Battery Energy - 2022 - Hadouchi - The Origin of Fast Charging Lithium Iron Phosphate For Batteries

Received: 13 September 2021 | Revised: 25 October 2021 | Accepted: 10 November 2021
DOI: 10.1002/bte2.20210010
REVIEW
The origin of fast‐charging lithium iron phosphate

for batteries
Mohammed Hadouchi1,2 | Toshinari Koketsu1 | Zhiwei Hu3 | Jiwei Ma1
1
Shanghai Key Laboratory for R&D and
Application of Metallic Functional Abstract
Materials, School of Materials Science Since the report of electrochemical activity of LiFePO4 from Goodenough's
and Engineering, Institute of New Energy
for Vehicles, Tongji University, Shanghai,
group in 1997, it has attracted considerable attention as cathode material of
China choice for lithium‐ion batteries. It shows excellent performance such as the
2
Laboratoire de Chimie Appliquée des high‐rate capability, long cyclability, and improved safety. Furthermore, the
Matériaux, Centre des Sciences des
raw materials cost of LiFePO4 are lower and abundant compared with con-
Matériaux, Faculty of Science, Mohammed
V University in Rabat, Rabat, Morocco ventional Li‐ion battery oxides compounds. The lithium extraction from
3
Department of Physics of Correlated LiFePO4 operates as biphase mechanism accompanied by a relatively large
Matter, Max Planck Institute for volume change of ∼6.8%, even though, nanosized LiFePO4 shows exceptionally
Chemical Physics of Solids, Dresden,
Germany
high‐rate capability during cycling. In the aim to explain this remarkable
feature, recent reports using cutting‐edge techniques, such as in situ high‐
Correspondence resolution synchrotron X‐ray diffraction, explained that the origin of the ob-
Zhiwei Hu, Department of Physics of
Correlated Matter, Max Planck Institute served high‐rate performance in nanosized LiFePO4 is the absence of phase
for Chemical Physics of Solids, separation during battery operation at high current densities. In this review,
Nöthnitzer Strasse 40, 01187 Dresden,
the importance of understanding lithium insertion mechanisms towards ex-
Germany.
Email: zhiwei.hu@cpfs.mpg.de plaining the significantly fast‐charging performance of LiFePO4 electrode is
highlighted. In particular, phase separation mechanisms, are unclear and
Jiwei Ma, Shanghai Key Laboratory for
deserve considerable attention. Several proposed models for Li diffusion and
R&D and Application of Metallic
Functional Materials, School of Materials phase separation in LiFePO4 are summarized. In addition, the crystallographic
Science and Engineering, Institute of New aspects, defect structures of LiFePO4 are also reviewed. Finally, the status of
Energy for Vehicles, Tongji University,
201804 Shanghai, China.
development of other olivine‐type LiMPO4 (M = Co, Mn, and Ni) are
Email: jiwei.ma@tongji.edu.cn summarized.
Funding information KEYWORDS

National Natural Science Foundation of batteries, crystallography, energy storage
China, Grant/Award Number: 21805209
1 | INTRODUCTION large‐scale applications such as e‐mobility (electric ve-

hicles [EVs], hybrid electric vehicles [HEVs], plug‐in hy-
Lithium‐ion batteries show superior performances of brid electric vehicles [PHEVs]), and power storage
high energy density and long cyclability,1 and widely applications. Since the first demonstration of its electro-
used in various applications from portable electronics to chemical activity of LiFePO4 for lithium‐ion batteries
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided
the original work is properly cited.
© 2022 The Authors. Battery Energy published by Xijing University and John Wiley & Sons Australia, Ltd.
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2 of 19 | HADOUCHI ET AL.
(LIBs) by Goodenough's group in 1997,2,3 LiFePO4 and its towards explaining the origin of the outstanding rate
family attracted considerable attention as the cathode capability. Even the presence of phase transformation
materials. Compared to common oxide cathodes accompanied by relatively large volume changes due to
(e.g., LiCoO2,4 LiMn2O4,5 Li(Ni,Co,Al)O2, and Li(Ni,- structural rearrangements, the origin of high‐rate cap-
Co,Mn)O26), the materials are abundant, environmentally ability in LiFePO4 nanoparticles is related to a solid‐
benign, and their cost are low. Besides, LiFePO4 shows solution mechanism that can be formed during cycling at
high chemical and thermal stability, contributing to the high current rates rather than phase separation between
improved safety and cyclability. Its charge–discharge LiFePO4 and FePO4. In this review, we summarized the
curves show a characteristic flat curve at ∼3.4 V versus progress made in understanding the electrochemical me-
Li+/Li, and with the limited theoretical capacity of chanism during the past two decades of research and
∼170 mA h g−1. The conductivities of LiFePO4 is low development on LiFePO4 cathode materials. Besides, the
(∼10−9 S cm−1) and it is difficult to be practical at the crystal structure, the electrochemical mechanism, and the
pristine state. However, its electrochemical performances electrochemical performances of LiFePO4 family are also
can be largely improved by several synthetic techniques reviewed.
such as nanostructuring, carbon coating, and doping. Al-
though theoretical performances such as working poten-
tial and energy density (∼580 Wh/kg) are rather low 2 | C RY S T A L S T RUCT URE A ND
compared with oxides, its working potential range can be BRIEF H IS TORY OF LiFeP O 4
advantageous to minimize side reactions between cathode
and electrolytes, especially at large polarizations during The crystal structure determination of LiFePO4 has
the high‐rate charging. Besides, the working potential, been carried out by Yakubovich et al.15 It crystallizes in
which is equivalent to ∼0.35 V versus standard hydrogen olivine‐type structure with orthorhombic symmetry,
electrode, is suitable for aqueous electrolytes, and water‐ space group Pnma, characterized by a distorted hex-
containing hydrate‐melt electrolytes‐based LIBs. All the agonal anion close packing, while the Li and Fe occupy
above advantages make LiFePO4 an attractive candidate octahedral sites and phosphorus atom adopt tetrahedral
as a cathode material for LIBs and is largely studied in environment. As shown in Figure 1A, in the crystal
worldwide. Outstandingly, LiFePO4 offers high‐rate structure of LiFePO4, each FeO6 octahedron is sur-
performance.7–10 The high‐rate capability of electrode rounded by four FeO6 octahedra through common
materials is an important characteristic that is required to corners, forming zigzag layers in the (b, c) plane. The
fulfill the commercial demands for fast‐charging batteries. stacking of these layers along the a‐axis through shar-
For the development of high‐rate capability LIB electrode ing one edge and two corners of PO4 tetrahedra leads to
materials, two main factors should be optimized, that is, a three‐dimensional (3D) framework producing 1D
the lithium diffusion and the electrical conductivity of the tunnels where the Li+ cations are located. The de-
electrode material.11 The diffusion of Li can be improved lithiated phase FePO4 crystallize in the same structure
by developing suitable particle size and morphology as LiFePO4 (Figure 1B,C). With the extraction of li-
which can offer short and fast Li diffusion pathways. Also, thium from LiFePO4, the volume decreases by ∼6.8%.
the structure and its changes at atomic scale during bat- The structural similarity between LiFePO4 and FePO4
tery operation plays a crucial role in the Li diffusion, guarantees the excellent electrochemical cyclability of
therefore designing an electrode with an open framework LiFePO4.
(e.g., tunnels) that operates with a single‐phase mechan- X‐ray absorption near‐edge spectroscopy (XANES)
ism can offer the high‐rate capability.12 Furthermore, to and extended X‐ray absorption fine structure (EXAFS)
improve the energy density, interest has also grown in have been used to investigate local atomic and electronic
developing other olivine‐type LiMPO4 (M = Mn, Co, and structure and the electrochemical stability of LiFePO4
Ni) phosphates.13,14 electrode.17–21 Deb et al.18 carried out the XANES and
The LiFePO4 is also interesting from the viewpoint of EXAFS measurements during battery operation of LiFe-
the electrochemical insertion mechanism. It operates PO4 electrode, they demonstrated that during delithia-
through biphase mechanism which is still under debate tion process of LixFePO4 to 3.9 V the valence state of Fe
and investigation. Although the biphase mechanism be- changes from 2 to 3, accompanied with small volumetric
tween the end members LiFePO4–FePO4 results in ∼6.8% changes of the FeO6 octahedra which testify the high
volume change upon delithiation process, LiFePO4 nano- stability of the structure upon charging leading to su-
particles can be cycled at high current rates, which is a perior electrochemical performance. Furthermore,
remarkable feature of LiFePO4. Recent works made huge Leriche et al.17 designed an operando electrochemical
progress in understanding the electrochemical mechanism cell for synchrotron measurements and investigated the
HADOUCHI ET AL. | 3 of 19
F I G U R E 1 Crystal structure and in situ X‐ray absorption spectroscopy (XAS) of LiFePO4. (A) Li+ cations in the tunnels running along
the [001] direction. Unit cells of (B) LiFePO4 and (C) FePO4. The drawings were drawn using Diamond software using the CIF file in
Ref. 16, with permission of the International Union of Crystallography. (D) Normalized absorption of the Fe K‐edge recorded at the
equilibrium for various states of charge within the LiFePO4/FePO4 system. The top insert is the corresponding charge curve, and the bottom
insert is an expanded view of the pre‐edge part. (E) (upper part) Normalized absorption of the iron K edge for various compositions in the
FePO4/LiFePO4 system and (lower part) linear combination fit for the Li0.36FePO4 composition (reprinted from Ref. 17 Copyright 2010. The
Electrochemical Society)
LiFePO4–FePO4 electrochemical mechanism. The ob- 3 | L I T H I UM EX T RA C T I O N /

served Fe K‐edge positions shift progressively to higher INSERTION M ECHANISM OF
energies during delithiation confirms the oxidation of LiFePO 4
FeII to FeIII (Figure 1D). Form the fitted XANES spectra
they concluded the biphasic nature of the electro- The electrochemical extraction of Li+ from crystal
chemical mechanism between LiFePO4 and FePO4 end‐ structure of LiFePO4 operates through a bi‐phase me-
members (Figure 1E). chanism, that is, LiFePO4 ⇄ FePO4 + Li+ + e−, giving a
In summary, the LiFePO4 material crystallizes in the flat plateau at ∼3.4 V versus Li+/Li. This voltage lies in
olivine‐type structure with orthorhombic system. Its 3D the stability window of the carbonate electrolytes, which
structure built from the corner‐sharing of FeO6 octahe- makes LiFePO4 an excellent cathode material in terms of
dra and PO4 tetrahedra produces 1D tunnels where the electrochemical stability. The electrochemical activity of
Li+ cations are accommodated. During discharge, the LiFePO4 was first brought to light in 1997 by
LiFePO4 cathode operates through biphase mechanism Goodenough et al.2 The electrochemical extraction was
with a large volume change of ∼6.81% between LiFePO4 limited to 0.6 Li+ per formula unit giving a capacity of
and FePO4 end members. The XANES and EXAFS 110 mA h g−1, even though the theoretical capacity of the
measurements during battery operation confirm the full removal of lithium is 170 mA h g−1. It has been
oxidation of FeII to FeIII. shown that LiFePO4 cycles well at ambient temperature.
However, a reversible capacity loss occurs at higher ∼6.81% and the density increased by ∼2.59%.2 The unit
current densities, which could be due to limiting “in- cells of LiFePO4 and FePO4 are shown in Figure 1B,C,
terface diffusion” within a single grain. To overcome this respectively. Also, the two‐phase mechanism was de-
limitation high‐temperature studies were undertaken in scribed by “shrinking core model’’ in which the lithium
the aim to enhance the lithium diffusion rate and insertion proceeds from the surface of the particle
therefore increase the reversible capacity at higher cur- moving inward behind a two‐phase interface as illu-
rent densities. Indeed, Andersson et al.22 and Takahashi strated in Figure 2A. Moreover, LiFePO4 suffers from the
et al.23 showed that the performance was largely im- decrease in capacity at higher current densities, which
proved at elevated temperature but still did not reach the was explained to be associated with the movement of a
theoretical capacity of 170 mA h g−1 at 80°C. Since the two‐phase interface. More precisely, with the surface
lithium insertion/extraction mechanism plays a crucial area in the FePO4 is decreasing, the lithium that can pass
role to understand and optimize the cathode perfor- through the interface is suggested to be limited to sustain
mance, the lithium extraction/insertion process in the current which leads to the capacity loss at higher
LiFePO4 has been given immense attention. The inser- current densities. In this context, Andersson et al.,24
tion/extraction mechanism was first described by Padhi investigated the origin of this capacity loss and explained
et al.2 as a two‐phase process between LiFePO4 and its source related to (i) the synthesis route which affects
FePO4 through chemical delithiation via NO2PF6 in the particle size, thus, affecting the electronic con-
acetonitrile. Both endmembers of LiFePO4 and FePO4 ductivity of the particles and (ii) the electrode mor-
crystallizes in the same space group. Upon chemical phology (particle distribution, binder…). Furthermore,
extraction of lithium from LiFePO4, a and b lattice they proposed two new possible models “mosaic model,”
parameters decreased, while a small increase in the c which considers the viability of the extraction/reinser-
parameter was observed. The volume decreased by tion to occur at many sites within a given particle of
F I G U R E 2 Li‐ion extraction/insertion models. (A) Schematic representation of the of LiFePO4/FePO4 interface on lithium insertion to a
particle of FePO4 (reprinted from Ref. 2 Copyright 1997 The Electrochemical Society Inc.). (B) Schematic representation of two possible
models for lithium extraction/insertion into a single particle of LiFePO4: (b‐1) Mosaic model and (b‐2) radial model (reprinted from Ref. 24
Copyright 2001. Elsevier Science B.V.). (C) Polyhedral representations of the interfacial region between LiFePO4 and FePO4
phases (reprinted from Ref. 25 Copyright 2006. American Chemical Society); (c‐1). Hypothesis of a disordered LixFePO4 phase with a
gradient of Li content between FePO4 and LiFePO4 end members, which is not verified by HR‐EELS measurements; (c‐2) front phase
evolution during delithiation, deduced from HR‐EELS; (c‐3) front phase evolution during lithiation, deduced from HR‐EELS. Small vertical
arrows indicate the movement of (Li+, e−) pairs, the longest ones symbolizing an energetically favored extraction/insertion from/into the
channels. The large red arrows indicate the direction in which the interfacial region is moving. HR‐EELS, high‐resolution electron energy
loss spectroscopy
LiFePO4 and “radial model” (e.g., shrinking core model) The possibility of the existence of a solid‐solution
as illustrated in Figure 2B. Later on, Srinivasan et al.26 LixFePO4 region in LiFePO4–FePO4 system is an
developed a mathematical model improving the shrink- important subject that has attracted a great deal of
ing core model by considering both the diffusion of Li interest.27,30 Indeed, Yamada et al.,27 revealed, using
through the shell and the phase boundary movement. In neutron powder diffraction at RT, the formation of in-
this spirit, Yamada et al.27 suggested that solid solution termediate LiαFePO4 and Li1−βFePO4 phases containing
could happen at room temperature (RT) in LiFePO4 a mixture of Fe3+ and Fe2+. The occupancy of lithium
nanoparticles, as demonstrated by Rietveld refinements sites in both phases were α = 0.05 and 1−β = 0.89. Fur-
of X‐ray and neutron diffraction data, as well as calori- thermore, Meethong et al.,30 studied the size‐dependent
metric measurements, thus confirming the shrinking lithium miscibility gap in nanoscale Li1−xFePO4. They
core model. However, the mechanism of how such two‐ showed that, the miscibility gap in Li1−xFePO4 decreases
phase insertion proceeds has been clarified by Chen with decreasing the particle size in the nanoscale regime.
et al.28 using electron microscopy on large hydro- Interestingly, Gibot et al.,31 demonstrated the possibility
thermally grown LiFePO4 crystals following the chemi- to drive the two‐phase room‐temperature insertion pro-
cal delithiation. They reported the occurrence of cess in LiFePO4 electrodes into a single‐phase one by
disordered transition zones in the bc‐plane, as the phase modifying the material's particle size and ion ordering.
boundary progresses in the direction of the a‐axis, with Indeed, the study was performed on electrodes made of
the Li‐ions moving in a direction parallel to the phase LiFePO4 nanoparticles (40 nm) synthesized by a low‐
boundary (e.g., along the b‐direction). Although the size temperature precipitation process which showed sloping
of the particles could have a critical bearing on the voltage charge/discharge curves, characteristic of a
transport of Li+ ions and electrons into and out of single‐phase mechanism.
the individual particle, this study has clearly revealed Since the observation of different mechanisms and
that the well‐adopted core‐shell model does not apply to remarkable rate performances in nanosized LiFePO4,25
individual crystallites. Afterward, Laffont et al.25 com- tremendous efforts and significant progress have been
bined high‐resolution transmission electron microscopy made in understanding the LiFePO4 phase transforma-
(HR‐TEM) coupled with high‐resolution electron energy tion, especially of single LiFePO4 nanoparticle.9,32–40
loss spectroscopy and described a “new core‐shell” Malik et al.38 have demonstrated, by first‐principle cal-
model. Their results are in line with those of Chen culations, that the reason LiFePO4 nanoparticles func-
et al.28 and further invalidate the former shrinking core tions as a cathode at a reasonable rate is the availability
model. Indeed, they found that whatever the material of a single‐phase transformation path at a very low
being charged (or discharged), the two‐phase mechan- overpotential, allowing the system to avoid nucleation
ism occurs by a successive emptying (or filling) of the and growth of a second phase. Interestingly, Bai et al.,41
Li+ channels (along the b‐axis), leading to partially de- developed a theory using a novel electrochemical phase‐
lithiated (or lithiated) particles both made of a core of field model of reaction‐limited intercalation in aniso-
FePO4 enclosed by a shell of LiFePO4. Also pointed out tropic nanoparticles and they proposed that phase se-
that the nanometer interface between the single‐phase paration can be avoided above a critical current density.
areas composed of LiFePO4 or FePO4 is the super- They showed that phase separation upon discharge is
position of these two end members rather than a solid governed by surface reactions, which gives unstable
solution. The schematic representation of this new core‐ “quasi‐solid solutions” and homogeneous particle filling
shell model is shown in Figure 2C. Later on, Delmas can occur at higher current densities, instead of the
et al.,29 investigated the redox processes undergone by common belief of the existence of Li‐rich and Li‐poor
nanosized carbon‐coated LiFePO4 samples using X‐ray phases during the discharge of nanosized LiFePO4. Later
photoelectron spectroscopy analyses and in another on, Liu et al.,9 provided experimental evidence of the
work through X‐ray diffraction (XRD) and electron mi- existence of a continuous metastable solid solution phase
croscopy. They proposed a new model, that is, “domino‐ in LiFePO4 nanoparticles during high‐rate cycling using
cascade model” which differs from the Chen et al.28 and in situ synchrotron XRD (see Figure 3).
Laffont et al.25 model by only the interface character. The above experimental finding confirms the hy-
Indeed, the domino‐cascade model suggests the coex- pothesis that phase transformations in nanoparticulate
istence of LiFePO4 and FePO4 particles that are single‐ LiFePO4 occurs, at least at high rates, via a solid solu-
domain (the coexistence of fully intercalated and fully tion mechanism rather than a distinct moving phase
deintercalated individual particles) rather than regions boundary between LiFePO4 and FePO4, which explains
inside a single particle in the above‐mentioned new core‐ the excellent rate capability of nanosized LiFePO4. Re-
shell model. cently, Li et al.,40 performed phase‐field simulations to
F I G U R E 3 Color view of in situ X‐ray diffraction (XRD) pattern of LiFePO4 under different electrochemical cycling conditions.
(A–C) Images show the second galvanostatic cycle at 5, 10, and 20 C current rates, respectively. (D) Images show the evolution of the
charge‐relax experiment, where a current equivalent to 10 C is applied for 90 s (highlighted with the horizontal gray bands) followed by an
open‐circuit relaxation of 10 min. The dashed white lines indicate the peak positions of the LiFePO4 and FePO4 phases at the end of the
second relaxation period, which are used to draw the boundaries of the miscibility gap, as determined from the (200) and (301)
reflections (reprinted from Ref. 9 Copyright 2014 American Association for the Advancement of Science)
investigate the surface diffusion in intraparticle phase two‐phase mechanism. The Lithium extraction/insertion
transformations. They combined XRD and microscopy mechanism of LiFePO4 electrode was described using
experiments as well as ab initio molecular dynamics several models such as the “shrinking core model” in
simulations to demonstrate that surface ion diffusion is which the lithium insertion proceeds from the surface of
promoted by solvent molecules and they concluded that the particle moving inward behind a two‐phase interface,
is the main reason for the phase separation after re- and the domino‐cascade model which suggests the co-
laxations (see Figure 4). They also suggested that low- existence of fully intercalated and fully deintercalated
ering surface diffusivity is highly important to suppress LiFePO4 and FePO4 individual particles that are single‐
phase separation. domain (rather than regions inside a single particle in the
At an early age, LiFePO4 suffered from inferior rate above‐mentioned core‐shell model). However, with the
capability, which was explained to be associated with a research progress, the design of LiFePO4 carbon‐coated
F I G U R E 4 The distribution of lithium in ionically connected particles shows that phase separation occurs primarily via surface
diffusion. (A) Intraparticle phase separation after short, 8 h electrolyte exposure (B) and (C) interparticle mosaic under long electrolyte
exposure (reprinted from Ref. 40 Copyright 2018 Springer Nature Publishing)
nanoparticles showed high‐rate performance. This re- to about 140 nm. They prepared nanoparticles by a low‐
markable behavior has attracted a great deal of interest temperature precipitation method that demonstrated a
among researchers, and they found that a single‐phase high specific capacity of ∼147 mA h g−1 at 5C‐rate as well
mechanism occurs at high current rates in LiFePO4 na- as good cyclability over 400 cycles, without the need of
noparticles rather than two‐phase which explained the carbon coating. These experimental results might suggest
origin of high‐rate capability. that particles nanostructuring is more important than
carbon coating for achieving good electrochemistry.
Furthermore, Gaberscek et al.,42 carried out a theoretical
4 | THE EFFECT OF STRUCTURE study that consistently explained the main reason for the
A N D M O R P H O L O G Y ON T H E relatively small importance of carbon coatings is the fact
ELECTROCHEMISTRY OF LiFePO 4 that the ionic conductivity (ca. 10−11–10−10 S cm−1 at RT)
is much smaller than the electronic (>10−9 S cm−1 at
Tremendous efforts have been made towards improving RT). However, for high rate capability (high electronic
the electrochemical performances through particle size and ionic conductivities) nanostructuring and carbon
optimization, in particular, nanostructuring, carbon coating are highly desirable. Indeed, several efforts have
coating, doping, and defect formation. Among them, been made to coat LiFePO4 using various carbon source,
particle size optimization and carbon coating are well for example, sucrose,47–50 citric acid,51 poly(ethylenegly-
studied as the effective way.42–45 Cation doping is first col),52 poly(vinyl alcohol),53,54 and ascorbic acid.55 In this
reported to be highly effective,46 but it was later pointed context, Cho et al.,42 studied the relation between the
out that the effect of unintentional carbon coatings that carbon coating thickness and the electrochemical per-
improved the electrochemical performances, which can- formance of LiFePO4. They used a carbon vapor de-
not be neglected. position technique and showed that the amount of
carbon and its coating thickness and uniformity in
LiFePO4/C materials play a crucial role in determining
4.1 | Size and carbon coating effects on electrochemical performance. LiFePO4 coated with a thin
LiFePO4 and uniform carbon film delivered a maximum discharge
capacity of ∼151 mA h g−1 at 0.2 C‐rate and with a capa-
Delacourt et al.,25 have shown that excellent electro- city retention rate of 80% after 415 cycles. Another way to
chemical performance of carbon coating‐free LiFePO4 enhance the electrochemical performances by replacing
can be achieved if the particle size is extremely narrowed the carbon and Teflon additives with polypyrrole (PPy)
and polyaniline (PANI) was reported to be effective in to the low tap density as the drawbacks. So, the volu-
several works.56–59 Huang et al.,56 reported an improved metric energy density has a direct relationship to particle
rate capability and capacity of C‐LiFePO4/PPy cathode morphology, and it needs to be designed to balance those
containing 16 wt% of PPy bonded to the active material by contradicting parameters. For instance, the spherical
a carbon coating. The same group prepared later, LiFe- particles have a higher tap density than irregular parti-
PO4/polymer composite cathodes using PPy and PANI via cles due to easy close‐packing. Following these con-
electrochemical deposition and chemical polymerization. siderations, Xie et al.,60 prepared carbon‐coated spherical
They demonstrated that the prepared carbon‐coated LiFePO4 particles with excellent electrochemical perfor-
LiFePO4/PPy via electrodeposition showed enhanced mances and high tap density of 1.6 g cm−3 was obtanied.
electrochemical performances mainly the rate capability.57 Furthermore, Oh et al.,44 reported double carbon‐coated
The specific capacity approached the theoretical at 0.1 C nanoporous microscale LiFePO4 particles with a high tap
and a capacity retention rate of more than 70% at a high density of 1.5 g cm−3 and excellent rate performances
rate of 20 C was reported. (Figure 5A,B). Recently, Hwang et al.,61 performed car-
In addition to electrochemical performances, volu- bon coating of hierarchically mesoporous LiFePO4 nano/
metric energy density is also a critical parameter in de- microspheres using a liquid carbon dioxide (l‐CO2) based
termining battery performance. In general, the efforts to coating approach. The l‐CO2 result in an ultrathin carbon
improve those electrochemical performances such as layer (1.9 nm) distributed all over the primary nanosized
high carbon content, nanoscaling of the particle size lead LiFePO4 particles (20–140 nm in diameter), forming a
F I G U R E 5 Electron microscopy and electrochemical performances of LiFePO4 nanoparticles. (A) SEM images were obtained from a
focused ion beam cut of LiFePO4 at low and high magnification. Bottom, cross‐sectional TEM image of LiFePO4 and the corresponding EELS
image (where red: C, blue: Fe, and green: P). (B) Rate capability of Li/C‐LiFePO4 cells (reprinted from Ref. 44, Copyright: 2010 WILEY‐VCH
Verlag GmbH & Co. KGaA, Weinheim). (C) FE‐SEM images, HR‐TEM images for H‐LFP (without carbon coating) and C‐LFP‐S
(carbon‐coated LFP) using liquid carbon dioxide (l‐CO2) as the coating solvent. (D) Rate capabilities of H‐LFP and C‐LFP‐S (reprinted from
Ref. 61, Copyright: 2017 Elsevier Ltd.). EELS, electron energy loss spectroscopy; FE‐SEM, field emission scanning electron microscopy;
HR‐TEM, high‐resolution transmission electron microscopy; SEM, scanning electron microscopy; TEM, transmission electron microscopy
core (LiFePO4)‐shell (carbon) structure. This unique supervalent metals Li1–xMxFePO4 (Mg2+, Al3+, Ti4+,
structure provides facile penetration of liquid electrolytes Zr4+, Nb5+, or W6+) drastically increases the electronic
and rapid electron and Li‐ion transport. This composite conductivity of LiFePO4 by a factor of ∼108. The resulting
exhibits high reversible capacity, high energy and power materials showed high energy density at low current
density (168 mAh g−1 at 0.1 C, 109 Wh kg−1, and rates. This study has fascinated several research groups
3.3 kW kg−1 at 30 C, respectively) with excellent cycle life and many reports on LiFePO4 cation doping were pub-
(84% cycle retention at 10 C after 1000 cycles) and high lished.71–80 However, Doeff et al.,81 reported that those
tap density (1.4 g cm−3; Figure 5C,D). performance improvement is rather caused byresidual
The above results clearly demonstrate that both na- carbon content derived from the combustion of organic
nosized and carbon‐coated LiFePO4 exhibits highly de- moieties in the precursors. Moreover, Ravet et al.,82
sirable properties: A specific capacity approaching the suggested that the excellent electronic conductivity re-
theoretical one, excellent rate capability, outstanding ported by Chung et al.46 is due to carbon for low‐
cyclability, and a high tap density. It is worth noting temperature samples, and to low‐valency iron derivatives
that, the synthesis procedure plays a crucial role in the imparting semi‐metallic conductivity in samples treated
coating, especially grinding used to form these compo- above 750°C. Later on, Nazar's group, evidenced that the
sites leads to the efficient coating as well as reduced enhanced conductivity of the composition of LixZr0.01-
particle size. Furthermore, research has been extended FePO4 (x = 0.87–0.99) was due to the presence im-
to the addition of carbon‐nanotubes to LiFePO4 aiming purities, that is., Fe2P and/or iron phosphocarbide,
to increase the rate of performances to an ultrahigh Fe75P15C10, formed by carbothermal reduction of
level which is highly important for application in EVs LiFePO4 in the presence of carbon, under reducing at-
and PHEVs, and many works reported improved capa- mosphere, resulting from both the oxalate precursor and
city and excellent rate performance.62–70 In this context, alkoxide in the Zr‐dopant.83
Toprakci et al.,63 developed LiFePO4/CNT/C composite To date, cation doping approaches with multivalent
nanofibers by combining electrospinning and sol‐gel metal ions have not yet been shown to be an effective
methods. The prepared LiFePO4/CNT/C nanofibers ex- way for improving the electronic conductivity and thus
hibited a specific capacity of 169 mA h g−1 at 0.05 C, as the electrochemical performances of LiFePO4. This in-
well as both good cycling performances and excellent efficiency could be caused by the substitution of Li+ by
rate capability, were obtained. Furthermore, Wu et al.,64 divalent and trivalent cations, which produces vacancies
developed LiFePO4 composite by decorating carbon‐ in Li sites, may impede the diffusion pathways of Li+.84
coated LiFePO4 nanoparticles with carbon nanotubes However, Ban et al.,85 combined experimental and the-
(LFP@C/CNT), the prepared LFP@C/CNT delivers a oretical studies to investigate the Si‐F anionic codoping
capacity of 160 mA h g−1 at 0.2 C with excellent rate of LiFePO4. They reported that Si‐F codoped LiFePO4
capability, that is, the cathode retained about 59% of the leads to improved electrical conductivity and therefore
initial capacity at an ultrahigh rate of up to 120 C in greatly improved electrochemical performance as com-
addition to high low‐temperature performance, that is, pared to undoped LiFePO4. Although, the fact that
about 71.4% of capacity is retained at −25°C. whether or not the electrochemical performances
The design of fast‐charging LiFePO4 electrode re- LiFePO4 could be enhanced solely by cation and/or anion
quires optimized carbon coating, particle size, and doping still in debate and significant efforts should be
architecture. Finding the suitable synthesis method to spent to give a convincing evidence.
make both efficient carbon‐coating the desired particle
size has been the main goal of several research groups.
The reports showed that the carbon‐coated LiFePO4 na- 4.3 | Defect structure of LiFePO4
noparticles exhibit the most promising performances: A
specific capacity approaching the theoretical value, ex- Cation defects in metal oxides makes significant impact
cellent rate capability, ultralong cycle life and a high tap on the reversible guest‐ion insertion.86
density. In the materials with 2D and 3D diffusion channels,
cation defects can work as the extra guest‐ions diffusion
path and their host sites, unlocking the superior intrinsic
4.2 | Doping in LiFePO4 nature of the active materials.87–89 On the other hand, in
the materials with 1D diffusion channels where the ion
Chung et al.,46 investigated the possibility of improving mobile directions are largely restricted, the existence of
the electronic conductivity of bulk LiFePO4 through su- defects, even at a small concentration, can largely impede
pervalent doping. They claimed solid‐solution doping of the guest‐ion diffusion. So, it is important to understand
those defects of the olivine structure to improve their diffusion in LiFePO4 using Li isotope exchange and nu-
electrochemical performances. clear magnetic resonance combined with Monte Carlo
In the olivine structured LiFePO4, the cation mixing simulations. They concluded that the cross‐over of Li can
of Li and Fe atoms, so‐called antisite defects, can easily occur but the diffusion of Li across the paired defects are
occur. The concentration of the defects depends on the estimated as low as 10−16 cm2 s–1. Those defects are,
synthetic process, and largely observed in the samples however, easily reduced by heat treatment at high
synthesized via low‐temperature hydrothermal process.90 temperature, and the significant improvement of the
Normally, the concentration of the defects is low (1% or electrochemical performance are reported.90
less),91 and not easily experimentally detectable. At sin- In contrast to those defects in the olivine structure,
gle antisite defects, Li and Fe atoms switched their po- antisite defects can promote Li insertion in β phase of
sitions (see Figure 6A). Fe on the channel will block LiFePO4 (Orthorhombic Cmcm, the crystal structure; see
further Li diffusion along [010] direction, and requires Figure 6C,D). Here, β‐LiFePO4 is metastable poly-
further diffusion across the channels along [001] direc- morphous of LiFePO4 with a higher mass density and
tion, whose energy activation barrier is ca. 9 times appears at high pressure (65 k bar) and high temperature
larger.94 So, the antisite defects lead to inferior electro- (900°C).95 While each LiO6 octahedron in the olivine
chemical performance. This is one of the reasons why LiFePO4 is edge‐shared, each LiO4 tetrahedron in
experimentally obtained diffusion coefficient along [010] β‐LiFePO4 is corner‐shared with FeO6 octahedral and
direction is much lower compared with the theoretically PO4 tetrahedral.95 So, each LiO6 octahedron is not con-
anticipated diffusion coefficient (ca. 10−8 cm2 s−1). On nected other, offering limited reversible capacity for
the other hand, at a paired antisite defects (see Li‐ion insertion. Guo et al.,93 attempted to incorporate
Figure 6B), Li‐ions can still be diffusible and the cross‐ antisite defects to construct Li‐ion diffusion paths (see
over of Li‐atoms along two different channels can occur. Figure 6E,F). They synthesized the β‐LiFePO4 with
Liu et al.,92 studied those effects of antisite defects on Li particle sizes of 4–6 μm via solvothermal method, and
F I G U R E 6 Defect structures of LiFePO4. (A) Configuration of a single Li−Fe antisite and (B) the configuration of paired Li−Fe antisite
defects (reprinted from Ref. 92 with a permission from American Chemical Society). Li‐ion migration paths in β‐LiFePO4 and its defective
structure, and migration barriers. (C, D) Li migration to adjacent tetrahedral sites. (E, F) Newly formed Li‐ion migration passages in the
defective domain and migration energy barrier, showing much easier Li‐ion migration (reprinted from Ref. 93 with a permission from
American Chemical Society)
subsequently ball‐milled so as to incorporate antisite LiCoPO4 exhibits high energy density, still suffers from
defects in the large‐scale. As a result, by optimizing the capacity fading. Bramnik et al.,99 investigated the de-
ball‐milling time, a Li/β‐LiFePO4 cell showed an im- lithiation mechanism in attempt to shed light on the
proved capacity of 128 mA h g−1 at 0.1 C‐rate. Combined origin of capacity fading. They concluded from XRD data
with density functional theory calculations, they ex- that this fast deterioration of electrochemical perfor-
plained the reversible Li insertion behavior with the help mance during charging is due to the amorphization of
of the surrounding amorphous domain. the samples during the first charge as well as the pre-
Briefly, the importance of defects in LiFePO4 needs to sence of an unknown impurity phase. Furthermore, they
be emphasized. In particular, in the 1D diffusion mate- investigated in another study the relation between the
rials, the single antisite defects can largely impede the synthesis method and Li extraction–insertion mechanism
Li‐ion diffusion, resulting in poor electrochemical in LiCoPO4. They clarified using in situ and ex situ XRD,
performances.92 Even a paired antisite defect enables the that the electrochemical mechanism strongly depends on
cross‐over of diffusion channels, theoretically the calcu- the synthesis route, for example, for the samples pre-
lated diffusion coefficient is very low as 10−16 cm2 s–1 and pared at 600°C the amorphization of the cathode mate-
also impedes Li‐ion diffusion. On the other hand, an- rial was identified while for the sample prepared at 800°C
other polymorph of β‐LiFePO4, which is inactive at a two‐phase mechanism between LiCoPO4–CoPO4 was
pristine state, was activated by the introduction of anti- suggested.100 Moreover, they reported in a more recent
site defects with the help of amorphous region and shows study,101 based on in situ XRD, the appearance of a third
a reversible capacity of 128 mA h g−1.93 phase during the delithiation of LiCoPO4 which found to
crystallize in the same pristine structure. Many attempts
to improve the electrochemical performances were re-
5 | OLIVINE F AMILY O F ported such as, modifying the synthesis method,102,103
P H O S P H A T E S ( L i M P O 4 , M = CO , carbon coating,104–110 and cation doping.111–115 Particu-
MN, N I) larly, in the last decade, LiCoPO4, the potential high
energy Li‐ion cathode (∼800 Wh kg−1) has gained more
Padhi et al.,2 have tried to extract lithium electro- attention. Accordingly, many works on improving its
chemically from LiMPO4, with M = Co, Mn, Ni, using cycling performances through nanosizing and doping
LiClO4 dissolved in propylene carbonate and dimethox- were published.114,116–131 For instance, Wang et al.,122
yethane as the electrolytes. However, due to the oxida- prepared carbon‐coated LiCoPO4 via solvothermal
tion of electrolyte at higher voltage, that is, 4.4 V versus method with a microstructure in the size of about
Li+/Li, the lithium extraction was unsuccessful. In early 5–8 μm, which delivered an initial discharge capacity of
2000, Amine et al.,96 proved the reversible extraction and 136 mAh g−1 at 0.1 C rate and retains 91% of it over
insertion of lithium from and into olivine LiCoPO4 at 50 cycles. Unfortunately, LiCoPO4 is one of the most
4.8 V versus Li+/Li using LiPF6/sulfolane electrolyte. The high‐voltage cathode materials which operate outside the
electrochemical extraction was limited to 0.42 Li+ per electrochemical stability limit of most electrolytes.
formula unit, with a charge capacity of 86 mA h g−1 and a The unsuitability of the electrochemical potential of the
discharge capacity of 70 mA h g−1. The in situ XRD re- cathode with the electrolyte causes irreversible side re-
sults showed that lithium can be extracted and inter- actions during cycling, which consumes the electrolyte
calated in a reversible manner in the olivine LiCoPO4 and causes capacity fade.116,131 Consequently, there have
with the appearance of a second phase during charge to been numerous reports on developing new electrolytes
5.3 V versus Li+/Li. Lithium cobalt phosphate starts to and additives that are stable at higher voltages.132–136
gain more attention due to its promising high energy Although, these electrolytes come with the high cost and
density owing to high equilibrium voltage, that is, 4.8 V suffer from low‐ionic conductivity at low temperatures
versus Li+/Li. In 2001, Okada et al.,97 reported that a which prohibited generally high voltage cathode mate-
capacity of 100 mA h g−1 can be delivered by LiCoPO4 rials and particularly LiCoPO4 from a wide range of
after the initial charge to 5.1 V versus Li+/Li and exhibits applications.
a small volume change of 4.6% upon charging. Later on, Lithium nickel phosphate, LiNiPO4, similar to the
Lloris et al.,98 improved the electrochemical performance cobalt homolog, crystallize in olivine‐type structure. Its
of lithium cobalt phosphate using a novel solid‐state electrochemical activity was first demonstrated by
procedure (addition of carbon black as dispersing agent Minakshi et al.137 that lithium extraction/insertion can
during heat treatments) which produced a lower average be achieved in aqueous LiOH electrolytes after many
particle size than conventional preparations. A discharge unsuccessful attempts in nonaqueous electro-
capacity of 125 mA h g−1 was achieved. Even though, lytes.2,97,138–140 Noting that the reported works about
the electrochemical performance of LiNiPO4 are ex- were obtained. Also, excellent capacity retention of
tremely limited due to the difficulty in synthesizing a 98% after 200 cycles at 5 C was reported.
pure phase. More recently, research has been oriented to
Contrary to LiNiPO 4, lithium manganese phos- cation‐doping towards improving the lithium diffu-
phate, LiMnPO4 , showed promising electrochemical sion for better performance.157–161 For instance, Luo
performances. Goodenough's group have first in- et al., 157 prepared Er‐doped LiMnPO4/C via hydro-
vestigated the electrochemical behavior of Li thermal method. The prepared composition of LiM-
(Mn x2+ Fe1−x 2+)PO4 (x = 0.25, 0.50, 0.75, 1.0) solid‐ n0.97 Er 0.03 PO 4/C presented good rate performance,
solution and reported that the width of the 4.1 V that is, 142.5 mA h g−1 at 0.05 C, 105.6 mA h g −1 at 5 C,
plateau corresponding to Mn 3+ /Mn 2+ relative to that and 95.5 mA h g −1 even at high current rate of 10 C.
of the 3.4 V plateau (Fe 3+/Fe2+ ) increases as the Mn The observed enhancement of rate capability was
content is increased. However, the total capacity de- explained by the occupation of Er3+ the Mn2+ sites
creases rapidly for x > 0.8 due to an abrupt increase in creating Mn vacancies which may alleviate
the polarization. 2 The reversible extraction and in- the Jahn–Teller effect, and thus improve the Lithium
sertion of lithium into olivine LiMnPO4 was firstly diffusion. In the same context, Yang et al., 159 syn-
demonstrated by Li et al., in 2002, 141 a reversible ca- thesized Fe‐doped LiMnPO4@C nanofibers using a
pacity of ca. 140 mA h g−1 was obtained during several feasible electrospinning method. Among a series of
cycles with reasonably good cycling performance. compositions (LiFexMn 1−x PO4 @C, x = 0, 0.25, 0.5,
They pointed out that, when lithium is extracted from 0.75, 1), the composition LiFe 0,5Mn0,5PO4 @C showed
LiMnPO4 , a new phase Li x0 MnPO4 forms, in which excellent performances, a capacity of 150 mA h g−1 up
the lithium content x0 is negligible, so the electro- to 500 cycles at 0.2 C was achieved and 102 mA h g−1
chemical lithiation/delithiation reaction of LiMnPO4 can be obtained at 5 C over 2000 cycles, demonstrat-
proceeds via the same “two‐phase mechanism” as that ing long lifespan.
of LiFePO 4. The volume change during the lithium As a summary, we carried out a comparison be-
extraction was 10.7% which is higher than LiFe- tween carbon‐coated LiMPO4 (M = Co, Fe and Mn)
PO4 –FePO4 system. In the following years, LiMnPO4 cathode performances in Figure 7. Theoretically, Li-
attracted more attention as a promising low‐cost and CoPO4 outpaces the other olivine phosphates in terms
high energy density cathode material and many works of energy density resulting from its high operating
regarding particle size optimization142–151 and carbon voltage of ∼4.8 V versus Li+ /Li (see the right‐hand
coating 152–154 were published. Recently, Kwon panel in Figure 7), but unlike Fe‐ or Mn‐based olivine
et al.,149 investigated the effect of particle shape on phosphates, LiCoPO4 still suffer from poor capacity
the electrochemical performances of nanosized and rate capability (see the left‐hand panel in
LiMnPO4 . By using the thermal decomposition Figure 7). LiMnPO4 , however, shows promising re-
method, they prepared nanoparticles with various sults in terms of high energy density and approaches
shapes, that is, elongated spherical, thin nano‐rod, the capacity and the rate performance of LiFePO 4 ,
thick nano‐rod, cubic, and platelet shapes. They re- besides its equilibrium voltage of ∼4.1 V suitable for
ported that the particles exhibiting the shortest b‐axis most commercial electrolytes. Although, for high en-
offer higher capacity due to higher Li+ diffusion ki- ergy density applications, further improvement in
netics. Moreover, Yang et al., 155 prepared mesoporous cycling and the rate performances is still required for
carbon‐coated LiMnPO 4 nanofibers via the electro- both LiCoPO 4 and LiMnPO 4 to meet the cathode re-
spinning method. The carbon‐coated LiMnPO4 na- quirement for commercialization.
nofibers showed high reversible capacity of
149.8 mAh g−1 at 0.2 C with good cycling stability over
300 cycles, also demonstrated outstanding cycle life 6 | SUMMARY AND
even at 5 C over 2000 cycles with a capacity of PERSPEC TIVES
63.1 mA h g −1 . Following the development of synth-
esis techniques, Li et al., 156 synthesized hierarchical The development of fast charging, large autonomy,
carbon‐coated LiMnPO 4 microspheres using MnCO3 and lighter batteries at the lower cost and longer
microspheres via freeze‐drying process followed by lifetime necessary for today's technological advance-
heat‐treatment. The prepared carbon‐coated LiMnPO4 ment in major fields such as EVs and HEVs applica-
microspheres demonstrated high electrochemical tions. This rising demand creates a challenge for
performances, that is, high specific capacity of materials chemists to innovate new cathode materials
158.4 mA h g −1 at 0.05 C and 104.3 mA h g −1 at 5 C which can meet the required performance for battery
F I G U R E 7 Electrochemical performances of LiFePO4, LiMnPO4, and LiCoPO4. The experimental (left‐hand panel) and theoretical
(right‐hand panel) values, which were obtained from the references (Ref. 61 for LiFePO4 with a permission from Elsevier, Ref. 156 for
LiMnPO4 with a permission from Electrochemical Society Inc., and Ref. 122 for LiCoPO4 with a permission from Elsevier)
manufacturers. The olivine LiFePO4 is one of the C O NF L I C T O F I N T E R E S T S

promising cathode materials that has attracted con- The authors declare that there are no conflict of
siderable attention. It operates around ∼3.4 V with interests.
biphase mechanism. Remarkably, LiFePO4 carbon‐
coated nanoparticles display improved electrochemical A U T H O R C O N TR I B U T I O N S
performances especially high‐rate capability, which was All authors contributed equally to the writing of the
explained by the presence of a fascinating none- manuscript.
quilibrium continuous solid solution, at high current
rates, rather than the common biphase mechanism. ORC ID
However, extensive research is needed by coupling the Mohammed Hadouchi https://orcid.org/0000-0001-
efforts of experimentalists, through cutting‐edge in situ 5526-7368
techniques, and theorists to understand more deeply the Toshinari Koketsu http://orcid.org/0000-0002-
reason behind the different electrochemical mechanisms 2796-7866
of LiFePO4 nanoparticles (i.e., single‐phase mechanism), Zhiwei Hu https://orcid.org/0000-0003-0324-2227
particularly at high current rates. On the other hand, for Jiwei Ma http://orcid.org/0000-0003-4209-7667
the other olivine members, that is, LiMPO4 (M = Co, Mn,
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LiMnPO4, Li+ diffusion orientation and diffusion coefficients Department of Chemistry, Faculty of
for high volumetric energy Li+ ion cathodes. J Power Sources. Science, Mohammed V University in
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Rabat (Morocco) since December 2020.
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into microclusters as a high‐performance cathode in lithium‐
Previously, he was a postdoctoral fellow
ion batteries. ACS Appl Mater Interfaces. 2017;9(33): at Tongji University in Shanghai (China) since July
27618‐27624. 2019. His research activity involves the synthesis,
151. Zhu C, Wu Z, Xie J, et al. Solvothermal‐assisted morphology characterization and in‐situ/ex‐situ structural inves-
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34(9):1544‐1549.
152. Oh S‐M, Oh S‐W, Yoon C‐S, Scrosati B, Amine K, Sun Y‐K.
High‐performance carbon‐LiMnPO4 nanocomposite cathode Dr. Toshinari Koketsu is currently
for lithium batteries. Adv Funct Mater. 2010;20(19): working as a postdoctoral fellow of the
3260‐3265. Electrochemical Energy, Catalysis, and
153. Bakenov Z, Taniguchi I. Electrochemical performance of Materials Science Laboratory, Technical
nanocomposite LiMnPO 4/C cathode materials for University Berlin in Germany since
lithium batteries. Electrochem Commun. 2010;12(1):
January 2021. Previously, he was a
75‐78.
154. Bakenov Z, Taniguchi I. Physical and electrochemical prop-
postdoctral fellow at Tongji University in China. His
erties of LiMnPO4/C composite cathode prepared with dif- research interests are designing defective cathode
ferent conductive carbons. J Power Sources. 2010;195(21): materials and advanced metal anodes for next‐
7445‐7451. generation rechargeable batteries and their physico-
155. Yang H, Liu J, Wang X, et al. Positive surface pseudocapa- chemical characterizations.
citive behavior‐induced fast and large Li‐ion storage in me-
soporous LiMnPO4 @C nanofibers. ChemSusChem. 2019;
12(16):3817‐3826. Dr. Zhiwei Hu is presently working as
156. Kluger G, Glauser T, Krauss G, Seeruthun R, Perdomo C, a group leader of X‐ray spectroscopies
Arroyo S. Facile fabrication of hierarchical LiMnPO4 at the department of Physics of Corre-
microspheres for high‐performance lithium‐ion batteries lated Matter in Max‐Planck Institute
cathode. J Electrochem Soc. 2019;166(2):A118‐A124. for Chemical Physics of Solids, Dres-
den, Germany. His research fields focus
on the relation of the charge, orbital and spin understanding the relationship of structure‐property
degrees of freedom to the magnetic and transport using various ex situ and in situ techniques, including
properties of the strongly correlated materials and structural and interfacial characterizations.
renewable energy materials using X‐ray absorption
spectroscopies.
How to cite this article: Hadouchi M, Koketsu T,

Dr. Jiwei Ma is a Professor at Tongji Hu Z, Ma J. The origin of fast‐charging lithium
University in Shanghai, China. He re- iron phosphate for batteries. Battery Energy. 2022;
ceived his PhD in 2013 at the University 1:20210010. doi:10.1002/BTE2.20210010
of Poitiers in France. His research inter-
ests are designing defective materials for
rechargeable batteries and fuel cells, and

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Received: 13 September 2021 | Revised: 25 October 2021 | Accepted: 10 November 2021

The origin of fast‐charging lithium iron phosphate

Mohammed Hadouchi1,2 | Toshinari Koketsu1 | Zhiwei Hu3 | Jiwei Ma1

Funding information KEYWORDS

1 | INTRODUCTION large‐scale applications such as e‐mobility (electric ve-

Battery Energy. 2022;1:20210010. onlinelibrary.wiley.com/r/batteryenergy | 1 of 19

LiFePO4–FePO4 electrochemical mechanism. The ob- 3 | L I T H I UM EX T RA C T I O N /

manufacturers. The olivine LiFePO4 is one of the C O NF L I C T O F I N T E R E S T S

How to cite this article: Hadouchi M, Koketsu T,

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