Kim 2019
Kim 2019
Kim 2019
Materials Chemistry A
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REVIEW View Journal | View Issue
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Lithium-ion batteries (LIBs) continue to draw vast attention as a promising energy storage technology due to
their high energy density, low self-discharge property, nearly zero-memory effect, high open circuit voltage,
and long lifespan. In particular, high-energy density lithium-ion batteries are considered as the ideal power
source for electric vehicles (EVs) and hybrid electric vehicles (HEVs) in the automotive industry, in recent
years. This review discusses key aspects of the present and the future battery technologies on the basis of
the working electrode. We then discuss how lithium-ion batteries evolve to meet the growing demand on
high charge capacity and electrode stability. An account of a stand-alone energy device (off-grid system)
that combines an energy harvesting technology with a lithium-ion battery is also provided. The main
Received 1st November 2018
Accepted 17th January 2019
discussion is categorized into three perspectives such as the evolution from the conventional to the
advanced LIBs (e.g., Li-rich transition metal oxide and Ni-rich transition metal oxide batteries), to the state-
DOI: 10.1039/c8ta10513h
of-the-art LIBs (e.g., Li–air, Li–sulfur batteries, organic electrode batteries, solid-state batteries, and Li–
rsc.li/materials-a CO2 batteries), and to the hybridized LIBs (e.g., metal halide perovskite batteries).
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2. Conventional and present and O2:2p in the energy diagram (Fig. 3a). In a high voltage
range, the oxidation state changes from Co3+ into Co4+, followed
technologies by the removal of electrons from the O2:2p band, which in turn
2.1 Single transition metal oxide batteries causes some phase transitions in the crystal structure.20 Several
The concept of lithium-ion battery was rst demonstrated in the attempts have been made to replace Co with different transition
early 1970s by Whittingham employing metal dichalcogenides metal elements that minimize the overlap with the O2:2p
band, and offer ecological and economical advantages (e.g. Ni
(e.g. TiS2) as an intercalation compound.13,14 The layered struc-
ture of TiS2 comprising Ti and S sheets in a close-packed and Mn). LiNiO2 (LNO) is known to be isostructural with LCO,
arrangement allows the intercalation of Li+ into the host which is generally denoted as the O3-structure based on Delmas
material. This was further investigated by Goodenough, sug- notation.21 As implied in the energy diagram (Fig. 3a), LNO only
gesting a design consideration of the electrodes for lithium-ion involves the eg band, which lies well above the O2:2p band,
batteries.15 Mizushima and Goodenough et al. introduced Lix- during the Li+ deintercalation. This is a major benet of using
CoO2 (LCO) with an ordered rock-salt structure as a new cathode LNO, as it doesn't undergo changes in the lattice oxygen even at
material for batteries in the early 1980s.16 Since then, LCO has a deep deintercalation level of Li+.22–24 In spite of these advan-
tages, LNO is not a promising cathode material as it suffers
been vastly used due to the successful commercialization of the
LiCoO2/C cell by Sony in 1991.17 The LCO cathode benets from from critical drawbacks. It is challenging to synthesize a stoi-
high energy density, good electrical conductivity, high open- chiometric LNO with pure Ni3+ element at high temperatures,
circuit voltage (4.0 V), and low self-discharge.16,18,19 The octa- because of the instability of Ni3+ above 250 C.25 The synthesis
hedral array of the edge-shared CoO6 is the key for the good process to make LNO with a layered a-NaFeO2 structure nor-
electronic conductivity. Its high energy density is attributed to mally employs Ni2+/Li+-based precursors (e.g. LiOH–Ni(OH)2) at
the two-dimensional migration channel of Li+, which is a high temperature (700 C).19,26 As a consequence, the pres-
m) is unavoidable
ence of Ni2+ in the lithium 3a-site (trigonal, R3
a layered structure of three CoO2 layers per unit cell with
aer the synthesis, resulting in poor rate capability by impeding
a stacking order of ABCABC. LCO has a theoretical capacity of
274 mA h g1, when one mole of Li+ is deintercalated. However, Li+ diffusion.27 It has also been found that LNO undergoes
only 140 mA h g1, which is half of the theoretical capacity, can a series of phase transitions at different intercalation
be utilized practically because of its physical/chemical insta- states.26,28,29 The cathode can be electrochemically activated
bilities stemming from band overlapping between Co3+/4+:t2g when it exits as a trigonal structure. However, when 0.5 < x <
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Fig. 2 Evolution of working electrodes for lithium-ion batteries. (a) Conventional systems: olivine, spinel, and Li-layered transition metal oxide
cathodes. (b) Advanced systems from conventional systems. Crystal structures of Ni-rich transition metal oxide cathodes and Li-rich transition
metal oxide cathodes with an integrated structure between Li2MnO3 (monoclinic, C2/m) and LiTO2 (trigonal, R3m), where T represents Mn, Co,
and Ni. Reproduced from ref. 200 with permission (Copyright 2015, American Chemical Society) and reproduced from ref. 201 with permission
(Copyright 2016, Elsevier), respectively. (c) Comparison of the working electrodes of Li–sulfur: reproduced from ref. 202 with permission
(Copyright 2016, Royal Society of Chemistry), all-solid-state LIBs: reproduced from ref. 203 with permission (Copyright 2015, WILEY-VCH), Li–
air, Li–CO2: reproduced from ref. 159 with permission (Copyright 2017, Royal Society of Chemistry), and organic electrode LIBs: reproduced
from ref. 119 with permission (Copyright 2018, WILEY-VCH). (d) Photo-assisted charging process with a photoelectrode incorporated into
a lithium–oxygen battery. Reproduced from ref. 204 with permission (Copyright 2014, Nature Publishing Group).
0.75, LixNiO2 transforms into a monoclinic phase.26,29 Such resulting from the low-spin Ni3+:d7(t62ge1g) is another major
phase transitions in the crystal structure can lead to severe problem (Fig. 3b). This was rst reported by Rougier et al.,
capacity fading of electrochemical cells. Jahn–Teller distortion revealing the appearance of a NiO6 distortion in LNO.30 Two
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Fig. 3 (a) The energy vs. density of states with the relative Fermi level (EFC) and redox couples of Co4+/3+, Ni4+/3+, and Mn4+/3+ for LiCoO2, LiNiO2,
and LiMnO2, respectively. Reproduced from ref. 205 with permission (Copyright 2008, Royal Society of Chemistry). (b) Illustration of the Jahn–
Teller effect of NiO6 with energy splitting in an octahedral complex.
types of different bond lengths (four 1.91 Å and two 2.09 Å transition metal. A mixed transition metal cathode that
bonds) in NiO6 caused the distortion of the octahedron struc- combines Mn, Co, and Ni with a layered structure of a-NaFeO2-
ture of LNO. LiMnO2 has also been considered as an alternative type is oen denoted as an NMC cathode. It benets from the
electrode material, which can replace LCO due to its high high charge capacity of LiNiO2, the rate capability of LiCoO2,
theoretical capacity.31,32 LiMnO2 offers a high capacity of and the structural stability due to Mn4+.36,37 NMC delivers
285 mA h g1 and possesses higher power density.31,33 More- a reversible capacity of 160 mA h g1 in the voltage range
over, LiMnO2 is inexpensive, and it is environmentally benign between 2.5 V and 4.4 V, and can offer 200 mA h g1 when the
compared to LCO and LNO. Although the chemical formula of cell is charged between 2.8 V and 4.6 V.38 NMC is also cheaper
LiMnO2 is similar to that of LCO and LNO, the structure is not than LCO, as the proportion of Co is reduced by Ni and Mn. On
identical to the layered O3-structure as it crystallizes in an the one hand, the presence of Co3+ appears to be useful in
orthorhombic phase (space group: Pmmm).34 LiMnO2 with suppressing the structural distortion stemming from the Ni3+
a layered structure is not thermodynamically stable. An ion- Jahn–Teller effect by disrupting the Ni2+/Mn4+ cation ordering
exchange method between Na+ and Li+ in layered NaMnO2 to some extent.39–41 However, in spite of the synergetic merits
has been shown to yield a layered structure of LiMnO2.32 It has between the transition metals, NMC batteries can undergo
been reported that LiMnO2 undergoes a phase transition from surface reconstruction or unstable SEI formation on the elec-
the layered structure to a spinel structure (LiMn2O4), resulting trode with transition metal decomposition.42–44
in a poor cycle life on charge and discharge.35
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the O2 lattice in the spinel structure.19,45,46 Li+ can migrate Another class of cathode is the olivine LiFePO4 (LFP), which
through vacant tetrahedral (8a) and octahedral sites (16c), was introduced as a new type of cathode material belonging to
which offer a three-dimensional diffusion network. The phospho-olivines. Its reversible Li+ extraction and insertion was
migration of Li+ from and into the spinel cathode involves two rstly demonstrated in 1997 by Padhi and Goodenough et al.,
notable voltage-plateaus. At a higher voltage (4.0 V), Li+ (de) revealing a redox potential of 3.45 V vs. Li0/Li+.50 LFP is a pol-
intercalates from/into tetrahedral 8a sites, maintaining the yanion material crystallized in an orthorhombic system (space
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cubic structure. On the other side, at a lower voltage (3.0 V), group: Pnma) with a slightly distorted hexagonally close-packed
Li+ migrates from/into the vacant 16c octahedral sites. Close to (HCP) oxygen arrangement (Fig. 2a). P is located in tetrahedral
this voltage range, LiMn2O4 undergoes an asymmetric lattice sites, whereas Li+ and Fe2+ occupy octahedral sites. The strong
distortion resulting from the Jahn–Teller effect of high-spin P–O bond in (PO4)3 is the key factor that stabilizes the whole
Mn3+:3d4(t32ge1g).47 This leads to the phase transition from olivine structure, reducing O2 release during charge and
a cubic structure to a tetragonal structure, which in turn results discharge. The major advantages of using the LFP cathode are
in rapid capacity fading. A two-phase region is oen identied the good thermal and electrochemical stability, environmental
when 0.1 < x < 0.8 in Lix+1Mn2O4.48 Hence, the use of this benignity, and cheaper material cost.51 However, this type of
cathode is limited by a particular voltage range. Another major cathode suffers from low Li+ diffusion and electronic conduc-
problem arises, when the electrolyte includes LiPF6 salt with tivity, resulting in loss of capacity. The Li+ diffusion channel of
a trace amount of HF. This will trigger the Mn disproportion- LFP is based on a one-dimensional (1D) channel, where the
ation reaction (2Mn3+ / Mn2+ + Mn4+), causing the dissolution diffusion takes place along the edge-shared LiO6 units. It is
of the cathode into the electrolyte on charge–discharge.49 therefore that the Li+ diffusivity in LFP can be easily affected by
the point defects or impurities present in the 1D diffusion path
(Fig. 4a). The electrochemical properties of LFP could be
described by a at plateau occurring at approximately 3.45 V in
the galvanostatic prole (Fig. 4b). The plateau is characteristic
of Li+ (de)intercalation in the two-phase system of LiFePO4/
FePO4, which is strongly associated with the cell perfor-
mance.3,52,53 Thus, previous studies have attempted to explore
the correct nature of the two-phase region of the LFP cathode to
suggest better material designs or engineering treatments for
the improvement of cell performance and stability. Various Li+
(de)intercalation mechanisms that reasonably address the two-
phase region were proposed, such as the shrinking-core
model,53 new-core shell model,54 and domino-cascade model.55
3. Advanced technologies
3.1 High voltage lithium-ion batteries
High voltage cathodes (4.5–5.0 V) have been considered as
a potential candidate for advanced lithium-ion batteries. Spinel
LiMn1.5Ni0.5O4, olivine LiCoPO4, olivine LiNiPO4 and inverse
spinel LiNiVO4 are the major materials in this category.56 They
are designed to achieve higher charge capacity by enabling
a deeper level of Li+ deintercalated state. Among them,
LiMn1.5Ni0.5O4 demonstrates high cyclability with the voltage
range of 4.7–4.8 V. It also reveals a fair thermal stability up to
250 C.57 One major problem of these high voltage cathodes is
the severe decomposition of the electrolytes, as the conven-
tional carbonate-based electrolytes become unstable in the
voltage range higher than 4.4 V.
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Fig. 5 (a) Galvanostatic profile of Li1.2Ni0.13Co0.13Mn0.54O2 (Li-rich battery) with the cut-off voltage of 4.8 V (charge rate: 50 mA g1). The red plot
indicates the first charge. Reproduced from ref. 208 with permission (Copyright 2016, Nature Publishing Group). (b) X-ray absorption near edge
structure (XANES) spectra of the transition metal K-edge positions of Ni K-edge, Co K-edge, and Mn K-edge. The evolution of the corresponding
oxidation states of Ni, Co, and Mn in the Li1.2Ni0.13Co0.13Mn0.54O2 electrode. Reproduced from ref. 208 with permission (Copyright 2016, Nature
where M ¼ Ni, Co, and Mn, and Li2MnO3 (monoclinic, C2/m) unit cells and their atomic arrangements
Publishing Group). (c) LiMO2 (trigonal, R3m)
in the transition-metal layer. S1 and S2 represent site occupation by excess Li atoms and Mn atoms, respectively. Reproduced from ref. 209 with
permission (Copyright 2016, American Chemical Society). (d) SEM image and high resolution transmission electron (HR-TEM) observation of the
Li1.2Co0.1Mn0.55Ni0.15O2 electrode, showing the distance (4.7 Å) between two lattice fringes ((003) and (001)). Reproduced from ref. 63 with
permission (Copyright 2013, Elsevier).
layered oxide cathode has been introduced by Thackeray et al., (Fig. 5a).62–64 Voltage decay on further cycling is another major
demonstrating an integrated structure of the two distinct crys- drawback of this battery system.65,66 The electrochemical prop-
tallographic phases between Li2MnO3 (monoclinic, C2/m) and erties of the Li-rich batteries can be characterized by a two-stage
LiTO2 (trigonal, R3m), where T represents the 3d-transition reaction in the galvanostatic prole during the initial electro-
metals (Fig. 2b and 5c).58–60 The intimate integration is likely chemical cycle. At a lower voltage, a slope can be identied up to
to be attributed to the interleaving of close-packed layers 4.5 V vs. Li/Li+, which is attributed to the redox reaction of
between the (001) planes from Li2MnO3 and the (003) planes Ni2+/Ni3+/Ni4+ and Co3+/Co4+ (Fig. 5b). At a higher voltage,
from LiTO2 with the interlayer spacing of 4.7 Å (Fig. 5d).60 The a plateau like region occurs between 4.5 V and 4.8 V during the
major advantages of the Li-rich layered transition metal oxide initial charge, where Li+ ions deintercalate from the Li2MnO3
batteries are the superior theoretical capacity (>250 mA h g1) component.60,67,68 The irreversible capacity loss during the
with high chemical potential (>4.6 V vs. Li0), high discharge initial cycle could be attributed to lithia (Li2O) extraction from
capacity, good thermal stability, and lower cost compared to the Li2MnO3, which in turn results in the formation of a layered
traditional batteries (e.g. LCO, NMC, LFP).59–61 These high- MnO2 component (Li2MnO3 / Li2O + MnO2).60,61,67 Similar to
energy density batteries, however, suffer from irreversible the NMC cathode, the Li-rich cathode undergoes a phase tran-
capacity loss (40–100 mA g1) during the initial cycle sition from a layered structure into a spinel structure on charge–
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Fig. 6 (a) Plot of the relationship between thermal stability, discharge capacity and capacity retention for various types of Ni-rich cathodes.
Reproduced from ref. 210 with permission (Copyright 2013, Elsevier). (b) Schematics of lithium transition-metal oxide particles with a Ni
concentration gradient. Reproduced from ref. 72 with permission (Copyright 2012, Nature Publishing Group). (c) Cycling performance of
LiNi0.5Co0.2Mn0.3O2 in the voltage range of 3.0–4.3 V, 3.0–4.5 V, and 3.0–4.8 V (charge rate: 0.4C), and its degradation mechanism. Reproduced
from ref. 42 with permission (Copyright 2014, WILEY-VCH).
discharge.63,64,69,70 Especially, a previous study by Gu et al. batteries. A recent study by Lee and Ceder et al. has reported
reveals the origin of the phase transition.69 It has been sug- a reversible Mn2+/Mn4+ double redox cathode of the Li-rich
gested that the spinel phase transition of LiMO2 (M ¼ Ni, Mn, transition metal oxide battery.71 The introduction of high-
Co, R3m) is triggered by transition metal migration into the Li- valent cation (Nb5+, Ti4+) substitution with a partial replace-
layer. On the other hand, the phase transition to the spinel from ment of O2 by F results in a high charge capacity (>300mA h
Li2MnO3 (C2/m) is associated with lithia (Li2O) removal, which g1) and energy density (1000 W h kg1).71 The participation of
in turn causes lattice strain in the electrode. Transition metal Mn in the charge compensation mechanism not only enhances
redox couples are the crucial factor that is strongly associated the battery capacity, but also offers advantages in terms of
with the achievement of high charge capacities for lithium-ion resource cost and environment issues.
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4. State-of-the-art technologies
4.1 Li–sulfur batteries
As a next generation battery technology, sulfur (S) is a promising
candidate for cathode materials (Fig. 7c). It offers a very high
theoretical capacity of 1675 mA h g1, about 10 times that of
current transition metal oxides. It has higher abundance than
cobalt and nickel in the earth's crust, and is of very low cost.76,77
The schematic of the working principle of a Li–S battery and its
galvanostatic prole are shown in Fig. 7a and b. In spite of these
signicant advantages, a number of technical challenges hinder
the further applications of sulfur cathodes. They suffer from low
electrochemical potential vs. Li/Li+, low electrical conductivity,
and like other conversion type electrodes, sulfur suffers from
a signicant volume expansion of 80%, causing material
Fig. 7 (a) Illustration of the Li–S battery working principle with redox
cracking and detachment from the electrode conductive
reactions. Reproduced from ref. 202 with permission (Copyright 2015,
network.78,79 Also, the sulfur based cathode is of low vapor- Royal Society of Chemistry). (b) Galvanostatic profile of the Li–S
ization temperature, leading to a pure sulfur loss during the battery with multiple reduction stages. Reproduced from ref. 202 with
electrode drying process under vacuum.80 In addition, inter- permission (Copyright 2015, Royal Society of Chemistry). (c)
mediate reaction products formed during charge and discharge, Comparison of energy densities between the Li–S battery and various
energy storage systems. Reproduced from ref. 211 with permission
i.e., polysulde Li2Sn (3 # n # 8), are soluble in the electrolyte,
(Copyright 2015, WILEY-VCH).
and thus lead to the shuttle mechanism and capacity loss.81–84
The long-chain polysuldes dissolved in the electrolyte will
migrate back to the anode, and they will be reduced into lower
order polysuldes. This process is followed by the migration of sulfur in a carbon matrix, showing good reversible capacity
the lower order polysuldes back to the cathode, resulting in with high cycle numbers for Li–S and Na–S batteries.85 The
a re-oxidation. The shuttle effect will produce insoluble prod- performance improvement of the Li–S battery can be explained
ucts such as Li2S2 and Li2S, causing self-discharge and overall by the suppression of the polysulde intermediates owing to the
poor coulombic efficiency. These technical barriers prevent the entrapped sulfur in the carbon matrix. Another study has shown
mass commercialization of sulfur cathodes for Li–S batteries the development of a carbonized mesoporous wood ber as
despite decades of research. a host material to intercalate sulfur, and thereby providing high
A number of studies have attempted to address the technical cycling stability for Li–S batteries.86 A unique approach to
barriers of Li–S batteries. Luo et al. reported oxygen-stabilized suppress the shuttle effect of LiS batteries has also been shown,
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using selenium (Se) doping with the formation of a stable solid- The aqueous cells require a surface protecting or lithium ion
electrolyte interphase (SEI).87 conducting layer such as LISICON-type glass ceramic (lithium
superionic conductor, Li(1+x+y)AlxTi2xSiyP(3y)O12) to prevent
direct contact of the Li metal surface with H2O.76 These treat-
4.2 Li–air batteries
ments with surface coating layers, however, do not sustain long
Lithium–air battery (Li–O2) with an organic electrolyte was enough to hinder the formation of lithium dendrites.92 To
demonstrated by Abraham et al. in 1996 (Li–O2).88 The working
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Fig. 9 Design of the electrolyte structure. (a) Schematic illustrations of the electrolyte structure in a dilute LiTFSI/DMSO-based Li–O2/CO2 cell,
and relevant discharged components. As an intermediate, peroxodicarbonate (C2O62) coordinates with solvated Li ions and dissociates into
Li2CO3 as the typical final product. (b) Raman spectra of LiTFSI/DMSO solutions with various mole ratios. Spectra are fitted by Gaussian–Lor-
entzian distribution functions, and the SNS stretch region in TFSI (blue outlined) is magnified for clarity. In the LiTFSI/DMSO electrolyte with
a 1 : 3 mole ratio, neither free DMSO molecules nor solvent-separated ion pairs (SSIPs) were observed. Instead, sheathed by DMSO molecules, Li+
and TFSI were completely aggregated (AGG) within a contact ion pair (CIP) fluid network. (c) Schematic illustration of the newly introduced
super-concentrated fluid network electrolyte composed of [Li(DMSO)3]+–[TFSI]. Reproduced with permission.27 Electrochemical performance
of Li–O2/CO2 batteries. Galvanostatic voltage profiles of Li–O2/CO2 (1 : 1, v/v) cells with a specific LiTFSI/DMSO (1 : 3, mole ratio) electrolyte. (d)
Initial cycle at current densities from 200 to 600 mA g1 (left). Full discharge–charge profiles over 20 cycles controlled by potential limits from
2.6 to 3.65 V at 400 mA g1 (right). (e) In situ Raman spectra collected at the end of each discharge state (red) and charge (blue) state among
typical cycles during cycling with a fixed capacity of 200 mA h g1 (at 400 mA g1 current density). Reproduced from ref. 107 with permission
(Copyright 2018, Royal Society of Chemistry).
interphase by mitigating the attack from superoxide. This will as compared to Au and Pt metals. The improvement mechanism
lower the charging overpotential of the Li–O2 battery.108,109 by MoS2/IL has been revealed with the DFT calculations. EMIM+
There are also key issues that need to be addressed at the tends to form isolated Mo sites which prevent O2 dissociation and
oxygen electrode. The oxygen electrode in Li–air battery requires enable oxygen reduction. The ionic liquid EMIM-BF4 facilitates
high electronic and ionic conductivity, electrochemical the formation of Li2O2 by the dissolution of superoxide species
stability, fast oxygen diffusivity, porous structure to store the (O2). The performance of the MoS2/IL cathode/electrolyte (0.1 M
discharged product Li2O2, and high activity for the OER (oxygen LiTFSI) system is tested by a capacity-limited (500 mA h g1)
evolution reaction) and ORR (oxygen reduction reaction) cycling up to 50 cycles at a current density of 0.1 mA cm2. The
processes. There are a wide range of carbon materials utilized as discharge begins at 2.9 V and the target capacitance is obtained at
electrodes in Li–air batteries, such as carbon black, carbon a potential 2.69 V. The charging process is completed at a poten-
ber, carbon nanotubes, rGO and graphene-based mate- tial of 3.49 V, showing a discharge/charge polarization gap of
rials.110–112 Unfortunately, all carbonaceous electrode materials 0.8 V. This increased to 0.85 V aer 10 cycles, and the further
can notably degrade by the interactions with superoxide and discharge capacity of MoS2/IL was 1250 mA h g1. To develop Li–
peroxide moieties. Most recently, therefore, non-carbonic O2 batteries with long-term stability, the electrochemical stability
oxygen electrodes have been of great interest. Non- of DMSO should be improved. Moreover, additional surface
carbonaceous materials such as Au,89 nano-porous Au,89 passivation layers would be required to prevent the Li metal from
TiC,113 Ti4O7,114 Ru,92 RuO2,115 MoS2,116 Mo2C (ref. 117) and degrading via side reactions.
Co3O4 (ref. 118) are widely studied for the oxygen electrode.
These metals and metal oxides exhibit excellent stability with
little oxygen reduction. Asadi et al. showed that MoS2 nano- 4.3 Organic electrode batteries
akes with the ionic liquid (IL) 1-ethyl-3-methylimidazolium Using organic materials as electrodes for lithium-ion batteries
tetrauoroborate (EMIM-BF4) can serve as an effective cocata- has been proposed over the last few decades, but they have drawn
lyst for discharge and charge processes in Li–O2 batteries.116 The less attention than the metal based electrodes.119,120 This battery
MoS2/IL system shows superior reaction rates as well as lower type benets from good sustainability, eco-friendly feature, ex-
overpotentials for the oxygen reduction and evolution reactions, ibility in material design, and resource abundance, owing to the
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Fig. 10 Comparison of organic molecules for organic electrode lithium-ion batteries. The N]N reaction indicates the reduction of two nitro
groups by lithium-ions to yield an azo group with the formation of Li2O. Reproduced from ref. 121 with permission (Copyright 2018, WILEY-VCH).
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Fig. 11 (a) Illustration of an all-solid-state Li–sulfur battery. (b) SEM observation of the cross-section of an all-solid-state Li–sulfur battery with
the Li7P2.9–S10.85Mo0.01 electrolyte (SE). Reproduced from ref. 212 with permission (Copyright 2017, Royal Society of Chemistry).
property, low-cost, and good chemical stability.136 The bonding 4.5 Li–CO2 batteries
of Li+ in PEO with chain segment dynamics was identied in
In recent years, the battery community has shown an increased
previous studies.140,141 Li+ can migrate along the polymer chains
interest in Li–CO2 batteries. This battery technology enables
and/or motion with PEO segments.141 However, the lithium-ion
carbon dioxide (CO2) xation while storing energy. Previous
conductivity (107 S cm1) at room temperature is not only
research by Takechi et al. (2011) revealed a novel battery
lower than those of the carbonate electrolytes, but also those of
employing gases, namely, Li/CO2–O2 exhibited a high irrevers-
inorganic solid-electrolytes.142 Improvement of conductivity in
ible discharge capacity, which is three times as much as the
the solid-electrolytes was therefore a key issue for a long time, capacity of a Li–air battery.154 Later on, Lim and Kang et al.
and it still remains unclear whether crystalline or amorphous developed a reversible Li/CO2–O2 battery using dimethyl sulf-
structures can enhance the ion conductivity. Using polymers as
oxide (DMSO) that leads to the reversible formation of Li2CO3.155
solid-electrolytes has the common advantages of good exibility,
Whereas the previous Li gas batteries utilized a CO2 and O2 gas
high stability with Li-metal, and low shear modulus, but they
mixture, Xu and Archer et al. have introduced a primary Li–CO2
suffer from low thermal stability, low ionic conductivity, and low
battery that employs pure CO2 gas as the working electrode for
oxidation chemical potential. These issues should be challenged
achieving charge capacities.156 A year later, Liu et al. demon-
for the practical use of the solid polymer electrolytes (SPEs).
strated a pure and reversible Li/CO2 battery using LiCF3SO3 in
Thin-lm solid electrolytes have also drawn attention as they TEGDME (1 : 4 in mole) as the electrolyte.157 The charge capacity
lead to the development of thin-lm batteries that have higher of the Li–CO2 can be achieved by the following electrochemical
energy density, higher exibility in application design, and
reaction:157,158
higher compactness as compared to the conventional lithium-
ion batteries. The thin-lm solid electrolyte for secondary 3CO2 + 4Li+ + 4e / 2Li2CO3 + C (2.8 V vs. Li/Li+)
lithium batteries was rst demonstrated in the early 1980's using
the Li/Li3.6Si0.6P0.4O4/TiS2 composite.143 There are various
methods that can be used for thin-lm deposition such as radio Li2CO3 is the key component that determines the revers-
frequency sputtering (RFS),144 pulsed-laser deposition (PLD),145 ibility of this battery application. However, Li2CO3 is an insu-
chemical vapor deposition (CVD),146 and atomic layer deposition lator and thus requires a high over-potential to be oxidized on
(ALD).147,148 One of the extensively examined thin-lm batteries is charge. Recent studies by Zhou's group have utilized ruthenium
the lithium phosphonitroxide glass (LiPON) battery. This appli- (Ru) as a cathode catalyst to effectively reduce the high over-
cation was initially reported by Bates et al. in 1992,149 and further potential, thereby improving the reversibility of the Li–CO2
studied by a group in Oak Ridge National Laboratory (ORNL, battery (Fig. 12).158,159 Li/CO2 battery is undoubtedly an attractive
U.S.).150 LiPON could be fabricated by RF-magnetron sputtering technology as it can simultaneously deal with energy and
using Li3PO4 as a target in nitrogen gas. The main advantage of environmental issues. However, high over-potential and low
using LiPON is the good stability with lithium metal and coulombic efficiency are the major problems that need to be
a number of cathode materials. It has been reported that the tackled for practical use.
stability window of LiPON was between 0 V and 5.5 V with
respect to the Li-metal electrode.151 LiPON also benets from its
good hardness and thermal stability.152 Hence, the thin-lm 5. Towards hybridization with Li-ion
LiPON battery (LiNi0.5Mn1.5O4/LiPON/Li) could provide a cycle batteries
life of 10 000 cycles with the capacity retention of 90% up to 5.1 Application of metal halide perovskite
5 V.153 LiPON has recently become a commonly used solid-
electrolyte for the all-solid-state thin-lm batteries, but its rela- Metal halide perovskite (MHP) refers to a class of semi-
tively lower conductivity than oxide-based materials must be conducting materials that can be represented by the general
overcome to develop high-capacity thin-lm batteries. formula of ABX3. MHPs adopt a similar crystal structure to oxide
perovskites such as calcium titanate (CaTiO3). The halide
This journal is © The Royal Society of Chemistry 2019 J. Mater. Chem. A, 2019, 7, 2942–2964 | 2953
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Fig. 12 Schematics of the (a) reaction mechanism of a Li–CO2 battery on charge without a Ru catalyst, (b) reaction mechanism of the Li–CO2
battery on charge with a Ru catalyst, and (c) discharging process. Reproduced from ref. 159 with permission (Copyright 2017, Royal Society of
Chemistry).
anions (X ¼ I–, Br–, Cl–) and metal cations (B ¼ Pb2+, Sn2+) approaching 200 mA h g1 (Table 1). The microscopic views of
form the BX6 octahedron (Fig. 10). The corner-shared BX6 how Li ions interact with a hybrid perovskite structure during
octahedra extend to a three-dimensional (3D) network stabi- the charging–discharging process are still under intense
lized by the presence of larger cations (A being larger than B; debate.175,176,178 The fundamental microscopic understanding
A+ ¼ CH3NH3+, NH2CH]NH2+, Cs+, etc.). MHPs received will play a major role in providing insights to questions such as
tremendous attention in the past years aer their rst (i) why CH3NH3PbI3 perovskites show lower discharge capacity
successful application in photovoltaic (PV) devices in compared to that of CH3NH3PbBr3, i.e., what role do halides
2009.160–163 In 2017, Tsutomu Miyasaka (Toin University of play in the Li-ion storage mechanism? (ii) What are the physico-
Yokohama, Japan), Nam-Gyu Park (Sungkyunkwan University, chemical dynamical processes involved during charging–dis-
Republic of Korea), and Henry Snaith (University of Oxford, charging in MHP materials? A maximum theoretical capacity of
United Kingdom) received recognition as the 2017 Citation 55.96 mA h g1 was calculated for CH3NH3PbBr3 assuming that
Laureates by Clarivate Analytics for their discovery and one Li+ could intercalate per formula unit.178 However, the
application of perovskite materials to achieve efficient energy above reported experimentally measured discharge capacities
conversion.164 Since the successful demonstration in PV are approximately four176 to six174 times larger than the theo-
technology, applications of MHPs have been rapidly extended retical capacity. It has been proposed that reversible Li+ storage
to other technologies, such as light-emitting diodes (LEDs),165 takes place by Li ion intercalation into the host electrode
lasers,166 X-ray detectors and imaging for medical applica- without severe distortion and degradation of the CH3NH3PbBr3
tions,167,168 eld effect transistors (FETs),169,170 etc. A few recent lattice.176 Lithiation reaching molar contents of x ¼ 3 in Lix-
studies suggest that MHPs also have potential for battery CH3NH3PbBr3 was reported (Fig. 13).176,178 Alternatively, Dawson
applications (Table 1).171–180 et al.178 proposed that conversion reactions with Li are more
For example, the room temperature chemical diffusion energetically favorable in CH3NH3PbX3 (X ¼ I, Br, Cl) than Li
coefficient of lithium ions (Li+) within the CH3NH3PbBr3 intercalation. The authors carried out density functional theory
perovskite lattice exhibits a value as high as Dm 107 cm2 s1 (DFT) calculations to simulate four primary Li concentrations, x
meaning that the ionic conductivity is in the order of 103 ¼ 0.037, 0.125, 0.5, and 1.0 in LixCH3NH3PbX3, where x ¼ 1.0
U1 cm1 for highly lithiated electrodes.181 As a comparison, represents full Li intercalation. At a low Li concentration,
graphitic carbon and LiC6 (resulting from Li+ interaction with insertion of Li-ions into CH3NH3PbI3 is more favorable than
graphite employed as the anode in conventional Li ion that for other two perovskites (CH3NH3PbBr3 and CH3NH3-
batteries) have Dm 1012–105 cm2 s1 and Dm 108–1010 PbCl3). At full Li intercalation (x ¼ 1.0), the PbX6 octahedra
cm2 s1, respectively.182,183 Xia et al.174 applied for the rst time undergo structural distortion in all three MHPs. In particular,
CH3NH3PbBr3 and CH3NH3PbI3 organic–inorganic hybrid the distortion strength is more pronounced in CH3NH3PbBr3
perovskites in Li-ion batteries as the anode material. The rst and CH3NH3PbCl3, which suggest the existence of conversion or
discharge capacity for CH3NH3PbBr3 was 331.8 mA h g1 at decomposition reactions when approaching full Li intercala-
a current density of 200 mA g1 (Table 1). This capacity is tion. On the basis of electrochemical characterization, X-ray
approximately the same compared to that of commercially diffraction (XRD), and DFT, two potential conversion reaction
available graphite. The capacity of CH3NH3PbBr3 decreased mechanisms were proposed:178
rapidly in the rst 30 cycles, but aer that it decreased slowly
from 157.4 mA h g1 (31st cycle) to 121 mA h g1 (200th cycle) Li + CH3NH3PbX3 / CH3NH3X + LiPbX2 (1)
with relative retention of 76.9% in the subsequent 170 cycles.
Vincente and Garcia-Belmonte176 also employed CH3NH3PbBr3 2Li + CH3NH3PbX3 / CH3NH3X + 2LiX + Pb (2)
and reported that long-term specic capacity attains values
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Table 1 Summary of metal halide perovskite-based Li-ion batteries. The electrochemical performances were tested in a standard CR2032 coin
cell configuration if there is no statement. Abbreviations: PVDF ¼ poly(vinylidene fluoride); EC ¼ ethylene carbonate; EMC ¼ ethylmethyl
carbonate; DMC ¼ dimethyl carbonate; DEC ¼ diethyl carbonate; FEC ¼ fluoroethylene carbonate; MA ¼ CH3NH3; PA ¼ CH3(CH2)2NH3; AB ¼
acetylene black; EDBE ¼ 2,20 -(ethylenedioxy)bis(ethylammonium); Li(TFSI) ¼ Li bis(trifluoromethane)sulfonimide
Structure
CH3NH3PbI3: Conductive carbon black: 1 M LiPF6 in EC + EMC + Li-foil 43.6 (1st cycle; 200 mA g1) ref. 174
PVDF binder (80 : 10 : 10 mass ratio) DMC (1 : 1:1 vol ratio)
on copper foil
CH3NH3PbBr3: Conductive 331.8 (1st cycle; 200 mA g1)
carbon black: PVDF binder
(80 : 10 : 10 mass ratio)
on copper foil
CH3NH3PbBr3: Conductive 1 M LiPF6 in EC + EMC + Li-foil 550 (1st cycle; 200 mA g1); ref. 176
carbon black: PVDF binder DMC (1 : 1:1 vol ratio) 150–200 (aer 10 cycles)
(80 : 10 : 10 mass ratio)
on copper foil
CH3NH3PbBr3: Carbon super P 1 M LiPF6 in EC + Li-foil 134.3 (20 mA g1) ref. 178
Li: PVDF binder (80 : 10 : 10 mass ratio) DMC (1 : 1 wt)
on copper foil
CH3NH3PbBr3/ITO Three-electrode cell Li-foil 475 (0.1 mA cm2) ref. 180
CH3NH3PbIBr2/ITO (0.1 mA cm2; 0.1–1.5 V @ RT): 425 (0.1 mA cm2)
CH3NH3PbI3/ITO 1 M LiPF6 EC + DEC (1 : 1 vol ratio) 340 (0.1 mA cm2)
CsPbBr3: Conductive carbon black: 1 M LiTFSI in 1,3-dioxolane/ Li-foil 102.6 (1st cycle) ref. 177
PVDF binder (50 : 25 : 25 mass ratio) dimethoxyethane (1 : 1 volume ratio)
on copper foil
(MA)2(PA)2Pb3Br10: AB: PVDF Three-electrode cell Li-foil 375 (425 mA g1) ref. 180
on Cu foil (0.1 mA cm2; 0.1–1.5 V @ RT):
1 M LiPF6 EC + DEC (1 : 1 vol ratio)
C6H9I3NOPb (1D): Conducting 1 M LiPF6 in EC:DMC Li foil 1580 (1st cycle; 100 mA g1) ref. 179
carbon: PVDF (60 : 30 : 10) (1 : 1 ratio) + 5% FEC
on Cu foil
(C4H9NH3)2PbI4 (2D) 1605 (1st cycle; 100 mA g1)
CH3NH3PbI3 (3D) 476 (1st cycle; 100 mA g1)
C6H9I3NOPb (1D): Conducting carbon: 1 M NaClO4 in EC:DMC Na-foil 961 (1st cycle; 100 mA g1)
PVDF (60 : 30 : 10) on Cu foil (1 : 1 ratio) + 5% FEC
(EDBE)[CuCl4]: Conductive carbon black: 1 M Li(TFSI) in dimethoxythane Li-foil 25 (28 mA g1) ref. 172
PVDF (8 : 2 : 1 mass ratio) on copper
or aluminum foils
The conversion reaction represented in eqn (1) involves reaction in eqn (2) is similar to the reaction found in conven-
phase separation (decomposition) of the perovskite, with Li tional battery materials. The cation of a metal oxide or uoride
being intercalated in the PbX2 layered structure. The conversion is reduced by Li metal to form the corresponding metal and
lithium oxide/uoride (e.g., CoO + 2Li / Co + Li2O).178,184,185 In
the case of MHPs, the conversion reaction involves the forma-
tion of CH3NH3X, 2LiX, and metallic-Pb as products. Ramirez
et al.180 investigated the electrochemical properties of CH3-
NH3PbIxBr3x with x ¼ 0, 1, 2 in a simple three-electrode cell
using MHP deposited lms (500 nm; 1 mg) on indium-tin
oxide (ITO) as the working electrode and Li-foil as both
counter and reference electrodes (Table 1). The Li extraction
reaction achieved charge capacities of 70–160 mA h g1 for the
rst cycle, followed by an irreversible capacity. The calculated
number of Li-ions per mole of electrode material was 9.7, 6.6,
and 8.7 for CH3NH3PbI3, CH3NH3PbIBr2, and CH3NH3PbBr3,
Fig. 13 Metal halide perovskite structure with B metals assembled respectively. Improvement in charge–discharge capacity was
around X anions to form a BX6 octahedron. Cations fill the space found when iodine was completely substituted by bromine. The
formed by the eight corner-shared adjacent octahedra and balance
the charge of the whole network. Multiple Li+ ion intake in the
MHPs with partial substitution (CH3NH3PbIBr2) led to lower
perovskite lattice is schematically represented. Reproduced from ref. charge–discharge capacity, indicating a competition between
176 with permission (Copyright 2017, American Chemical Society). the crystalline structure and bromine content. A recent study on
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Li-ion batteries assembled with the CsPbBr3 composite as the performance when employed as anodes for ion batteries
working electrode achieved the rst charge–discharge capacity because they can allow more intercalation into the free space
of 94.8 and 102.6 mA h g1, respectively.177 XRD patterns of between layers.173,179,180 Tathavadekar et al.179 performed
CsPbBr3 before and aer electrochemical lithiation showed a systematic study on C6H9I3NOPb (one dimensional, 1D), (C4-
a slight increase of the lattice constant conrming Li H9NH3)2PbI4 (two dimensional, 2D), and CH3NH3PbI3 (3D)
intercalation. Furthermore, metallic-Pb was probed by X-ray MHPs (Fig. 14) for accessing the specic capacity and stability
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photoelectron spectroscopy (XPS) on CsPbBr3 aer the electro- associated with MHP dimensionality. The specic capacity
chemical lithiation using a wider potential window that also (tested up 250 cycles) and stability improved dramatically by
relates to eqn (2).177 These initial reports show that the tuning the dimensionality of MHPs from 3D to 2D to 1D
composition of 3D ABX3 MHPs plays a major role in the Li-ion (Fig. 14g and Table 1). The 3D CH3NH3PbI3 showed a rst
storage performance. Considering the structural diversity, discharge capacity of 476 mA h g1 at a current density of
better performance of Li-ion storage may be achieved by tuning 100 mA g1. More dramatic enhanced performance data in the
the 3D MHP composition. case of 2D and 1D with 1605 mA h g1 and 1580 mA h g1 were
One of the key aspects of material properties for commer- reported, respectively, which are nearly four times higher than
cialization in Li ion battery technology concerns the high that of the 3D case. These high rst discharge capacities suggest
tolerance for volume expansion (i.e., preservation of structural that the low dimensional structures provided better access for
integrity) over many charge–discharge cycles and high revers- Li-ions to the lead atoms in the MHP structures with which
ibility with minimum instabilities during the phase transition LixPb alloys are formed. The large drops from the rst discharge
of active materials and uncontrolled reactions at the electrode/ capacity to the rst reversible capacity for all the 3D–2D–1D
electrolyte interfaces.182,186 Among the different structures of cases are attributed to the irreversible reactions in the electrode
MHPs, low-dimensional MHPs are generally reported to be material and solid electrolyte interphase (SEI) formation.
more robust in terms of long-term stability in performance over However, it has been proposed that the formation of a stable SEI
time as reported in several studies in the eld of photovol- layer prevents further degradation of the MHP material
taics.187–190 In the eld of Li ion batteries, low-dimensional observed from a stable capacity in subsequent cycles. As shown
MHPs have been demonstrated to further show superior in Fig. 14h, the benzidine-based 1D case showed a robust
Fig. 14 (a) Perovskite structures of (a) C6H9I3NOPb (1D), (b) (C4H9NH3)2PbI4 (2D), and (c) CH3NH3PbI3 (3D). (d), (e), and (f) represent the cor-
responding 3D perspectives. (g) Galvanostatic charge–discharge cycling stability measurements for 1-2-3D perovskites at a current density of
100 mA g1 in the potential window of 2.5 to 0.01 V. (h) Cycling stability at different charge–discharge rates varying from 100 mA g1 to
500 mA g1 in the potential window of 2.5 to 0.01 V for the 1D perovskite case up to 250 cycles. Reproduced from ref. 179 with permission
(Copyright 2017, The Royal Society of Chemistry).
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cycling performance holding the capacity at 585 mA h g1 at Great efforts are being made in this direction with several
a current density of 100 mA g1 up to 50 cycles, 525 mA h g1 proposed innovative designs.12,193–195 Two design principles are
at a current density of 250 mA g1 up to 136 cycles, and oen discussed: (i) conventional design of solar charging
453 mA h g1 at a current density of 500 mA g1 up to 250 batteries that involves use of batteries and solar modules as two
cycles. Ramirez et al.180 have also studied the performance of separate units connected by electrical wires (Fig. 15a
another 2D class of semiconducting MHPs (Ruddlesden- and b)193,194; (ii) advanced design that involves the integration of
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Popper (RP) layered perovskites), namely propylammonium- in situ battery storage in solar modules and therefore, offering
methylammonium lead bromide (CH3NH3)2(CH3(CH2)2NH3)2- compactness and fewer packaging requirements with the
Pb3Br10 consisting of an alternating arrangement of large potential of low-cost (Fig. 15c).12 The overall efficiency of an
organic layers and inorganic layers. The layered structure in integrated solar cell–battery system is a product of sun energy-
MHPs was demonstrated to be important for allowing revers- to-electricity power conversion efficiency (PCE) of the solar
ibility of the Li insertion–extraction of 100% with capacities of cell and energy storage efficiency of the battery. An insightful
375 mA h g1. On the basis of electrochemical impedance review article by Gurung et al.195 describes the current status on
spectroscopy (EIS), cyclic voltammogram (CV), charge– solar charging battery systems. In this section, because of our
discharge proles, and XRD, the proposed mechanism for research group expertise and concerted efforts towards Li-ion
lithiation consists of a Li-ion intercalation mechanism in the batteries and MHP based solar cells, we limit our description
MHP material followed by the Pb(II) / Pb(0) reduction process to the above two integrated systems focused on the use of
and alloying–dealloying process of the LixPb intermetallic MHPs.43,191,192,196–198 Xu et al.193 demonstrated that four single
compounds (LiPb, Li8Pb3, Li10Pb3, and Li22Pb5).179,180 However, junction CH3NH3PbI3 based perovskite solar cells connected in
in the delithiation process the Pb(0) / Pb(II) reaction is not series could be used to directly photo-charge a Li-ion battery
favorable, and as a result Pb-metal centers remain in the matrix composed of an LiFePO4 cathode and an Li4Ti5O12 anode
of organic molecules. This MHP disintegration is not harmful (Fig. 15a). This system achieved an overall photoelectric
because the matrix of organic molecules functions as a strain conversion and storage efficiency of 7.8% at 0.1C and 7.36% at
absorbing environment (cushion effect) against the typical 0.5C discharge. This integrated device showed an energy
electrode pulverization due to volume expansion. Furthermore, storage efficiency of 60%. Gurung et al.194 performed a similar
the presence of organic parts in MHPs was suggested to help study, but they used a single CH3NH3PbI3 based perovskite
avoid the detachment of LixPb alloys from the electrode.179 solar cell adding inline a commercially available low-power
The toxicity of a material applied to technology is another direct current–direct current (DC–DC) boost converter
concern for investors and consumers, where handling mistakes (BQ25504EVM; Texas Instruments) with maximum power point
during fabrication, leakage during operation, or the disposal tracking (MPPT) to efficiently charge their integrated Li-ion
phase may cause severe damage to the environment and to battery composed of an LiCoO2 cathode and an Li4Ti5O12
human beings.191,192 Initial studies have attempted the use of 2D anode (Fig. 15b). The DC–DC converter circuit helps boost the
MHP materials composed of a conducting organic material and low voltage of the single junction solar cell to the required
Pb-free active inorganic material as Li-ion storage mate- charging voltage of 2.4 V Li-ion battery. In addition, this DC–DC
rials.171,172,175 However, the reported performances are low with converter circuit extracts the maximum power from the perov-
typical specic capacity less than 50 mA h g1 (Table 1).171,172,175 skite solar cell by the MPPT. This approach leads to the highest
It has been proposed that Sn and Cu-based systems may be reported overall efficiency of 9.36% and average storage effi-
viable options as replacements for the Pb-case; for example, Sn ciency of 77.2% at 0.5C discharge. This work shows that it is
was calculated to have higher alloying capacity than Pb.172,179 important to have an appropriate matching of voltage and
The MHP research applied to energy storage technology is still current between solar cells and batteries for attaining high
at a premature stage and further concerted efforts are needed to efficiency by means of an external MPP tracker. Alternatively,
claim any superiority of these materials over previously a simpler design of a single device with merged functionalities
researched non-perovskite based anode materials. However, of sun energy harvesting and storage was reported by Ahmad
based on our survey of reported studies, the concept of low- et al.12 (Fig. 15c). 2D perovskite materials [(RNH3)2MX4 with R ¼
dimensional materials may have important implications for organic moiety, M ¼ metal, X ¼ halide] can be used for both
further improvements of MHP-based electrodes as well as energy storage (battery functionality) and photo-charging
development of new useful materials for energy storage (photovoltaic functionality) simultaneously. The authors
applications. studied rst the application of 2D lead halide based perovskites,
(C6H9C2H4NH3)2PbI4 (CHPI) and (C6H9C2H4NH3)2PbBr4
(CHPB) as anodes in coin cell nonphoto-chargeable batteries.
5.2 Photo-rechargeable batteries Capacities of 90–100 mA h g1 and 410 mA h g1 were
Batteries are energy limited and require recharging. On the achieved in the rst cycle employing CHPI and CHPB, respec-
other hand, batteries can be used to address the intermittency tively. The hybrid solar cell–battery device architecture is
concern of solar cells. Development of photovoltaic-battery composed of a 2D perovskite-rGO-PVDF (rGO ¼ reduced gra-
integrated systems with high energy density, efficiency, phene oxide; PVDF ¼ poly(vinylidene uoride)) lm sandwiched
stability, and low-cost is a topic of importance for unin- between a separator and a transparent collector electrode
terruptible utilization of electricity generated from solar energy. uorine-doped tin oxide, FTO. This photo-battery is rst
This journal is © The Royal Society of Chemistry 2019 J. Mater. Chem. A, 2019, 7, 2942–2964 | 2957
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Fig. 15 (a) Photo-charging of a Li ion battery by a perovskite solar cell. Reproduced from ref. 193 with permission (Copyright 2015, Nature
Publishing Group). (b) Photo-charging diagram of an Li4Ti5O12–LiCoO2 cell using a CH3NH3PbI3 based perovskite solar cell. The BQ25504EVM
converter (Texas Instruments) is employed to provide DC to DC boost conversion and maximum power point tracking capability. Reproduced
from ref. 194 with permission (Copyright 2017, WILEY-VCH). (c) Device structure and schematic representation of photo-charging and dis-
charging of a perovskite photo-battery. Reproduced from ref. 12 with permission (Copyright 2018, American Chemical Society).
charged to saturation by a broadband light source (l 420– storage materials and technologies. The integrated solar cell–
650 nm; 100 mW cm2) and then discharged through an LED. A battery system technology is still at a very early stage, but for
capacity of up to 100 mA h g1 can be delivered in this photo- a few reports demonstrating the feasibility to harvest solar
battery. The proposed mechanism of energy storage is shown energy to charge batteries. In particular, the design aiming
in Fig. 15c. Li ions migrate to the 2D perovskite anode where integration of in situ battery storage in solar cells is of great
a combination of intercalation and conversion mechanism advantage offering compactness and fewer packaging require-
takes place.12 Another new type of solid-state electrochromic ments with the potential of low-cost. Commercialization of such
batteries powered by perovskite solar cells have been designed integrated systems is still far from the present and it will
by Xia et al.199 These electrochromic batteries were demon- depend signicantly on the individual material and device
strated to deliver a capacity of 75 mA h g1 at 1 A g1. architecture in both solar cell and battery research. Regarding
Sustainability and clean energy have driven the innovation and this aspect, MHP materials may be key for the advancement of
development of advanced technologies of solar cell and energy such technology. The exceptional performance of MHPs as sun
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energy harvester materials for solar cells was demonstrated and oxidation changes between Ni2+/Ni3+ and Ni3+/Ni4+ signi-
ascribed to their excellent material properties such as direct cantly contribute to the charge compensation mechanism, and
band gap, outstanding high absorption coefficient, abrupt thus extra capacities can be achieved when the NMC cathode
optical band edge, large charge carrier diffusion length and low has a higher Ni concentration. Although the high-capacity
exciton binding energy. The exploration of MHP materials in feature is derived from the conventional LiNiO2, recent
the eld of Li-battery is still scarce. However, the initial studies studies have attempted to nd the precise and optimum stoi-
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have demonstrated that low-dimensional MHPs show superior chiometric ratio between Ni (high concentration), Mn, and Co
performance when employed as anodes because they can allow to develop a high-performance battery with improved stability
more intercalation into the free space or within the organic and/or good rate capability. We therefore consider the emer-
layers.173,179,180 Furthermore, low-dimensional MHP materials gence of Li-rich and Ni-rich layered oxides as the initial evolu-
provide key aspects of high tolerance for volume expansion over tion towards advanced technologies for high energy and power-
many charge–discharge cycles, high reversibility with minimum density lithium-ion batteries. However, there are also critical
instabilities during phase transition in active materials, and drawbacks of these battery systems. Li-rich layered oxide
controlled reactions at the electrode/electrolyte interfaces.182,186 batteries undergo an irreversible capacity loss during the initial
The ABX3 chemical composition engineering and/or alloying cycles. At a higher cut-off voltage (>4.5 V), lithia (Li2O) is
strategy has been scarcely explored and further exploration for extracted from Li2MnO3 with phase transformations, resulting
an optimal composition is expected to bring subsequent years in dramatic capacity fading during subsequent charge and
of key ndings for the Li-ion battery community and solar cell– discharge. Also, Ni-rich layered oxide batteries suffer from
battery integrated systems. electrode degradation by the undesired redox reactions with the
electrolyte. Surface reconstruction or clustering by NiO at
6. Conclusion and outlook higher voltage ranges is another major problem which needs to
be addressed. Engineering the active material by substituting
The evolution of lithium-ion batteries strongly relies on the with other transition metals or employing surface coatings is
development of working electrodes. Notwithstanding that the likely to be helpful in ameliorating the battery performance and
current review covers a limited number of electrode types, the stability. Moreover, replacing conventional electrolytes with
surveys certainly add to the comprehensive outlook on the specially designed electrolytes can be a reasonable treatment for
advances of the battery technologies. In the early period, mitigating the aggressive electrolyte decomposition at a high
different classes of electrode materials were proposed such as operating voltage. However, some inherent limitations persis-
olivine, spinel, and layered materials. This classication is tently remain, preventing them from being used for high-
based on the type of Li+ (ionic) diffusion pathways rather than capacity batteries. Hence, alternative material technology, i.e.,
the chemical composition. Since the successful commerciali- conversion electrodes, has been renewed in recent years. This
zation of LCO, developing batteries with a balance between old concept (chemistry) is rising again, leading to the develop-
discharge capacity, thermal stability, capacity retention, and ment of new energy storage technologies such as Li–sulfur, Li–
lifespan has become a central issue of battery research. This air, and Li–CO2 batteries. We regard this as an evolution into
leads to the development of mixed transition metal oxide the state-of-the-art technologies for lithium-ion batteries.
cathodes (e.g. NMC), which can provide synergetic benets over Owing to the conversion mechanism, the discharge capacity
a single transition metal cathode. However, growing demands and the energy-density could be dramatically enhanced.
for lithium-ion batteries to operate with higher discharge However, there are also technical barriers that limit the
capacities and longer cycle numbers have led to a renewed successful commercialization of these applications such as
interest in tailoring the existing NMC electrode. The develop- over-potential (Li–air and Li–CO2), shuttling effect (Li–sulfur),
ment of Li-rich (or excess) layered oxide cathodes, oen denoted poor rate capability, high interphase resistance (solid-state
as xLi2MnO$(1 x)LiTO2 (T ¼ Mn, Ni, Co), has drawn much batteries) and low cycle life.
attention due to their superior theoretical capacity We are also anticipating the evolution of lithium-ion battery
(>250 mA h g1) with high operation voltage (>4.6 V vs. Li0). As technologies towards self-sufficiency, namely, a stand-alone
discussed, the origin of the high charge capacity in this battery energy system (or off-grid) for autonomous electronic devices
system can be explained by the intimate integration between has drawn much attention, recently. The major advantage of
the (001) planes from Li2MnO3 and the (003) planes from LiTO2 using this technology is the high energy efficiency with reliable
with the interlayer spacing of 4.7 Å by the interleaving of close- power at reasonable cost, providing electricity in a remote
packed layers. Simply, this can be regarded as an NMC cathode location. Photo-rechargeable batteries are a good example of the
with a Li+ booster by Li2MnO3. The development of Li-rich stand-alone energy system, as they combine energy harvesting
transition metal oxide cathodes involves both compositional materials with energy storage materials. A key factor that leads
and structural modications of the conventional material. The to the successful development of the autonomous device is the
ever-growing markets of electric vehicles (EVs or HEVs) are now seamless integration of the power source (e.g. battery electrode)
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a promising solution to meet the urgent demand, due to their voltaic material for solar-cells. A problem can arise, however,
high discharge capacity (220 mA h g1). The two-stage when an attempt is made to combine the organohalide
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