 [316]
MnCo2O4 nanowires on Ni foam 2264/1634 1038/45th cycle 388/1600 [317]
NiCo2O4 hollow spheres 1401/928 706/100th cycle 533/2000 [318]
NiCo2O4/graphene nanosheets 1698/1035 954/50th cycle 437/1000 [319]
Mesoporous NiCo2O4 1095/799 1000/400th cycle 718/2240 [320]
NiCo2O4 nanoflakes 1292/1018 884/100th cycle 902/2000 [321]
NiCo2O4 nanobelts 1414/934 981/100th cycle 1062/2000
NixCo3–xO4 nanosheets 2489/1340 1330/50th cycle 293/1600 [322]
Mesoporous NiCo2O4 microspheres 1712/1214 705/500th cycle 393/1600 [323]
Mesoporous ZnCo2O4 microspheres 1600/1205 1256/100th cycle 430/4000 [324]
Mesoporous ZnCo2O4 microspheres 1332/979 721/80th cycle 382/5000 [325]
ZnCo2O4 nanowire arrays/carbon cloth 1530/1370a) 1200/160th cycle 605/4500 [326]
ZnCo2O4 nanostructure on Ni foam 2053/1508 1122/50th cycle 1100a)/2000 [327]
ZnCo2O4 nanowires on Ni foam 1704/1166 1100/60th cycle 240/2778 [328]
2D ultrathin ZnCo2O4 nanosheets 1311/1087 950/200th cycle 372/2000 [329]
ZnxCo3–xO4 hollow polyhedra 1272/969 990/50th cycle 575/9000 [330]
Porous ZnCo2O4 nanowires 1332/1092 1197/20th cycle – [331]
a)Values
are estimated from graph.
candidates to replace the currently used graphite due to their influences the electrochemical performance of electrode mate-
high theoretical capacity. We have provided a comprehensive rials. There is great potential for the design of nanostructure
review of recent progress and development on conversion morphologies with advantages in all the following aspects. First,
reaction-based transition metal oxides. the transport of both electrons and lithium ions is influenced by
Here, we emphasize some important aspects and develop- the morphology of the nanomaterials.[337] Specifically, lithium
ment directions for designing high performance anodes based ion diffusion is directly affected by the particle size. For ion
on conversion reactions: (1) Transition metal oxides should transport via solid-state diffusion in electrode materials, the
be carefully chosen because many properties, such as working following relationship can be established as
voltage, theoretical capacity, and electrical conductivity, are
dependent on the species and phases. In addition, composites τ = L2/D
(22)
with other suitable materials such as carbonaceous materials, or
use of mixed metal oxides can overcome the problems associ- where τ is the characteristic time constant for diffusion, L
ated with single-component transition metal oxides. Although is the diffusion length, and D is the ion diffusion coefficient.
we focus on transition metal oxides, the anionic species can Therefore, nanosized electrode materials can exhibit high
significantly affect the electrochemical properties, including rate capabilities by decreasing the diffusion length of the
the reaction potential and voltage hysteresis, in various conver- lithium ion within the active materials. Moreover, nanostruc-
sion reaction-based MxAy compounds (M = transition metal, tured electrode materials have high surface-to-volume ratios,
and A = N, F, S, P, or H).[336] (2) The morphology significantly which can increase the contact area between the electrode
Table 2. Comparison on the measurement conditions and capacity for various metal oxide nanostructures.
Materials Electrode composition Mass loadinga) Cell type Current density Capacity Ref.
(active materials: [mg cm−2] [mA g−1] [mAh g−1]/
conductive agent: cycle
binder)
Fe α-Fe2O3 multishelled hollow microsphere 60:30:10 0.6 Coin cell (CR2032) 50 1700b)/50 [41]
Spindle-like mesoporous α-Fe2O3 80:10:10 ≈1 Coin cell (CR2016) 200 911/50 [48]
Fe3O4 nanocrystals-carbon composite 80:10:10 ≈1.5 Swagelok-type 92.4 680b)/30 [65]
Mn Mn3O4-graphene composite 80:10:10 2 Coin cell (CR2032) Various Various [65]
Co Pompon-like Co3O4 microsphere 80:10:10 1.9 Lab-made coin cell 100 850b)/50 [125]
Binder-free CoO-graphene composite 100:0:0 0.53 Coin cell (CR2025) 1000 604/5000 [151]
a)
Calculated by the weight of active material; b)Values are estimated from the graph.
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Conversion Reaction-Based Oxide Nanomaterials For Lithium Ion Battery Anodes

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Conversion Reaction-Based Oxide Nanomaterials For Lithium Ion Battery Anodes

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Conversion Reaction-Based Oxide Nanomaterials for

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1. Introduction ........................................ 2147

12. Mixed-Transition Metal Oxides ............. 2162

13. Summary and Outlook ......................... 2164

1. Introduction q = nF / m = 26801( n/ m)[mAhg −1 ] (3)

a well-deﬁned plateau at about 0.8 V corresponding to the

Numerous methods have been developed to fabricate [195]

ZnO + 2Li + + 2e − ↔ Zn + Li 2O (10) RuO2 has a high electronic conductivity similar to

AB 2 O 4 + 8Li + + 8e − ↔ A + 2B + 4Li 2 O(1stlithiation) + 4Li 2 O (21)

Similar to many single-transition metal oxides,

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