REVIEW

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Comprehensive Understanding of Structure Transition in

LiMnyFe1−yPO4 during Delithiation/Lithiation
Shuzhen Li, Hao Zhang, Yong Liu,* Li Wang,* and Xiangming He*

high power density, high energy conver-

The complexity of structural changes in LiMny Fe1−y PO4 (LMFP) during sion efficiency, long cycle life, environmen-
delithiation/lithiation poses unique challenges in kinetics and cycling, tal friendliness, and no memory effects,[1]
distinguishing it significantly from LiFePO4 . Therefore, comprehending the lithium-ion batteries (LIBs) have gained
delithiation/lithiation mechanism of LMFP is essential to optimize material significant popularity in portable electron-
ics and are rapidly expanding in the
design, synthesis, and battery application management. However, existing
fields of automobiles, aircraft, and energy
reports show apparent discrepancies and contradictions. This paper storage.[2] Cathode materials play a pivotal
elucidates the relaxation property of LMFP, providing a comprehensive review role in determining the specific energy and
of crystal structure and electronic structure change mechanisms during power performance of LIBs. Commonly
delithiation/lithiation based on in situ characterization. Regarding crystal used cathode materials include LiNiO2 ,[3]
LiMn2 O4 ,[4] LiNix Coy Mnz O2 (x+y+z = 1),[5]
structure transition, variations in LMFP’s compositional uniformity across
LiFePO4 (LFP).[6] Among these materials,
different literature, stemming from differences in the synthesis process, may LFP stands out with its unique olivine struc-
contribute to multiple mechanisms. Concerning electronic structure changes, ture characterized by (PO4)3− tetrahedra
the chemical environments between Fe and Mn are mutual interaction, and and strong P─O covalent bonds, which con-
the sluggish kinetics of the Mn2+ /Mn3+ reaction suggest partial charge tribute to its favorable cycle life and safety
compensation by oxygen in the phosphate group. Building on these findings, properties.[7] However, its energy density
remains relatively low, underscoring the
the paper addresses existing research deficiencies and identifies potential
need for the development of new cath-
directions for future investigations into the delithiation/lithiation mechanism ode materials that possess similar struc-
of LMFP, aiming to provide a solid theoretical foundation for developing new tures but offer higher specific energy.[8]
olivine-type cathode materials with superior electrochemical performance. Among the diverse olivine-structured
LiMPO4 materials (M═Ni, Co, Mn, one
or more),[9] LiMnPO4 (LMP) emerges as
a stand-out due to its affordability, safety,
1. Introduction and environmental compatibility. Notably, LMP boasts a high-
voltage platform (≈4.1 V vs Li/Li+ ),[10] strategically positioned
With the growing emphasis on energy and environmental con- below the electrochemical window of traditional organic elec-
cerns, the development of new energy sources and improved trolytes (<4.3 V vs Li+ /Li).[11] Despite sharing a comparable
energy utilization efficiency has become a paramount objec- theoretical specific capacity with LFP (≈170 mAh g−1 ), LMP
tive in the energy sector’s technological advancements. Energy leverages its elevated voltage plateau to achieve a potential en-
storage, in particular, has emerged as a pivotal technology in ergy density augmentation of ≈20% in comparison to LFP
energy generation, transportation, and utilization, witnessing (≈700 Wh kg−1 ).[12] However, LMP encounters challenges in ion
remarkable progress in recent years. With the advantages of diffusion rate and electron conductivity,[13] predominantly stem-
ming from the Jahn-Teller distortion induced by Mn3+ during
charge. This distortion substantially impedes Li+ diffusion, re-
S. Li, Y. Liu
Beijing Key Laboratory of Advanced Functional Polymer Composites sulting in sluggish kinetics that impedes attaining the desired
College of Materials Science and Engineering electrochemical performance levels, aligning with application
Beijing University of Chemical Technology requisites.[14]
Beijing 100029, China To surmount these limitations, the introduction of moder-
E-mail: [email protected]
ate Fe2+ doping into LMP has showcased enhanced electronic
S. Li, H. Zhang, L. Wang, X. He
conductivity,[15] accelerated Li+ migration rate, and mitigation of
Institute of Nuclear and New Energy Technology
Tsinghua University the Jahn-Teller effect. Furthermore, Fe2+ doping proves instru-
Beijing 100084, China mental in quelling the disproportionation reaction of Mn3+ and
E-mail: [email protected]; [email protected] maintaining a relatively high operational voltage.[14b,16] Notably,
the pioneering work of Padhi et al. in 1997 reported the charge–
The ORCID identification number(s) for the author(s) of this article
can be found under https://doi.org/10.1002/adfm.202310057 discharge behavior of LMFP across varied Mn compositions,[17]
sparking considerable enthusiasm among researchers to delve
DOI: 10.1002/adfm.202310057

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anism study. Notably, LFP and LMP are widely acknowledged

to exhibit predominantly two-phase reaction (phase transition
mechanism) throughout the delithiation/lithiation processes,[27]
while only single-phase reaction (solid solution mechanism) at
higher rates[28] and smaller nanoparticle sizes.[29] However, the
delithiation/lithiation mechanism of LMFP materials is pro-
foundly intricate. It interweaves a multitude of influential vari-
ables encompassing Fe/Mn ratios, synthesis methodologies,
charge/discharge rates, cycling parameters, particle sizes, defect
concentrations, and crystal orientations, among others.
In instances where mechanism studies concentrate solely on
specific factors, the results often diverge significantly, occasion-
ally leading to contradictions. This discrepancy can be attributed
to the fact that, even when LMFP with the same Fe/Mn ra-
tio is synthesized using the same method, they exhibit differ-
ent structure transition behaviors in various reports. An illustra-
tive case involves Lix Mn0.5 Fe0.5 PO4 /C synthesized by the solid-
state,[30] in stark contrast to the latter, which encompasses a
significantly broader range (0.4≤x≤1). Hence, the intricacy en-
Figure 1. A comparison of the number of publications related to LMFP
and its delithiation/lithiation mechanism (searched from Web of Science, shrouding LMFP’s delithiation/lithiation mechanism emerges
accessed July 2023). as a pivotal factor contributing to the limited breadth of reports
concerning its corresponding studies.
Deng et al. reviewed the study of the LMFP delithia-
into this material’s synthesis, applications, and mechanisms. As tion/lithiation mechanism in a section of a review in 2017.[12a]
of recent years, the LMFP solid solution has emerged as a piv- Also, a summary and description of the crystal structure transi-
otal trajectory within the realm of phosphate cathode materials, tion in a subsection of a review by Ji et al.in 2021.[31] However,
underscoring its critical significance for further advancements. neither of these studies has achieved a unified understanding of
In the comprehensive exploration of LMFP materials, advance- the LMFP delithiation/lithiation mechanism. These findings in-
ments in charge transport performance are achieved through spire us to comprehensively summarize and analyze the delithi-
primary particle size micronization,[18] surface coating with the ation/lithiation mechanism of LMFP, considering both crystal
conductive agent,[19] doping,[20] and meticulous control of defect structure transition and electronic structure changes. We aim
concentration.[21] Theoretically, the specific energy of LMFP in- to identify common conclusions and address remaining unre-
creases with the increase of Mn content,[22] yet empirical evi- solved issues. By leveraging various advanced characterization
dence demonstrated that for y ≥ 0.8[23] or y > 0.75, [17] the spe- techniques, we aspire to unveil the concealed verities underlying
cific energy decreases with increasing Mn content. This apparent these intricate phenomena, thereby contributing to the advance-
inconsistency stems from the distinctive delithiation/lithiation ment of LMFP materials characterized by superior electrochemi-
mechanisms unique to LMFP, setting it apart from LFP, where cal attributes. As shown in Figure 2, owing to the relaxation prop-
the electrochemical performance of LMFP is heavily influ- erty of LMFP, in situ characterizations provide a more realistic
enced by its structural evolution during the delithiation/lithiation portrayal of its complex delithiation/lithiation mechanism.
processes.[24] Structure transition will lead to changes in the coor- Consequently, with a focus on the crystal structure transition
dination environment and lattice structure of the transition metal during the energy conversion of LMFP, we mainly summarized
ions, while the phase transition in the nucleation and growth of the research results of in situ/operando X-ray diffraction (XRD),
new phases will also change with cycling. The cumulative im- in situ X-ray absorption spectroscopy (XAS), cyclic voltammetry
pact of these intricate factors determines the battery’s overall per- (CV), galvanostatic intermittent titration technique (GITT), and
formance metrics, encompassing cycle life, power density, and in situ electrochemical impedance spectroscopy (EIS) to iden-
energy density.[25] Accordingly, delving into the crystal and elec- tify various factors that may influence the structure transition.
tronic structure change mechanisms of LMFP, as well as the in- This comprehensive analysis aims to disentangle various factors
fluencing factors in the delithiation/lithiation processes, stands that potentially impinge on the structure transition. Among these
as a pivotal prerequisite and cornerstone for refining synthesis factors, such as Fe/Mn ratios, charge/discharge rates, particle
techniques, enhancing performance attributes, and circumvent- sizes, and antisite defects, the compositional uniformity of LMFP
ing the barriers in LMFP materials commercialization. emerges as the predominant contributor to the intricate crystal
With the continuous development of synchrotron radiation structure transition mechanism. Moreover, in terms of the elec-
technology and the array of advanced in situ characterization tronic structure, insights garnered from in situ XAS and Möss-
techniques,[26] the exploration of LMFP’s delithiation/lithiation bauer spectra divulge that the compositional uniformity of LMFP
mechanism and its multifaceted influences can now be ap- profoundly shapes the interactions between the chemical envi-
proached from diverse perspectives. However, as shown in ronments of Fe and Mn. Furthermore, the sluggish kinetics of
Figure 1, despite the increasing number of publications re- the Mn2+ /Mn3+ reaction leads to incomplete redox, which is one
lated to LMFP, especially over the last decade, there is still a of the main reasons for the poor electrochemical performance of
relatively limited amount of literature focusing on the mech- LMFP. LMFP samples in the literature with carbon coating are

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the domino-cascade model. Nevertheless, pronounced inhomo-

geneity in phase transition is observed for multiple particles at a
high rate (5C), which is a statistical behavior resulting from asyn-
chronous reaction between particles.[24]
Considering that the phase interface region corresponds to
the metastable intermediate phase Lix FePO4 (Lx FP) before phase
separation,[37] under specific conditions of rate,[38] particle size,
and temperature, particles can exhibit single-phase reaction
(solid solution mechanism) when the proportion of the non-
equilibrium solid solution region at the phase interface is sig-
nificant. For example, Masquelier et al. demonstrated diverse
phase transition behaviors predicated upon variations in parti-
Figure 2. Schematic diagram for the delithiation/lithiation mechanism of cle dimensions. By scrutinizing the voltage plateau slope and
LMFP: Due to the relaxation property, in situ characterizations provide
characteristic peak alterations through in situ XRD, it was ob-
more realistic results of the complex delithiation/lithiation mechanism
of LMFP. Among the pivotal determinants, encompassing Fe/Mn ratios, served that particles with a size of 140 nm exhibits a phase
charge/discharge rates, particle dimensions, and antisite defects, the com- transition mechanism, while those of 40 nm exhibits a solid-
positional homogeneity of LMFP emerges as a linchpin contributing to solution mechanism.[29a] Ichitsubo et al. reported that electro-
the multifaceted structure transition mechanism. Furthermore, this uni- chemical reaction in LFP particles with a size of 10 nm indi-
formity significantly modulates the interplay between the distinct chemical cates solid-solution mechanism, with the disappearance of the
environments of Fe and Mn within the electronic structure. Additionally, two-phase voltage plateau.[29b] Lim et al. investigated the crys-
the sluggish kinetics of the Mn2+ /Mn3+ reaction leads to incomplete ox-
idation/reduction, a prevailing factor influencing LMFP’s overall electro-
tal structure transition of Lx FP platelet particles (≈1 mm wide
chemical performance. and 150 nm thick) at different rates using operando liquid scan-
ning transmission X-ray microscopy. At a low rate (<0.2C), Li+
distribution showed inhomogeneous, indicating a tendency to-
denoted as “LMFP/C”, while samples without mentioned carbon
ward phase transition mechanism. When the rate beyond 0.2C,
coating are marked as “LMFP”. This nomenclature aids in dis-
it transitioned to solid solution mechanism.[39] For LFP with
cerning variations within the reported outcomes.
a particle size of ≈190 nm, in situ XRD revealed the forma-
tion of a non-equilibrium solid solution phase at a high rate
2. A Brief Review of the LFP Structure Transition (10C).[28a] At an even higher rate (60C), LFP exhibited a non-
Mechanism equilibrium solid solution phase as the primary composition dur-
ing the charge/discharge processes, indicating a solid solution
LFP and LMFP have highly analogous crystal structures. To fa- mechanism.[28d] Additionally, the structure transition of LFP ex-
cilitate a deeper understanding of the LMFP structure transi- hibits relaxation behavior.[40]
tion mechanism, it is necessary first to clarify the structure tran- The influence of rate and particle size on the structure tran-
sition mechanism of LFP. Currently, the delithiation/lithiation sition behavior of LFP can be attributed to kinetics, while the
processes of LFP are widely recognized as a two-phase reaction effect of temperature on LFP structure transition is more com-
(phase transition mechanism).[32] The robust localization of Fe plex. Masquelier et al. analyzed the structure transition behavior
ions leads to the dominant interaction between electrons and Li+ , of LFP at different temperatures using temperature-controlled
promoting phase separation between Li-rich and Li -poor regions, XRD. In the continuous heating process from ≈200 to ≈350 °C,
resulting in a two-phase state.[33] LFP gradually transformed from a two-phase (LFP+FP) to a
During the course of these research, two classic models have single-phase (Lx FP). When the temperature exceeded 500 °C,
been emerged, illustrated in Figure 3a,b. The early core-shell the single-phase Lx FP decomposed into a mixture of non-olivine
model[17,34] overlooked the anisotropy of Li+ transport channels phases. Similarly, during cooling, the single-phase Lx FP de-
and the insertion energy of crystal surface ions in the LFP.[35] composed into a two-phase mixture with components vary-
In contrast, the subsequent domino-cascade model[27a] suggests ing with the initial temperature T and Li content x. How-
that Li+ extraction/insertion and migration within the solid phase ever, when the temperature dropped below 140 °C, a multi-
primarily occur at phase interfaces, providing a better explana- phase mixture(LiFePO4 + Li0.75 FePO4 + Li0.25 FePO4 + FePO4 )
tion for various experimental observations of LFP. For LFP with appeared.[41] Fultz et al. analyzed the structure transition of LFP
particle sizes ranging from 50 to 300 nm, Cayron et al. confirmed using XRD Rietveld refinement after prolonged heating and sub-
the reliability of the domino-cascade model based on phase-field sequent cooling to room temperature, determining the eutectoid
modeling using various electron diffraction techniques. Both point of the LFP phase diagram (temperature (T) and Li content
single and multiple particles exhibit uniform two-phase reac- (x)) near x = 0.6 and 200 °C.[42] This can be attributed to the dif-
tion at low rates.[36] In a study on the dynamic phase transi- ferent types and stability of metastable Li1−x FP at various high
tion of LFP at multiple scales, hard X-ray microscopy revealed temperatures, which also depend on their thermodynamic prop-
that, for single micron-sized LFP particles, although they also ex- erties.
hibit inhomogeneity in interparticle phase transition at a high In summary, as shown in Figure 3c, due to the differences
rate (1C), the internal phase transition within individual parti- in the nucleation/growth rate and electrochemical reaction rate
cles remains a continuous two-phase transition, consistent with of the new phase,[43] the structure transition of LFP during the
the behavior observed at a low rate (0.02C), akin to the tenets of delithiation/lithiation processes is influenced by particle sizes,

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Figure 3. Schematic illustrations of LFP structure transition mechanism: a) Domino-cascade model;[27a] b) Core-shell model;[44] c) Two-phase transition
and size/rate/temperature-dependent non-equilibrium solid solution transition.[28a].

charge/discharge rates, and temperatures. The smaller the parti- of the Li-rich phase stabilizes. Moreover, there appears to be little
cle size and the higher the rate, the more favorable it is for form- difference in the unit cell volume change rate between different
ing a more considerable amount of metastable solid solution. On charge rates, SOC, and charge/discharge processes, suggesting
the other hand, the phase transition mechanism tends to occur that these conditions may not significantly impact the structural
in micron-sized particles during a low charge/discharge rate. Al- relaxation. Although it is explained in the literature that the non-
though reducing the particle size can shorten the phase transition equilibrium Li-rich solid solution formed during Li+ insertion
interval and lower the nucleation barrier, it also leads to decreased may separate into Li-poor and Li-rich phases during relaxation,
voltage and packing density, resulting in reduced energy density, the relaxation change of the Li-poor phase is not analyzed in the
which is unsuitable for practical applications. The solid solution literature.
mechanism at a higher charge/discharge rate may be one of the However, in a subsequent study by Yao et al., the non-
reasons why LFP has higher rate performance, but the problems equilibrium insertion path of Li+ during the relaxation process of
of asynchronous particle reaction and reduced particle utilization Li0.6 Mn0.75 Fe0.25 PO4 /C was analyzed. The XRD analysis showed
efficiency will also accompany it. that the peak position of the Li-rich phase moves to a low an-
gle within the relaxation time from 0 to 84 h, reflecting the for-
mation of defective small domains of non-equilibrium Li-rich
3. The Crystal Structure Transition Mechanism of solid solution during the Li+ insertion process. During the relax-
LMFP ation process, these small domains separate into two equilibrium
phases(Li-rich phase and Li-poor phase) and kept gathering., ex-
Compared to LFP material, LMFP exhibits a more complex elec- hibiting a fluctuating upward trend, as shown in Figure 4b.[46]
tronic structure and poorer charge transport capability, resulting The investigation into the relaxation properties of LMFP, as re-
in a more intricate crystal structure transition mechanism. The ported above, primarily relies on statistical data derived from the
structure transition of LMFP is not only influenced by characteri- analysis of multiple particles through XRD, it is more intuitive to
zation methods (in situ/ex situ) but also by factors such as Mn/Fe show the relaxation and phase separation between interparticles,
ratios, charge/discharge rates, particle sizes, relaxation and de- as shown in Figure 5a. Notably, considering the similarity of the
fect concentrations. Moreover, all these factors are susceptible to structural properties of LMFP and LFP, it is also very likely that
the synthesis methods and process conditions. the relaxation effect also still existing the introparticles for single-
particle,[35d,47] as shown in Figure 5b. It can be seen that the
relaxation property influences the structure transition of LMFP
3.1. Relaxation Property of Crystal Structure Transition Behavior to a large extent. Nonetheless, it is worth noting that the relax-
ation characteristics of LMFP might have been overlooked in sev-
Like LFP,[40,44] LMFP has a certain degree of relaxation effect eral studies, especially those exploring the delithiation/lithiation
in its crystal structure transition during Li+ extraction/insertion. mechanisms through ex situ characterization methods. In this
Yao et al. investigated the relaxation property of LMFP in the regard, the unique high-resolution advantages of synchrotron-
single-phase reaction region of Lix Mn0.75 Fe0.25 PO4 /C (0.75 ≤ x based in situ/operando XRD, XAS, and Mössbauer spectra allow
≤ 1) under different charge rates, state-of-charge (SOC), and one to rapidly capture the crystal structure, electronic structure,
charge/discharge processes. During the relaxation period of 0– and compositional changes of LMFP at multiple scales during dy-
54 h, as depicted in Figure 4a, XRD analysis revealed an overall namic delithiation/lithiation processes.[48] Given the aforemen-
increase in the unit cell volume of the formed Li-rich phase with tioned considerations, this review places a particular emphasis
prolonged relaxation time under different conditions.[45] How- on the application of in situ/operando characterizations. By lever-
ever, it can be observed from the figure that the relaxation time aging these techniques, a comprehensive analysis of the struc-
has not reached the maximum point where the unit cell volume tural transition behavior of LMFP materials can be achieved.

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Figure 4. a) The cell volumes in the Li-rich phase continue to increase with the extension of relaxation time under different conditions (a1 -rates, a2 -SOC,
a3 -charge/discharge processes).[45] b) Changes in crystalline domain size as a function of relaxation time after the termination lithium insertion for
b1 -the Li-rich phase and b2 - the Li-lean phase, domain sizes of the two phases increase in a wave pattern.[46].

3.2. The Change Law of Crystal Structure Transition stage of the Fe2+ /Fe3+ reaction (≈0.5 ≤ x ≤≈0.6), while the
Mn2+ /Mn3+ reaction almost all showed a phase transition mech-
The research findings pertaining to LMFP synthesized through anism (0 ≤ x ≤ 0.51), as shown in Figure 6a-left.[30a] However,
solid-state exhibit noteworthy discrepancies. In 2005, Nikolowski the Lix Mn0.5 Fe0.5 PO4 /C synthesized by the same method was
et al. pioneered the utilization of synchrotron in situ XRD investigated by in situ synchrotron XRD at C/20, as shown in
to investigate the electrochemical delithiation process of Figure 6a-right, in the whole Fe2+ /Fe3+ reaction region and a
LiFe0.4 Mn0.6 PO4 at C/43 synthesized by the solid-state. This small portion of the Mn2+ /Mn3+ reaction region (0.4 < x < 1) are
study demonstrated that the single-phase solid solution region both solid solution mechanism.[30b] The significant difference
occurred only in a small range of ≈0.55 ≤ x ≤ ≈0.67.[49] Similarly, in conclusions between these reports mentioned above is due
the synchrotron radiation in situ XRD study of the first charge to the considerable influence of synthesis conditions on the
process (C/20) of Lix Mn0.5 Fe0.5 PO4 /C synthesized by solid-state composition and particle uniformity of materials synthesized
showed that the single-phase reaction only exists in the later by solid-state. It is speculated that the actual structure of LMFP

Figure 5. The relaxation property of multi-particles a) and single-particle b)[35d] in LMFP or LFP, a non-equilibrium solid solution phase gradually
transforms into the two-phase system with Li-rich phase and Li-poor phase.

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Figure 6. Transition diagrams of in situ XRD for structure transition intervals at different Li content or state of charge (SOC). a) Notably differing structural
transition mechanisms emerge in LMFP synthesized through solid-state methods during charge at a C/20 rate: The single-phase solid solution region
exists only in the Fe2+ /Fe3+ reaction region at ≈0.5 ≤ x ≤ ≈ 0.6 in the left figure,[30a] while all Fe2+ /Fe3+ reaction and part of the Mn2+ /Mn3+ reaction
are in the single-phase region in the right.[30b] b) A comparative examination between 0.9LMFP⋅0.1LVP (left) and LMFP (right) showcases a notably
expanded solid solution region for the former, culminating in an enhanced electrochemical performance.[50]

materials prepared through solid-state may differ between the not all substances or states engaged in these structural changes
aforementioned studies. Beyond the varying Mn/Fe ratios and maintain a crystalline nature. Thus, supplementing XRD with
synthesis approaches, the synchronicity of LMFP particles in the other characterization methods becomes imperative to obtain a
electrochemical reaction process also affects apparent structure comprehensive insight into diverse structural alterations. In situ
transition behavior, as XRD only reflects the statistical behavior XAS study of Li1−x Mn0.5 Fe0.5 PO4 /C synthesized by solid-state
of multiple particle structure transition. found that two single isostatic points in X-ray absorption near
Strategic modifications to the material composition hold edge structure (XANES) spectra in some Fe K-edges (0.00 ≤ x ≤
the potential to broaden the single-phase region and con- 0.38) and Mn K-edges (0.49 ≤ x ≤ 1.00). After normalization with
currently enhance the electrochemical performance of LMFP. principal component analysis (PCA), it was shown that the two-
Our research has successfully bolstered electron transport at phase regions of Fe2+ /Fe3+ and Mn2+ /Mn3+ are located at 0.00
the LiMn0.7 Fe0.3 PO4 /C interface by incorporating Li3 V2 (PO4 )3 ≤ x ≤ 0.38 and 0.49 ≤ x ≤ 1.00, respectively. Because the pres-
(LVP).[50] As shown in Figure 6b presents in situ XRD analy- ence of isosteric points indicates that the concentration changes
sis, revealing that LMFP experiences both single-phase and two- of each component in the chemical reaction near them are lin-
phase reactions during the charging process, with a reverse be- early correlated,[51] making it a two-phase region. The absence of
havior observed during discharge. These findings are in align- single isosbestic point in Fe K-edge spectra and Mn K-edge spec-
ment with the outcomes of other in situ characterization stud- tra within the range of ≈0.4 ≤ x ≤ ∼0.5 suggests that Fe2+ /Fe3+
ies. Specifically, the phase transition mechanism mainly occurs and Mn2+ /Mn3+ proceed by other reaction mechanisms, and the
in the Mn2+ /Mn3+ reaction region, and the solid solution mech- in situ XRD analysis further confirmed that the intermediate re-
anism primarily occurs in the Fe2+ /Fe3+ reaction region. Com- action region (≈0.4 ≤ x ≤ ≈0.5) is a solid solution mechanism.
parative analysis between LiMn0.7 Fe0.3 PO4 /C and its LVP-doped The kinetics of Li+ diffusion are intrinsically linked to struc-
counterpart demonstrated that the addition of LVP leads to an tural transitions. Since the structure transition of LMFP coin-
expanded single-phase reaction regime, thereby amplifying the cides with Li+ insertion/extraction, it is theoretically possible to
electrochemical performance.[50] Given that improved particle indirectly infer the structure transition during electrochemical
electron transport enhances the synchronization of inter-particle cycling through the analysis of charge transfer and Li+ diffu-
reactions, this suggests that the two-phase reaction exhibited by sion kinetics. Inherent limitations imposed by nucleation and
LiMn0.7 Fe0.3 PO4 /C in some charge states may be due to differ- growth kinetics, as opposed to ion diffusion in solid solutions, re-
ences in charge state between particles. For LiMn0.5 Fe0.5 PO4 /C, sult in generally sluggish kinetics for first-order phase transition
which is in the single-phase solid solution region for the whole reactions,[11a,52] meaning that the apparent Li+ diffusion coeffi-
charge/discharge processes, the electrochemical performance is cient (DLi + ) consistently registers lower values in the phase tran-
higher than that of LMFP for other Mn/Fe ratios (with different sition region compared to the solid solution region.[53] Therefore,
degrees of two-phase regions).[14a] This observation underscores the structure transition pathway can be inferred by examining the
the superior reaction kinetics associated with the single-phase variation of DLi + with SOC.
solid solution domain. Taken collectively, these case studies un- The analysis of CV and GITT has yielded insightful outcomes.
derscore the pivotal role of improving charge transfer unifor- CV tests have shown that DLi + increases with increasing Mn
mity within porous electrodes and mitigating lattice mismatch- content in LiFe1−x Mnx PO4 /C (0<x<0.2), as Mn doping leads to
induced strain between the Li-poor and Li-rich phases through ju- solid solution behavior in the material.[54] When the Mn dop-
dicious doping. Such measures hold the promise of significantly ing level is relatively low, the solid solution region increases
elevating the electrochemical properties of these materials. with increasing Mn content.[54] It is evident that the Mn/Fe ra-
Although XRD can directly characterize the crystal structure tios affect the structure transition in LMFP, thereby influencing
transition of LMFP during the delithiation/lithiation processes, the apparent Li+ diffusion kinetics. Combining CV and GITT,

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Hashambhoy et al. conducted a comparative analysis of DLi +

during charge and discharge processes for LiFe0.5 Mn0.5 PO4 /C,
as well as physical mixtures of LMP and LFP. They found that
the DLi + of LiFe0.5 Mn0.5 PO4 /C surpasses that of the (LMP+LFP)
mixture.[55] Although the DLi + measured by CV and GITT tech-
niques are apparent values, the authors suggested that the DLi +
in the Mn2+ /Mn3+ reaction region is consistently lower than
that in the Fe2+ /Fe3+ reaction region; this can be attributed to
the phase transition mechanism in the Mn2+ /Mn3+ reaction re-
gion and the Jahn-Teller effect caused by Mn3+ , which distorts
the Mn-O bond and brings Mn3+ closer to the Li+ diffusion
pathway, thereby elevating the activation energy barrier for Li+
migration.[56] These insights seem to rationalize the the lower
reactivity of the Mn2+ /Mn3+ redox compared to the Fe2+ /Fe3+ re- Figure 7. Structure transition intervals of LMFP at different Mn/Fe ratios
dox mentioned in most studies, as well as the incomplete redox during delithiation/lithiation processes: MI and MII (M═Mn, Fe) repre-
observed for Mn2+ /Mn3+ reaction. sent the solid solution region and two-phase region of Mn or Fe, respec-
The investigation into the structure transition dynamics of tively. “MnI + FeI ” is the solid solution region where Mn and Fe coexist.
The “H-T” and “S-T” marked in red represent hydrothermal and solvother-
LMFP has been approached through overpotential and War-
mal methods, respectively, while the ones not marked are solid-state. The
burg impedance analyses.[57] Surprisingly, the overpotential in- gray bidirectional arrows represent the charge and discharge processes,
creases at the beginning and end of the charge–discharge pro- respectively.
cess and during the solid-solution reaction phase in the interme-
diate region, which requires further explanation. This perplex-
of the single-phase region shared by Fe2+ /Fe3+ and Mn2 /Mn3+
ing behavior warrants further elucidation. Conventionally, within
is more likely when the Mn/Fe ratio approaches 1, suggesting a
two-phase regions, the presence of phase boundaries invariably
higher probability of uniform distribution of Mn and Fe in the
heightens the Li+ transport impedimentr, and the accompany-
lattice, thus culminating in an expanded domain of LMFP’s ho-
ing mismatch strain increases the overpotential of the phase
mogeneous solid-solution microcrystalline structure. Although
transition process.[58] The slope of the Warburg region, as de-
Schougaard et al. interpreted this shared solid-solution region as
rived from in situ EIS, deviations from ≈45° trajectory of this
related to lithium content-induced phase transition hysteresis,[60]
slope are discerned when Li+ diffusion occurs at phase bound-
the hysteresis behavior may originate from Jahn-Teller distortion,
aries. The gradient trend in a first-order phase transition sys-
which makes the reordering of bonds involving Mn3+ more chal-
tem is significantly different during the charge/discharge pro-
lenging during phase separation, since the transition from the
cesses, indicating different Li+ extraction/insertion paths during
solid-solution to the two-phase state is driven by bond enthalpy.
the two-phase reaction, as observed in other relevant reports.[59]
Although the crystal structure transition behavior of LMFP
In the Mn2+ oxidation reaction region, a gradual evolution is dis-
exhibits certain regularities, it is important to acknowledge the
cerned in the Warburg region slope, which may suggest the grad-
notable divergences that exist. A compelling illustration of this
ual formation of the Mn0.8 Fe0.2 PO4 phase near the surface of
phenomenon is apparent in Figure 7. Here, it becomes evident
Lix Mn0.8 Fe0.2 PO4 /C, consistent with the domino-cascade model.
that LMFP samples characterized by identical Mn/Fe ratios can
Furthermore, the sudden decrease followed by a constant angle
exhibit contrasting profiles of two-phase and solid-solution re-
during the initial lithiation process implies a smooth interfacial
gions, even when synthesized using the same methods (the red
boundary between Lix Mn0.8 Fe0.2 PO4 and Mn0.8 Fe0.2 PO4 , similar
text in the figure denotes “H-T” for hydrothermal and “S-T”
to the core-shell model.
for solvothermal, while unlabeled methods correspond to solid-
Based on various reports, we gain insights into the crystal
state). Expanding upon this observation, the solid-solution re-
structure transitions of LMFP under different Mn/Fe ratios dur-
gions also vary significantly for diverse electrochemical cycling
ing the delithiation/lithiation processes, as illustrated in Figure 7.
processes (as indicated by the gray bidirectional arrows in the
MI and MII (M═Mn, Fe) represent the solid-solution reaction re-
figure). This dynamic underscores the inherent irreversibility of
gion and the phase transition region for Mn or Fe, respectively.
structural transformations during the course of electrochemi-
“MnI + FeI ” conveys the coexistence of Mn and Fe in the solid-
cal cycling. Therefore, in addition to the Mn/Fe ratios, synthesis
solution region. It can be observed that Mn/Fe ratios strongly in-
methods, charge/discharge rates, particle sizes, and defects also
fluence the structure transition behavior of LMFP. With a surge
influence the crystal structure transition of LMFP. The specific
in Mn content, the extent of the Mn2 /Mn3+ reaction range within
details will be discussed in the next section.
the two-phase region steadily expands. Compared to Fe2+ /Fe3+ ,
the Mn2 /Mn3+ reaction is more inclined toward the two-phase
reaction, with only a tiny portion potentially in the single-phase 3.3. The Influencing Factors of Crystal Structure Transition
solid solution region. On the other hand, the Fe2+ /Fe3+ reaction Mechanism
is more prone to exhibit structure transition in both single-phase
and two-phase regions, with the single-phase region often located The factors influencing the delithiation/lithiation mechanism of
in the intermediate stage of the reaction. An exception emerges LMFP can be mainly categorized into macroscopic and micro-
in Fe-rich LMFP, where the Fe2+ /Fe3+ reaction distinctly gravi- scopic aspects, as shown in Figure 8. Among the macro-factors,
tates toward the two-phase region. Additionally, the occurrence apart from the characterization methods, the most significant

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charge processes. This array of observations collectively accentu-

ates the multifaceted nature and intrinsic sensitivity that encap-
sulate the captivating crystal structure transition dynamics inher-
ent to LMFP.

3.3.1. Mn/Fe Ratios

Experimental and computational phase diagrams are compared

to analyze the significant influence of Fe/Mn ratios on the struc-
ture transition behavior. In 2001, Yamada et al. performed a com-
parative analysis of multiple delithiation stages (chemical delithi-
ation) of Lix Mny Fe1−y PO4 using ex situ XRD and Mössbauer
spectra. The 2D phase diagram (0≤x, y≤1) of Lix Mny Fe1−y PO4
was divided into four regions, as illustrated in Figure 9a: (I)
the unstable region near the point (x, y) = (0, 1); (II) the two-
phase region of Mn2+ /Mn3+ reaction (y≥x); (III) the single-
phase region of Fe2+ /Fe3+ reaction, simultaneously connecting
regions (II) and (IV); (IV) the two-phase region of Fe2+ /Fe3+
reaction (y≤x).[69] This phase diagram encapsulated the inter-
dependence between the extent of delithiation and the Fe/Mn
ratios on the structure transition to a certain extent. How-
Figure 8. The macro and micro affecting factors of LMFP structure tran-
sition. ever, it does not reflect the potential single-phase region of the
Mn2+ /Mn3+ reaction, which may be due to differences in char-
acterization techniques (ex situ/in situ) and (de)lithiation meth-
ones are the Mn/Fe ratios and synthesis methods. Additionally, ods (chemical/electrochemical) used in subsequent studies,[27a]
the charge/discharge rates, delithiation/lithiation ways, cycling as well as the compositional uniformity of LMFP. In a subse-
number, carbon coating, and temperatures are also important quent computational study, Zhou et al. presented a computa-
factors. Simultaneously, the intricate interplay of micro-factors tional phase diagram of the Lix Mny Fe1−y PO4 system at 300 K
exerts a profound impact. This intricate milieu prominently fea- based on first-principles calculations, also encompassing four
tures the relaxation property, while simultaneously spanning an regions (Figure 9b).[70] However, unlike Yamada et al.’s experi-
array of material attributes inclusive of particle dimensions, in- mental phase diagram, the computational phase diagram exhib-
trinsic defects, morphology intricacies, and potential impurities. ited a single-phase region of Mn2+ /Mn3+ reaction close to x =
Such attributes are inherently determined by the synthesis meth- y, which the authors attributed to the Jahn-Teller effect of Mn3+ .
ods and processes. Furthermore, in the vicinity of x = y, the occurrence of a shared
Table 1 provides a detailed summary of the single-phase solid single-phase region of Fe2+ /Fe3+ and Mn2+ /Mn3+ reactions bet-
solution regions obtained during the delithiation/lithiation pro- ter aligned with the summarized rules of crystal structure tran-
cesses of LMFP under different conditions. Notably, an overarch- sition in the previous section. It is worth noting that the compu-
ing trend emerges, wherein the majority of documented LMFP tational phase diagram depicted a broader two-phase region for
samples were synthesized by solid-state. While uniformity per- the Fe2+ /Fe3+ reaction.
sists in the selection of raw materials, noteworthy variations The same study observed different single-phase regions
come to the fore, encompassing divergences in synthesis con- for varying Mn/Fe ratios, but the interval sizes are ≈0.2–
ditions, particle dimensions, carbon source preferences, and the 0.3. Operando XRD analysis of Lix Mny Fe1−y PO4 /C synthe-
strategic inclusion of carbon coating. However, a subset of inves- sized by solid-state demonstrated that the single-phase re-
tigations omits explicit documentation of critical factors such as gion for Lix Mn0.25 Fe0.75 PO4 /C is 0.25 ≤ x ≤ 0.55, while for
the carbon coating status or particle sizes associated with LMFP, Lix Mn0.5 Fe0.5 PO4 /C, the region is 0.50 ≤ x ≤ 0.70, with the re-
despite their potential to wield substantial influence over struc- maining regions exhibiting phase transition behavior. In the case
tural evolution.[61] For instance, carbon coating can reduce the of Lix Mn0.75 Fe0.25 PO4 /C, almost the entire range of Fe2+ /Fe3+ re-
surface disorder state of particles, enabling LFP to maintain the action in the single-phase region (0.75 ≤ x ≤ 0.95).[64,66] However,
two-phase reaction even at smaller particle sizes.[62] Moreover, when y ≤ 0.5, a portion of the Fe2+ /Fe3+ reaction still occurred in
LMFP nanoparticles with efficient carbon coating facilitate rapid the two-phase region, consistent with the phase diagram results
electron transfer on the surface and Li+ diffusion within the reported by Yamada et al.[69] Evidently, the single-phase region
bulk.[7b] Additionally, smaller particle sizes promote the forma- adjusts in response to varying Mn content, with Mn2 /Mn3+ reac-
tion of solid solution structure during the charge/discharge pro- tion consistently manifesting within the two-phase region.[64]
cesses. Furthermore, the investigated charge/discharge rates pre- The extent of lattice mismatch between lithiated and delithi-
dominantly focused on low rates such as C/20 and C/10. How- ated phases varies with different Mn/Fe ratios, exerting a pro-
ever, different studies focus on different electrochemical cycling found influence on the structure transition behavior. Ravnsbæk
processes, even within the same study, there are variations in et al. conducted in situ synchrotron XRD on LiMny Fe1−y PO4
the single-phase solid solution regions during charge and dis- (≈50 nm) samples synthesized via solid-state to analyze the lattice

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Table 1. The single-phase reaction regions of LMFP during delithiation/lithiation processes under varying conditions.

Mn/Fe Synthetic Raw materials Auxiliary Carbon Conditions Size Rates Characterization Charge(C)/ Single- Ref
ratios methods reagents source(wt.%)/ [nm] methods Discharge (Disc) phase
conditions region

0.1:0.9 hydrothermal FeSO4 . 7H2 O, ascorbic glucose (10)/ 200 °C, 3 h / C/5 PITT, in situ XRPD C and Disc 0–0.2 [63]
MnSO4 . 5H2 O, acid 600 °C, 1 h
H3 PO4 , LiOH·H2 O
solid-state FeC2 O4 ·2H2 O, Acetone / 350 °C, 10 h ≈50 C/10 operando C 0–0.55 [52]
MnCO3 , →700 °C, 5 h synchrotron PXD
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, Acetone / 350 °C, 10 h ≈50 C/10 operando Disc 0–0.45 [52]
MnCO3 , →700 °C, 5 h synchrotron PXD
NH4 H2 PO4 , Li2 CO3
0.2-0.8 solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h ≈50 C/10 operando C ≈0–≈0.5 [52]
MnCO3 , →700 °C, 5 h synchrotron PXD
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h ≈50 C/10 operando Disc ≈0–≈1 [52]
MnCO3 , →700 °C, 5 h synchrotron PXD
NH4 H2 PO4 , Li2 CO3
0.25:0.75 solid-state FeC2 O4 ·2H2 O, / carbon 600 °C 120 C/20 operando XRD and C and Disc 0.25-0.55 [64]
Mn(CO2 CH3 )2 . 4H2 O, Mössbauer
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, / glucose 700 °C, 10 h / C/20 operando C 0.23–0.3 [65]
MnCO3 , synchrotron PXD
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, / glucose 700 °C, 10 h / C/20 operando Disc 0.27–0.9 [65]
MnCO3 , synchrotron PXD
NH4 H2 PO4 , Li2 CO3
0.4:0.6 solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h ≈50 C/10 operando C ≈0.4– [11a]
MnCO3 , →700 °C, 5 h synchrotron PXD ≈0.7
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h ≈50 C/10 operando Disc ≈0.4–≈1 [11a]
MnCO3 , →700 °C, 5 h synchrotron PXD
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h 106 C/10 operando C 0.5–0.6 [11a]
MnCO3 , →700 °C, 5 h synchrotron PXD
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h 106 C/10 operando Disc 0.35–0.8 [11a]
MnCO3 , →700 °C, 5 h synchrotron PXD
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h 152 C/10 operando Disc 0.45–0.75 [11a]
MnCO3 , →700 °C, 5 h synchrotron PXD
NH4 H2 PO4 , Li2 CO3
0.5:0.5 solid-state FeC2 O4 ·2H2 O, / sucrose (5)/ 700 °C, 8 h / C/20 in situ XAS, XRD C ≈0.5– [30a]
MnCO3 , 700 °C, 4 h ≈0.6
NH4 H2 PO4 , Li2 CO3
Hydrothermal FeSO4 . 7H2 O, ascorbic glucose (10)/ 200 °C, 3 h / C/5 PITT, in situ XRPD C and Disc ≈0.4– [63]
MnSO4 . 5H2 O, acid 600 °C, 1 h ≈0.6
H3 PO4 , LiOH·H2 O
solid-state Fe2 O3 , MnO2 , / carbon 750 °C, 1 h 100– C/20 in situ synchrotron C 0.4–1 [30b]
MA+CTR (NH4 )2 HPO4 , 200 XAS, XRD
Li2 CO3
solid-state Fe2 O3 , MnO2 , / carbon 750 °C, 1 h 100– C/20 in situ synchrotron Disc 0.4–0.93 [30b]
MA+CTR (NH4 )2 HPO4 , 200 XAS, XRD
Li2 CO3
solid-state FeC2 O4 ·2H2 O, / carbon 600 °C 120 C/40 operando XRD and C and Disc 0.5–0.7 [66]
Mn(CO2 CH3 )2 . 4H2 O, Mössbauer
NH4 H2 PO4 , Li2 CO3
(Continued)

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Table 1. (Continued).

Mn/Fe Synthetic Raw materials Auxiliary Carbon Conditions Size Rates Characterization Charge(C)/ Single- Ref
ratios methods reagents source(wt.%)/ [nm] methods Discharge (Disc) phase
conditions region

solvothermal FeSO4 . 7H2 O, ethylene carbon and 185 °C,18 h 100– C/4 in situ synchrotron C 0.3–0.78, [67]
MnSO4 . H2 O, glycol sucrose (5)/ 200 WAXS and XAS 0–0.1
H3 PO4 , LiOH·H2 O 300 °C, 6 h→
500 °C, 6 h
solvothermal FeSO4 . 7H2 O, ethylene carbon and 185 °C, 18 h 100– 5C in situ synchrotron Disc ≈0.4– [67]
MnSO4 . H2 O, glycol sucrose (5)/ 200 WAXS and XAS ≈0.5
H3 PO4 , LiOH·H2 O 300 °C, 6 h→
500 °C, 6 h
sol-gel Fe(CO2 CH3 )2 , ethylene ethylene glycol 700 °C, 12 h / / GITT, CV C and Disc 0.5–1 [55]
Mn(CO2 CH3 )2 , glycol
H3 PO4 ,
CH3 COOLi·2H2 O
0.6:0.4 solid-state FeC2 O4 ·2H2 O, acetone / 280 °C, 3 h→ / C/43 in situ synchrotron C 0.55–0.67 [68]
MnCO3 , 550 °C, 24 h XRD,
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h ≈50 C/10 operando C ≈0.45–≈1 [52]
MnCO3 , →700 °C, 5 h synchrotron PXD
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h ≈50 C/10 operando Disc ≈0.5– [52]
MnCO3 , →700 °C, 5 h synchrotron PXD ≈0.95
NH4 H2 PO4 , Li2 CO3
0.75:0.25 solid-state FeC2 O4 ·2H2 O, / carbon 600 °C 120 C/40 operando XRD and C and Disc 0.75–0.95 [66]
Mn(CO2 CH3 )2 . 4H2 O, Mössbauer
Li2 CO3 , NH4 H2 PO4
0.8:0.2 solvothermal (Fe(NO3 )3 ·9H2 O, DMF, sucrose (5.2)/ 180 °C, 12 h ≈40 C/20 GITT, in situ EIS C and Disc 0.8–1 [57]
LiOH·H2 O HNO3 700 °C, 3 h and XRD
Mn(CO2 CH3 )2 . 4H2 O,
H3 PO4
solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h ≈50 C/10 operando C ≈0.6-≈∼1 [52]
MnCO3 , →700 °C, 5 h synchrotron PXD
NH4 H2 PO4 , Li2 CO3
solid-state FeC2 O4 ·2H2 O, acetone / 350 °C, 10 h ≈50 C/10 operando Disc ≈0.8– [52]
MnCO3 , →700 °C, 5 h synchrotron PXD ≈0.9
NH4 H2 PO4 , Li2 CO3

volume changes during delithiation/lithiation processes, thereby The presence of an evenly distributed equimolar combina-
assessing the lattice mismatch between LMFP, Lx MFP, and MFP. tion of Mn and Fe within the lattice of LiMn0.5 Fe0.5 PO4 /C man-
As depicted in Figure 10, during delithiation, the mismatch be- ifests as a complete solid solution mechanism during delithia-
tween LMFP and Lx MFP decreases with increasing Mn content, tion/lithiation processes, contributing to improved electrochem-
while the mismatch between Lx MFP and MFP significantly in- ical performance. Wang et al. synthesized LiMn0.5 Fe0.5 PO4 /C
creases with increasing Mn content. This phenomenon can be by microwave-assisted hydrothermal, energy dispersive spec-
attributed to the Jahn-Teller effect induced by Mn3+ . However, troscopy (EDS) and high-angle annular dark-field scanning
the Lx MFP → MFP at low Mn content (y = 0.1, 0.2) and LMFP transmission electron microscopy (HAADF-STEM) showed that
→ Lx MFP for high Mn content (y = 0.6, 0.8) exhibit continu- equimolar Fe and Mn formed a completely homogeneous LMFP
ous solid solution transition. In contrast, at y = 0.4, mismatch solid solution, as shown in Figure 11a. Operando XRD analysis
starts to occur in the Lx MFP → MFP transition. In addition, ex- during the first delithiation/lithiation processes revealed that the
cept for y = 0.1, all other Mn-containing LMFP samples undergo structure transition of LiMn0.5 Fe0.5 PO4 /C occurs entirely within
continuous solid solution transition during lithiation, showing the single-phase region, as shown in Figure 11b,c. However, for
a lesser lattice mismatch compared to the delithiation. Further LiMn0.375 Fe0.625 PO4 /C and LiMn0.75 Fe0.25 PO4 /C, the two-phase
capacity tests at different rates revealed that substantial lattice reaction can be found in the shaded areas in Figure 11d,e.[14a]
mismatch predominantly accounts for the limited capacity, even This observation suggests that the non-uniform distribution of
at a low rate (C/5).[52] Consequently, prudent control over the Fe and Mn leads to the formation of LFP or LMP microcrystalline
Mn/Fe ratio is imperative to mitigate interphase lattice mismatch domains, resulting in a two-phase region. Similarly, the ternary
effectively. olivine-type LiMn1/3 Fe1/3 Co1/3 PO4 /C solid solution synthesized

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Figure 9. The (x, y) 2D phase diagram of the Lix Mny Fe1−y PO4 (0 ≤ x, y ≤ 1). a) Experiment phase diagram: (I) the unstable region close to the point
(x, y) = (0, 1); (II) the two-phase region by Mn2+ /Mn3+ reaction (y ≥ x) (III) the single-phase region of Fe2+ /Fe3+ reaction connecting (II) and (IV);
and (IV) the two-phase region of Fe3+ /Fe2+ reaction (a part of y ≤ x);[69] b) First-principles calculations, phase diagram at 300 K: Region I corresponds
to a two-phase region associated with the Mn2+ /Mn3 ; Region II and III correspond to a single-phase region by Mn2+ /Mn3+ and Fe2+ /Fe3 ; Region IV
corresponds to a two-phase region by Fe2+ /Fe3 .[70]

via hydrothermal also undergoes an entirely single-phase reac- 3.3.2. The Composition Uniformity of LMFP (Synthesis Methods)
tion during delithiation/lithiation processes and exhibits high
reversibility.[56a] LMFP materials with different Mn/Fe ratios manifest distinct
These studies further demonstrate that the crystal structure crystal structure transition behaviors. If the material compo-
transition depends not only on the Mn/Fe ratios but also on the sition is non-uniform or there are compositional variations
uniform distribution of Mn and Fe within the crystal structure. among particles, the observed structure transition behavior in
However, achieving optimal homogeneity of Mn and Fe distri- the electrode represents a statistical average of phase transition
bution in LMFP while maintaining a consistent Mn/Fe ratio re- occurring in different regions or particles rather than an intrin-
mains a formidable challenge, even when utilizing identical syn- sic process. In these researches, the authors operate under the
thesis method. Proper synthesis method and rational coordina- assumption that materials synthesized at any given Mn/Fe ratio
tion of the Mn/Fe ratio are more likely to expand the single-phase inherently constitute homogeneous solid solutions. In fact, it
region, thereby reducing nucleation and growth of new phase is worth noting that the uniformity of material composition is
and lattice mismatch at the phase interfaces. Moreover, a com- significantly influenced by synthesis methods and processing
prehensive comprehension of the micro-compositional arrange- conditions. In scenarios where the material is a composite or
ment within LMFP serves as the foundational bedrock for an in- a blend of multiple compositions, or where phase segrega-
depth exploration of the delithiation/lithiation mechanism tion transpires during the initial lithium insertion/extraction

Figure 10. The unit cell volumes of LiMny Fe1−y PO4 (50 nm particles) as a function of overall Li-content are detected by the lower angular region of the
operando XRD during charge and discharge at C/10. Lx MFP →MFP is a continuous solid solution transition at lower Mn content(y = 0.1, 0.2), while
LMFP → Lx MFP is a continuous solid solution transition at higher Mn content (y = 0.6, 0.8).[52]

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Figure 11. a) EDS mapping of Mn, Fe, P, and O (left), HAADF-STEM image of LiMn0.5 Fe0.5 PO4 /C (middle) with more details shown in right (inset shows
a sketch representing Li in green, Mn or Fe in brown, and P in violet). b) Galvanostatic (dis)charge profiles of the LiMn0.5 Fe0.5 PO4 /C nanocrystals at a rate
of 0.2 C. c–e) Operando XRD patterns from 33° to 36.5° and 40° to 44° of LiMn0.5 Fe0.5 PO4 /C (solid solution machenism), LiMn0.375 Fe0.625 PO4 /C and
LiMn0.75 Fe0.25 PO4 /C during the (de)lithiation process, respectively, and the phase transition machenism can be found in the shaded areas. Reproduced
with permission.[14a] Copyright 2021, American Chemical Society.

stages, the elucidated mechanisms governing crystal structure tial existence of different microcrystalline domains in LMFP.[56b]
transition may substantially diverge from the anticipated norms. It is observed that there is a mutual attraction between M2+ -Li+
Theoretical calculations have been employed to scrutinize the and M3+ -VLi+ (vacancy) (M═Mn, Fe), while there is repulsion be-
potential coexistence of LFP and LMP phases within LMFP, tween M3+ -Li+ and M2+ - VLi+ . The nucleation of the new phase
as well as to investigate the impact of compositional unifor- is induced by the interaction between M2+ -Li+ and M3+ -VLi+ , as
mity on the structural transition mechanism of LFMP. Ther- shown in Figure 12a. Therefore, during delithiation, when Fe2+
mochemical assessments of LMFP materials, utilizing first- is completely oxidized to Fe3+ , Li+ is attracted to the surrounding
principles calculations, have unveiled a notable likelihood of Mn2+ and simultaneously repelled by the surrounding Fe3+ , lead-
phase separation. Specifically, the formation energy calculations ing to the preferential presence of Li+ around Mn2+ and a higher
for LiFe1−x Mnx PO4 , LMP, and LFP revealed that the formation concentration of vacancies around Fe3+ . As shown in Figure 12b,
energy of LiFe1−x Mnx PO4 is higher than the sum of the forma- if Fe and Mn are uniformly distributed in the crystal, Li+ and
tion energies of LMP and LFP. According to the Boltzmann dis- vacancies will also be uniformly distributed, resulting in struc-
tribution, LiFe1−x Mnx PO4 solid solution can exist in abundance ture transition occurring entirely as a single-phase reaction dur-
at high temperatures, but during the cooling process, phase ing delithiation/lithiation processes.
separation into LMP and LFP may occur, resulting in a mix- The potential structural composition of LMFP is analyzed
ture of products.[71] Similarly, in the study by Chu et al., phase- from an experimental perspective. While diverse synthesis meth-
separated LMFP was proposed.[72] By combining synchrotron ods exist for LMFP, the resemblance in crystal structures and
XAS with first-principles calculations and energy-dispersive X- the limited precision of elemental identification have hindered
ray spectroscopy, it was demonstrated that LiFe1−x Mnx PO4 /C comprehensive assessments of the uniformity of the fabricated
samples synthesized by solvothermal with different Mn contents LMFP materials. Consequently, an ongoing debate has revolved
consisting of both LFP and LMP phases. However, the interac- around whether LMFP manifests as a homogeneous solid solu-
tion between the two phase components at the grain interface tion (LMFP) or a multi-phase mixture (LMP + LFP + LMFP/LMP
can cause distortion in the MO6 structure (M═Fe and Mn) and + LMFP/LFP + LMFP/LFP + LMP), as underscored by recent
also affect the spin configuration of Fe ions.[72] Therefore, to en- discourse.[71,73] A majority of studies, grounded in solid-state syn-
hance the stability of the phase structure and the conductivity of thesis, have leaned toward the assumption of LMFP’s homogene-
the material, a rational Mn/Fe ratio emerges as an indispensable ity as a solid solution. This inference rests on the premise that
factor. high-spin Fe2+ and Mn2+ exhibit comparable ionic radii, thereby
Kang et al. provided a detailed explanation of the origin of enabling Fe2+ to be accommodated seamlessly within the LMP
single-phase reaction in multicomponent olivine-type materials lattice.[13b] The same explanation was provided by Yamada et al.
using first-principles calculations, further confirming the poten- for LiMny Fe1−y PO4 synthesized by solid-state.[74] However, the

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Figure 12. The arrangements of neighbor transition metals around vacancy/Li+ in Lix MPO4 (M═Fe, Mn): a) Li+ in LiMnPO4 and vacancy in FePO4 .
b) Li+ and vacancy in Lix Mnx Fe1−x PO4 . The favorable and unfavorable interactions between transition metals and Li+ or vacancies result in the formation
of solid solution phase.[56b] c) Multiple microcrystalline domains may exist in LMFP: LMFP + LFP + LMP, leading to different structure transition
mechanisms.

pursuit of atomic-level homogeneity in materials synthesized via However, contradictory results have emerged in other types
solid-state confronts inherent challenges, particularly when pro- of studies. George et al. synthesized LiFe0.5 Mn0.5 PO4 crystal
nounced disparities in Mn and Fe content exist, thereby fostering nanosheets via colloidal synthesis and observed only one pair of
the emergence of disparate microcrystalline domains. redox peaks in the CV test, attributing it to the highly uniform dis-
A noteworthy consideration is that distinct compositions may tribution of metal ions, as shown in Figure 13b2 . Nonetheless, af-
engender differing structural transition mechanisms, exempli- ter undergoing carbon coating and heat treatment, the uniformly
fied by LMFP’s adherence to a solid solution mechanism in con- distributed metal ions underwent rearrangement, resulting in
trast to the phase transition mechanism observed in LFP and the formation of Fe-enriched and Mn-enriched regions within the
LMP, as depicted in Figure 12c. Microcrystalline domains or com- lattice; this is evidenced by the appearance of two pairs of redox
position segregation can significantly affect the structure transi- peaks corresponding to Fe2+ /Fe3+ and Mn2+ /Mn3+ , as shown in
tion of LMFP during lithium insertion/extraction. The composi- Figure 13a,b1 ,b3 .[77] Similar electrochemical behavior is observed
tion uniformity of LMFP often varies due to different synthesis in other studies on LiFe0.5 Mn0.5 PO4 nanosheets synthesized via
methods and processing conditions, and even individual opera- solvothermal, where the separation of Fe and Mn redox centers
tors. Currently, an inadequate dataset hinders the comprehen- is only observed after carbon coating.[78] These studies suggest
sive comparison and analysis of the varying impact exerted by di- that carbon coating promotes the rearrangement of Fe and Mn,
verse synthesis methods on the structure transition mechanism. leading to the formation of Fe-enriched and Mn-enriched re-
Therefore, demonstrating the distribution characteristics of Mn gions within the crystal, thereby influencing the structure transi-
and Fe in LMFP should be considered an essential prerequisite tion and electrochemical performance during the lithium inser-
for studying the crystal structure transition mechanism.[30b] tion/extraction processes. Clearly, the conclusions drawn from
Two distinct lines of investigation have been undertaken these two types of studies are contradictory, prompting the ne-
to scrutinize whether carbon coating instigates the rearrange- cessity for further exploration to unveil the precise underlying
ment and enrichment of metal cations within the uniform reasons for these divergent observations.
solid solution matrix of LMFP, thereby triggering the segrega- In an effort to delve deeper, Drozhzhin et al. conducted in
tion of redox centers. Che et al. ascertained that Fe and Mn situ XRD analysis on Lix Mny Fe1 -y PO4 /C synthesized via hy-
in LiFe0.5 Mn0.5 PO4 /C synthesized via hydrothermal are uni- drothermal. For the Mn-poor Lix Mn0.1 Fe0.9 PO4 /C, as shown in
formly distributed at the atomic level within the lattice, sub- Figure 13c, the Mn2+ /Mn3+ reaction occurs entirely within the
stantiated electron energy loss spectroscopy (EELS), HAADF, single-phase region, and the equimolar Fe2+ /Fe3+ reaction also
and EDS.[73] Likewise, for LiFe0.5 Mn0.5 PO4 /C synthesized via occurs within the single-phase region. This may suggest that all
solvothermal[75] and microwave-assisted hydrothermal method, the Mn reacted with an equal amount of Fe to form LMFP solid
[14a]
results from selected area electron diffraction (SAED), EDS, solution microdomains, resulting in a single-phase region (0 ≤
and HAADF-STEM showed that both of them also exhibit x ≤ 0.2), while most of the Fe participated in the two-phase reac-
a homogeneous solid solution structure. Guda et al. synthe- tion. On the other hand, Li1−x Mn0.5 Fe0.5 PO4 /C exhibited a three-
sized LiFe0.5 Mn0.5 PO4 /C using solvothermal, confirmed through stage phase transition: the initial and final stages involved a two-
Mössbauer spectroscopy that Mn and Fe are uniformly dis- phase region, while the intermediate stage corresponded to the
tributed within the lattice.[76] These LMFP materials, which have solid solution region.[63] This behavior may also be attributed to
been demonstrated to be homogeneous solid solutions, do not the non-uniform distribution of Fe and Mn. In the case of Mn-
undergo metal ions rearrangement after the carbon coating pro- rich Lix Mn0.8 Fe0.2 PO4 /C nanoparticles (≈40 nm) synthesized via
cess. solvothermal, in situ XRD revealed that the single-phase reaction

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Figure 13. a) Possible forms of LMFP before and after carbon coating: Homogeneous solid solution (top) and two-phase separation (bottom). b) CV
response at 0.5 mV s−1 from colloidal platelet NCs has one pair redox peeks and from hydrothermal NCs under identical conditions has two pairs redox
peeks(b1 ), platelet NCs carbon coated at 500 °C for 12 h under Ar/H2 has two pairs redox peeks and while platelet NCs without H2 has one pair redox
peeks (b2 ), sketch depicting the phase segregation of Fe and Mn in olivine phosphates during a typical carbon coating process (b3 ). Reproduced with
permission.[77] Copyright 2014, American Chemical Society. c) Transition diagrams of selected in situ XRD for structure transition intervals at different
state of charge (SOC): Two-stage phase transition for Li1−x Fe0.9 Mn0.1 PO4 (left) and three-stage phase transition for Li1−x Fe0.5 Mn0.5 PO4 (right).[63]

occurs only within the Fe2+ /Fe3+ reaction region,[57] which closely rate performance of LMFP is significantly lower than that of
resembles the structure transition behavior observed in the Mn- LFP. Therefore, unraveling the rate-dependent structure transi-
poor Li1−x Mn0.1 Fe0.9 PO4 /C mentioned earlier. This confirms that tion mechanism inherent to LMFP holds the potential to enhance
a substantial discrepancy in the Mn/Fe ratios lead to the emer- its electrochemical performance.
gence of a non-uniform composition within the LMFP materials. The comparative analysis of the impact of chemical lithia-
As can be seen, the abovementioned studies that confirmed tion (independent of charge/discharge rates) and low-rate elec-
LMFP as a homogeneous solid solution were mainly based on trochemical delithiation on the structure transition mechanism
liquid-phase synthesis methods and an Mn/Fe molar ratio of 1:1. reveals intriguing insights. A comparison between the findings
In most reports, LMFP samples synthesized by solid-state with of Yamada et al.[79] and Nikolowski et al.[68] highlights distinct
different Mn/Fe ratios are directly assumed to be homogeneous structure transition behaviors exhibited by LiMn0.6 Fe0.4 PO4 sam-
solid solutions, which is likely to be inaccurate. In light of this, it ples prepared under identical conditions. In the study by Yamada
becomes imperative to delve into proficient characterization tech- et al., chemical lithiation was investigated, and ex situ charac-
niques capable of discerning between a homogeneous solid so- terization techniques such as XRD, XAS, and Mössbauer spec-
lution and a multiphase mixture within the LMFP. Such an en- troscopy showed that the Mn2+ /Mn3+ reaction region (Lx MFP,
deavor assumes significance as it underpins subsequent mech- 0≤x≤0.6) exhibits a two-phase reaction, while the Fe2+ /Fe3+ re-
anism investigations and optimization endeavors pertaining to action region (0.6≤x≤1) displays a single-phase reaction. In con-
synthesis processes. trast, the study by Nikolowski et al. focused on electrochemical
delithiation at a low-rate (C/43), and in situ synchrotron XRD
analysis revealed that the single-phase reaction region exists only
3.3.3. Charge/Discharge Rates within a small range (0.55–0.67 (0.7)). This indicates that a minor
proportion of Fe2+ and Mn2+ simultaneously participated in the
Similar to LFP, the structure transition mechanism of LMFP single-phase reaction, which differs significantly from the find-
is also influenced by the charge/discharge rates. However, the ing of the former study. The difference between the two studies

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Figure 14. Schematic of the variation of structure transition mechanism with C-rates for Lix Mn0.5 Fe0.5 PO4 /C. Compared with a low C-rate (C/4), inter-
phase (Lx MFP) is generated at a higher C-rate (5C).[67]

can be attributed to using ex situ characterization techniques to the discharge process up to x≤0.5. Interestingly, analysis of the
investigate chemical lithiation in the former, without considering variation in the fractions of Fe and Mn valence states during dis-
the discharge rate, while the latter employed in situ character- charge revealed nearly equal contributions of the Fe2+ /Fe3+ and
ization techniques for the study of electrochemical delithiation. Mn2+ /Mn3+ reactions to the total capacity.[67] However, the volt-
The differences in the timeliness of the characterization methods age profile shows no plateau corresponding to the Mn2+ /Mn3+
and reaction rate are significant factors that can lead to divergent reaction. Therefore, at a high charge/discharge rate, the mate-
conclusions. Furthermore, discrepancies stemming from varia- rial may predominantly exhibit the phase transition behavior of
tions in battery design, testing conditions, and methodologies the Fe2+ /Fe3+ reaction. Typically, the voltage plateau corresponds
employed during electrochemical analysis also contribute to the to a phase transition mechanism, but for the Fe2+ /Fe3+ reaction,
disparate outcomes observed.[48] the voltage plateau corresponds to a solid-solution mechanism,
The structure transition mechanism of LMFP at different which is commonly observed in most studies. This behavior is
charge/discharge rates are similar. Ravnsbæk et al. compared likely related to the localized electronic structure of LMFP.
the structural changes of LiMn0.2 Fe0.8 PO 4 during lithium in- Although the available reports are limited, the existing re-
sertion/extraction at different rates. In the first lithium extrac- search findings suggest that charge/discharge rates do influence
tion process, a first-order phase transition of LMFP→Lx MFP the structure transition pathway of LMFP materials. However,
and Lx MFP→MFP was observed at 1C, while an extended solid- unlike LFP, LMFP does not appear to exhibit a significant rate-
solution behavior is observed in the intermediate phase Lx MFP. dependence. The main reason may be that during the conven-
During lithium insertion at 1C, similar structure transition be- tional low-rate delithiation/lithiation of LMFP, a metastable in-
havior as C/10 is observed: MFP→Lx MFP followed a phase tran- termediate phase is already involved in the structure transition.
sition mechanism (although the specific value of x was not ex- Therefore, even at high charge/discharge rates, the behavior of
plicitly mentioned), and the solid solution composition evolved the metastable solid solution phase may not exhibit significant
from Lx MFP to LMFP.[52] Shih et al. performed in situ syn- changes. In other words, it is also possible that the Mn2+ /Mn3+
chrotron XRD analysis on Lix Mn0.25 Fe0.75 PO at C/20 and C/2, re- reaction kinetics is poor at high rates, where Li+ is unable to fully
vealing similar structure transition at both rates, but asymmet- extract/insert, resulting in the material exhibiting only the struc-
ric structure transition behaviors during lithium extraction and ture transition behavior of the Fe2+ /Fe3+ reaction. Nonetheless,
insertion.[65] the precise underlying reasons for this phenomenon necessitate
High charge/discharge rates can lead to the formation further data to provide a comprehensive explanation.
of an intermediate phase, Lx MFP. Meethong et al. investi-
gated the structural evolution of Lix Mn0.5 Fe0.5 PO4 /C during
delithiation/lithiation processes using in situ XAS and in situ 3.3.4. Particle Size and Antisite Defects
wide-angle X-ray scattering (WAXS).[67] Unlike other litera-
ture, the initial phase of Lix Mn0.5 Fe0.5 PO4 /C in this study is In general, as the particle size of the active material decreases, the
Li0.78 Mn0.5 Fe0.5 PO4 /C. As can be seen from Figure 14, during the Li+ diffusion path becomes shorter, the miscibility gap becomes
charge process at C/4, Lix Mn0.5 Fe0.5 PO4 /C exhibits two single- smaller, and the strain at the phase interfaces decreases, which
phase regions (0–0.1 and 0.3–0.78), with a narrow two-phase favors the formation of a single-phase region.[37] Consequently,
region (0.1–0.3). This contrasts with other studies where the this reduction in particle size contributes to accelerated Li+ dif-
single-phase region often occurs in the intermediate state of the fusion kinetics. For olivine-type cathode materials where Li+ only
charge/discharge processes. This discrepancy may be attributed diffuses along 1D channel.[80] Nanoscale particles not only signif-
to the initial lithium content in LMFP. The structure transition icantly enhance the apparent electrochemical reaction rate but
behavior during the discharge process at C/4 is similar to that also alter the structure transition behavior during electrochem-
during the charge process, but the range of the MFP phase is ical reaction. A pertinent example can be found in LFP which
noticeably reduced. However, an intermediate phase Lx MFP is frequently exhibits enhanced electrochemical performance when
formed during the transition from MFP to LMFP at 5C. Due engineered as nanoscale particles.[80] Furthermore, when the par-
to severe polarization at high rate, the literature only reported ticle size dwindles to dimensions smaller than 10 nm, the crystal

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Figure 15. Effect of particle size on the structure transition mechanism of LMFP during delithiation/ lithiation: a) Smaller particle size has a larger
metastable solid solution region. b) The two-phase ranges of Fe2+ /Fe3+ reaction increased with the increase of particle sizes during delithiation, which
is similar to the structure transition mechanism of LFP, while all of these are similar single-phase solid solution reaction during lithiation. c) Li-Fe/Mn
antisite defects: metal cations block Li+ diffusion channels and prevent the normal diffusion of Li+ , indirectly affecting the crystal structure transition.

structure transition during delithiation is primarily driven by a Therefore, it can be inferred that particle size may not exert a sub-
solid solution mechanism.[29b] stantial influence on the asymmetric structural transition behav-
The impact of particle size on the structure transition be- ior experienced during delithiation/lithiation processes. While
havior of LMFP has been a relatively understudied area. In most studies have reported the significant asymmetry in LMFP
2014, Ravnsbæk et al. conducted in situ synchrotron XRD crystal structure transition during delithiation/lithiation, the pre-
study on Lix Mn0.4 Fe0.6 PO4 with different particle sizes (52, 106, cise underlying causes remain subjects that warrant comprehen-
and 152 nm) during delithiation/lithiation processes.[11a] As ex- sive investigation and explanation.
pected, similar to the structure transition behavior of LFP, it was The presence of antisite defects in LMFP leads to poor elec-
observed that the lattice mismatch between the two phases in- trochemical performance, which may be related to the crystal
creases with increasing particle size. The range of metastable structure transition. LMFP exhibits pronounced anisotropy, espe-
intermediate Lx MFP narrowed (0.59≤x≤0.76 and 0.56≤x≤0.74) cially in terms of Li+ diffusion pathway, which are 1D. The Li─M
for larger particle sizes (106, 152 nm), while the smaller particle (M═Mn, Fe) antisite defects easily block the Li+ diffusion path-
size (52 nm) exhibits a broader range of Lx MFP (0.27≤x≤0.78) way (Figure 15c), reducing Li+ diffusion kinetics and even the uti-
during delithiation process. The difference is that the metastable lization of the material.[81] Therefore, antisite defects exert a sub-
intermediate gradually expands to the Mn2+ /Mn3+ reaction re- stantial influence on the local chemical environment and Li+ dif-
gion as the particles become smaller, as shown in Figure 15a. fusion rates,[31,71,82] resulting in different delithiation/lithiation
Furthermore, the metastable region during delithiation for the behaviors. Thus, the concentration of antisite defects is essential
smaller particle size (52 nm) is broader (0.30≤x≤0.94) compared for investigating similarities and differences in structure transi-
to the lithiation process; the metastable region expands to almost tion behavior. A previous study has demonstrated the presence
the entire Fe reaction region. Additionally, compared to the end- of Li+ - Fe2+ antisite by neutron diffraction (ND), and it has been
members MFP and LMFP, the stability of the intermediate phase shown that a direct correlation exists between the extent of the
Lx MFP increased with decreasing particle size, which favored a single-phase reaction region in LiFe0.5−x Mn0.5−x PO4−𝜎 . and the
reduction in the miscibility gap. Further analysis of the structure concentration of antisite defects. In essence, a higher concentra-
transition range revealed that although the initial Li content dif- tion of antisite defects corresponds to a broader region of single-
fered for LMFP samples of different particle sizes, as shown in phase reaction.[83] Further emphasizing the notable impact of
Figure 15b, observing the structure transition within the range these defects on the material’s structure transition behavior.
of the Fe2+ /Fe3+ reaction. It is found that larger particle sizes The synthesis method, process conditions, and Mn con-
corresponded to a more extensive range of the Fe2+ /Fe3+ two- tent significantly affect antisite defects. For mesoporous
phase reaction during delithiation process, exhibiting some sim- LiMn1−x Fex PO4 synthesized by the sol-gel, an increase in
ilarity to the structure transition of LFP. However, all three par- Mn content leads to a higher concentration of Li.─Mn antisite
ticle sizes of LMFP show more significant single-phase regions defect and a decrease in electrochemical performance.[11b] For
during delithiation than lithiation, indicating a continuous solid LiMn1−x Fex PO4 synthesized by hydrothermal, Li─Fe antisite
solution transition from Lx MFP to LMFP, significantly reducing defect is predominantly present, and the defect concentration
the mismatch strain during the Lx MFP to LMFP phase transition. depends on the synthesis time and material crystallinity.[84]

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Che et al. confirmed the Li─Fe antisite defect in LiFe0.5 Mn0.5 PO4 pact on various properties such as structural stability, ion diffu-
synthesized by hydrothermal through atomic-level HAADF- sion, electronic conductivity, phase transitions, and open-circuit
EELS, which results in lower electrochemical performance.[73] voltage.[47a] The Mn and Fe K-edge spectra often exhibit pre-edge
Furthermore, Mn doping “locks” the Li─Fe antisite defect, and peaks that result from the 1s → 3d transition and provide insights
even with an extended synthesis time, a significant reduction in into distortions of the crystal structure’s oxygen octahedra.[85] The
antisite defect cannot be achieved.[73] intensity of the pre-edge peaks reflects the number of vacancies
Indeed, existing reports often show variations in the electro- in the 3d orbitals.[79] These pre-edge peaks at the O K-edge re-
chemical performance of LMFP samples prepared by different veal the hybridization between the O 2p orbital and Fe 3d orbital,
synthesis methods, a comprehensive and systematic mechanism and their intensity serves as an indicator of the number of va-
study remains to be conducted. Considering the impact of syn- cant O 2p orbitals.[86] Furthermore, Fourier transforming the EX-
thesis methods and processes on material compositional unifor- AFS spectra yields valuable information about changes in M─O,
mity, factors such as compositional uniformity, concentrations M─P, M─M bonds (where M═Mn, Fe), offering deeper insights
of antisite defects, particle sizes, and crystallinity are intricately into the structural changes occurring during the electrochemical
linked to these variations, these differences in electrochemical processes of LMFP materials.
performance may be attributed to variations in structure tran-
sition behaviors. Therefore, a comprehensive understanding of
how these structural aspects impact the electrochemical response 4.1. Interaction of Mn2+ ↔Mn3+ and Fe2+ ↔Fe3+
of the material is therefore crucial for the optimization of mate-
rial synthesis processes. The Mössbauer spectra analysis provides valuable insights into
the chemical environment surrounding Fe in LMFP, especially
4. The Electronic Structure Variation of LMFP in relation to the influence of Mn content and the oxidation pro-
during Charge/Discharge cess of Mn2+ . Perea et al. conducted operando Mössbauer spectra
analysis on Lix Mny Fe1−y PO4 /C synthesized by solid-state and re-
The electronic structure variations within LMFP during delithia- ported the relationship between Mössbauer spectra parameters
tion and lithiation processes play a pivotal role in driving the ob- and Mn content in LMFP, as shown in Figure 16a.[64,66] Specifi-
served structure transition behavior. Significant differences exist cally, the Is increases from 1.233 to 1.240 as Mn content increases
in the electronic energy and structure around Mn and Fe. In the- from 0 to 0.75. This is because the substitution of Fe2+ (r = 0.78 Å)
ory, the oxidation/reduction reactions of Mn and Fe can influence by Mn2+ (r = 0.83 Å) increases the average distance of Fe─O
the electronic energy of neighboring Mn and Fe ions. Therefore, bonds, as the length of iron-ligand bonds has some influence
the distribution uniformity of Mn and Fe affects the electronic on the Is.[87] On the other hand, the Qs decreases from 2.96 to
structure changes in the material. A more homogeneous distri- 2.942 as Mn content increases from 0 to 0.75, which is consis-
bution of Mn and Fe promotes stronger and more pronounced tent with the Mössbauer spectroscopy results of Yamada et al.[88]
mutual electronic structure effects during the redox reactions. and Kosova et al.[89] For fully delithiated MFP, the Qs increases
Investigating the electronic structure changes in LMFP materials with increasing Mn content (Figure 16a). It can be observed that
allow for determining the proportion of Mn and Fe ions under- the impact of Mn content on the local chemical environment of
going oxidation/reduction reactions and enables qualitative and Fe is observed not only in the fully lithiated phases but also in
quantitative analysis of the mutual interactions between Mn and the fully delithiated phases. This highlights the significant role
Fe. that Mn plays in shaping the chemical and structural properties
Mössbauer spectroscopy and XAS are powerful techniques of LMFP throughout the charge and discharge processes.
commonly employed to characterize the electronic structure and In the operando Mössbauer spectra analysis of
chemical environment changes within LMFP during the delithi- Li1−x Mn0.5 Fe0.5 PO4 /C synthesized by solvothermal, as shown
ation and lithiation processes. Mössbauer spectroscopy involves in Figure 16b, it is found that the Qs value of Fe3+ gradually
the outer electron structure of Fe nuclei and is sensitive to the increases with lithium removal, but also shows a continuous
chemical environment surrounding the nucleus. It utilizes the increase in the whole Mn2+ /Mn3+ reaction region (0.5 ≤ x
hyperfine interactions between the nucleus and its surround- ≤ 1, shaded area of the figure, where Fe2+ has been wholly
ings to analyze atomic valence states, the ionicity and coordina- oxidized to Fe3+ ).[76] Although it has been mentioned that the
tion number of chemical bonds, crystal structure, electron den- Mn2+ /Mn3+ reaction occurs partially in the Fe2+ /Fe3+ reaction
sity, and magnetic properties. The main hyperfine interactions region,[30a] while a small amount of Fe2+ /Fe3+ reaction also
include the isomer shift (Is), quadrupole splitting (Qs), and mag- appears in the Mn2+ /Mn3+ reaction region.[86] However, in
netic hyperfine splitting. In LMFP materials, typically, only Is and combination with the XANES characterization of the Mn and
Qs are observed. Compared to XAS, Mössbauer spectra can pro- Fe K-edges, it can be seen that the redox reactions of Fe2+ /Fe3+
vide information about the local chemical environment of Fe3+ and Mn2+ /Mn3+ of LMFP samples synthesized by solvothermal
through the Qs variations when Mn2+ undergoes oxidation. occurred at two voltage plateaus and remained highly reversible.
XAS encompasses different energy regimes, including hard This excludes the possibility that Fe2+ continues to be oxidized
XAS, tender XAS and soft XAS, along with its components, which in the Mn2+ /Mn3+ reaction region, causing an increase in the
consist of X-ray absorption near-edge structure (XANES) and ex- Qs value. Therefore, the continuous increase in the Qs value
tended X-ray absorption fine structure (EXAFS). In battery ma- of Fe3+ in the Mn2+ /Mn3+ reaction region may be since the
terials research, XAS plays a critical role in probing the elec- Mn3+ -induced Jahn-Teller distortion reduces the symmetry of
tronic states near the Fermi level, which have a fundamental im- its neighboring Fe-O octahedra.[90] From this point of view, the

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Figure 16. a) Qs (Quadrupole splitting) value in Mössbauer spectra measured for LiMny Fe1−y PO4 and Mny Fe1−y PO4 , the data Mny Fe1−y PO4 is not con-
nected by solid line because it includes non-olivine phase, which is observed by spectroscopy but not by XRD. Is (Isomer shift) value for LiMny Fe1−y PO4
(bule line).[64,66] b) Qs value of Fe3+ obtained from the whole electrochemical process (top) changes continuously even at Mn2+ /Mn3+ reaction region;
the corresponding average oxidation state of Fe and Mn during delithiation/lithiation processes (bottom).[76]

correlation between the chemical environment changes of Fe3+ XANES analysis on LiMn0.25 Fe0.75 PO4 synthesized by the solid-
and the presence of Mn3+ provides a way to indirectly evaluate state.[91] They observed slight shifts in the Fe K-edge during the
the uniformity of Fe and Mn distribution within the LMFP Mn2+ /Mn3+ reaction region and similar subtle changes in the
materials. Mn K-edge during the Fe2+ /Fe3+ reaction region, as shown in
Operando Mössbauer spectroscopy analysis of LMFP materi- Figure 17a,b. By performing Fourier transform (FT) on the EX-
als with Mn/Fe ratios of 0.75:0.25[66] and 0.25:0.75[64] during the AFS data, as shown in Figure 17c,d, it was observed that the
delithiation process consistently showed an increasing Qs of Fe3+ peaks corresponding to Fe─O coordination shells exhibit a lin-
in the Mn2+ /Mn3+ reaction range, indicating that the local sym- ear change in the Fe2+ /Fe3+ reaction region. At the same time,
metry of Fe3+ is highly sensitive to changes in the Mn oxidation the shift in trend reversed in the Mn2+ /Mn3+ reaction region,
state. clearly indicating the influence of Mn on the local chemical en-
XAS analysis reveals the mutual influence of Fe and Mn vironment of Fe. The Mn─O coordination shells showed more
chemical environments. Stievano et al. conducted operando significant changes in the high-voltage region, attributed to the

Figure 17. Energy shift of Fe and Mn K-edges during delithiation: a) The white line peak intensity of Fe K-edge decreases gradually in the Fe2+ /Fe3+
reaction region, and the absorption edge moves toward the higher energy direction. In the Mn2 /Mn3+ reaction region, the absorption edge still moves
toward the high energy direction, but the white line peak intensity increases slightly. b) Mn K-edge is still slightly affected by the Fe2+ /Fe3+ reaction.
c,d) Fourier Transform EXAFS(FT-EXAFS) of Fe and Mn: the peak intensity of M─O (M═Fe, Mn) changes continuously during delithiation.[91].

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Figure 18. Jahn-Teller effect. The elongation or shortening of the Mn─O band will affect the electron configuration around the atoms and the stability of
the crystal structure, lead to a significant distortion in cell volume and increase the dynamic barrier, hinder the normal insert and migration of Li+ along
the b axis.

Jahn-Teller effect of Mn3+ . Even in the low-voltage region of the ics. Although there are few studies in this aspects, drawing in-
Fe2+ /Fe3+ reaction, although the changes in the Mn─O coordina- sights from studies on mitigating the Jahn-Teller effect in other
tion shells are not noticeable, they are still visible. Further analy- Mn-based cathode materials could prove valuable for optimizing
sis using principal component analysis (PCA) and multivariate LMFP’s structural stability and electrochemical behavior, such as
curve resolution-alternating least squares (MCR-ALS) revealed doping to modulate the electronic structure surrounding Mn[96]
that in the low-voltage region, although the Mn─O bond length and improving synthesis methods to control the size and propor-
remains unchanged, the Debye-Waller factors increases, indicat- tion of Mn/Fe-enriched regions.[97]
ing increased Mn─O octahedral distortion induced by Fe3+ . Sim-
ilarly, in the high-voltage region, where the Fe2+ /Fe3+ reaction is
theoretically complete, it is observed that although the Fe─O oc- 4.2. Incomplete Redox of Mn2+ /Mn3+ and Fe2+ /Fe3+
tahedra hardly changed, the lengths of Fe─P and Fe─M (M═Fe
or Mn) coordination bonds, as well as the Debye-Waller factors Fe2+ /Fe3+ and Mn2+ /Mn3+ are completely oxidized/reduced in
decreases continuously, indicating an improvement in the struc- the chemical lithium insertion/extraction process. Yamada et al.
tural order of the material. This study effectively demonstrates conducted ex situ XANES analysis of LiMn0.6 Fe0.4 PO4 after chem-
the value of utilizing XAS techniques to gain multiple perspec- ical delithiation, investigating the Fe and Mn K-edges changes
tives on the mutual influence of Fe and Mn chemical environ- during the chemical lithiation process.[79] By comparing the ab-
ments. However, in most XANES analyses, the chemical shifts sorption edges and pre-edge peaks, the analysis revealed that
in the Fe K-edge during the Mn2+ /Mn3+ reaction region and the during the lithiation process, when the Li+ content x is in the
Mn K-edge during the Fe2+ /Fe3+ reaction region are very weak, range of 0 ≤ x ≤ 0.6 (4.1 V), the Mn K-edge continuously shifts
allowing only simple analysis of the changes in Fe and Mn va- toward lower energy and the change of the pre-edge peak is
lence states, which may overlook the interaction of Fe and Mn consistent with the main peak, indicating a reduction reaction
chemical environments during delithiation/lithiation processes. from Mn3+ to Mn2+ within this range. However, the Fe K-edge
Jahn-Teller distortion is also one of the essential reasons for shows almost no change. Similarly, when 0.6 ≤ x ≤ 1 (3.5 V),
electronic structure changes. As mentioned in numerous stud- the Mn and Fe K-edges changes are opposite to the first stage,
ies, Mn3+ with a 3d4 configuration typically exhibits a high- indicating that the primary reaction during this stage is the re-
spin state and asymmetric electron occupation in the eg orbital, duction of Fe3+ to Fe2+ .[79] In theory, the oxidation/reduction re-
leading to Jahn-Teller distortion of the crystal structure.[92] As actions of Fe2+ /Fe3+ and Mn2+ /Mn3+ occur at their respective
shown in Figure 18, the distortion results in an unpaired elec- voltage plateaus. Therefore, in the case of chemical lithiation,
tron occupying the Mn-3d z2 orbital or (x2 -y2 ) orbital, causing the study demonstrated that the oxidation/reduction of Fe2+ /Fe3+
elongation[56b,93] or compression[94] of the MnO6 octahedra. The and Mn2+ /Mn3+ is complete, suggesting that the chemical shifts
Jahn-Teller distortion triggered by Mn3+ is one of the main rea- in the Fe and Mn K-edges approximated the ideal case.
sons for local electron structure changes in Fe3+ , and it also The observation of incomplete oxidation/reduction reac-
deforms the Li+ migration channels, reducing the Li+ migra- tions of Mn2+ /Mn3+ during electrochemical lithium inser-
tion rate and increasing the kinetic barrier for interfacial dif- tion/extraction processes highlights the importance of reaction
fusion at the two-phase boundary.[95] Consequently, the power kinetics and rate-dependent behaviors in LMFP. The slower ki-
performance of LMFP is lower than that of LFP material.[56a] netics of the Mn2+ ↔ Mn3+ reaction compared to the Fe2+
Alleviating the Jahn-Teller effect in LMFP can significantly en- ↔ Fe3+ reaction can lead to differences in the extent of oxi-
hance the structural stability and electrochemical reaction kinet- dation/reduction for these two redox couples. In the case of

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Figure 19. a) Fe and Mn K-edges XAS spectra of LiFe0.4 Mn0.6 PO4 /C recorded during the first charge: the Fe, Mn edge shifts showed that Fe is active
during the whole charge process while oxidation of Mn set in later. b) Electrochemical cycling curve and points at 57 Fe Mössbauer. c) 57 Fe Mössbauer
spectra of LiFe0.4 Mn0.6 PO4 /C at different SOC, Fe2+ and Fe3+ spectra are given as blue and red doublets, respectively. Fe2+ can be observed at 4.25 V
from the C point of 57 Fe Mössbauer spectra. Reproduced with permission.[100] Copyright 2015, American Chemical Society.

LiMn0.6 Fe0.4 PO4 /C synthesized by solid-state, the in situ XANES ↔ Fe3+ reaction is highly reversible. Although an irreversible
spectra revealed that the oxidation reactions of Fe2+ and Mn2+ oc- change in the Fe K-edge is observed in the in situ XAS after
cur at different rates, with Fe2+ oxidation much faster than Mn2+ . the first charge/discharge cycle, as shown in Figure 19a, the
This disparity in reaction rates results in incomplete oxidation of Mössbauer spectra are completely reversible during the initial
Mn2+ even at the end of charge, whereas Fe2+ is fully oxidized.[98] charge/discharge.[100] Therefore, the authors attributed the irre-
In situ synchrotron XANES measurements were performed on versible change in the Fe K-edge to the chemical environment
LiMn0.25 Fe0.75 PO4 /C at different discharge rates.[99] The results variation caused by local electronic structure changes rather than
showed that the Mn and Fe K-edges change at a low rate (C/20) a change in the oxidation state of the elements. Thus, relying
are consistent with the analysis by Yamada et al. , [79] with chem- solely on XAS or Mössbauer spectra may not provide a compre-
ical shifts observed only within their respective reaction regions hensive understanding of the changes in the oxidation state or
(0 ≤ x ≤ 0.25 (4.0 V), 0.25 ≤ x ≤ 1 (3.5 V)). However, at a high rate chemical environment of the elements. In contrast to the Fe K-
(C/5), slight differences were observed in the changes of the Mn edge, the Mn K-edge only shifts at the 4.0 V, and the reactivity
K-edge. Specifically, when x = 0.15, no further shift toward lower of the Mn2+ ↔ Mn3+ reaction (sensitivity of the spectral signal
energy is observed, indicating that Mn2+ /Mn3+ did not fully par- to the SOC) is significantly lower compared to the Fe2+ ↔Fe3+ re-
ticipate in the oxidation/reduction reactions at a higher discharge action (Figure 19a). Additionally, the partial oxidation of Mn2+
rate. Additionally, a shift in the Fe K-edge is observed starting at is supported by in situ XRD results showing the persistence of
x = 0.23, and for x ≥ 0.25, the behavior of the Fe K-edge changes the intermediate phase Lix Mn0.6 Fe0.4 PO4 at the end of charge.[100]
is similar to that observed at low discharge rate, suggesting that However, the LiMn0.6 Fe0.4 PO4 /C sample in the literature did not
the oxidation/reduction reactions of Fe2+ /Fe3+ appear less influ- reach its theoretical capacity, suggesting the possibility of active
enced by the discharge rate. particles deactivation.
For LiMn0.6 Fe0.4 PO4 /C synthesized by the sol-gel, in situ XAS The investigation of electronic structure changes and charge
indicated that the Fe K-edge shifts toward higher energy through- compensation mechanisms in cathode materials is crucial for un-
out the entire process (Figure 19a), and there are still symmetrical derstanding their electrochemical behavior. Horiba et al. inves-
double peaks of Fe2+ above the 4.0 V (point C in Figure 19b,c), tigated the electronic structure changes of Lix Mn0.5 Fe0.5 PO4 /C
indicating that the oxidation reaction of Fe2+ to Fe3+ occur- using XAS and resonant photoelectron spectroscopy (PES).[101]
ring throughout the delithiation process. Additionally, as demon- XAS testing of the Fe L-edge showed that the Fe2+ oxidation re-
strated by points A and F in Figure 19b, the symmetric dou- action continuously occurs during lithium extraction within the
ble peaks of Fe2+ remain unchanged, indicating that the Fe2+ Li+ content range of 0.5 to 1. Furthermore, a comparison of the

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Figure 20. XAS at the Mn L-edge on Lix MnPO4 a), Lix Mn0.9 Fe0.1 PO4 b) and Lix MnPO4 , compared with MnO, LiMnO2 , MnO2 c), the Fe L-edge on
Lix Mn0.9 Fe0.1 PO4 d), O K-edge on Lix MnPO4 e) and Lix Mn0.9 Fe0.1 PO4 (f) with different SOC (x-value): Mn2+ is hardly redox, while Fe and O participate
in the charge compensation throughout the delithiation process. Reproduced with permission.[86] Copyright 2015, Royal Society of Chemistry.

PES analysis between Lix Mn0.5 Fe0.5 PO4 /C and Lix FePO4 revealed the intensity of the characteristic peaks at 529.5 and 531 eV in
that the spectral lines are almost identical, indicating that the LiMn0.9 Fe0.1 PO4 is significantly stronger than that in LiMnPO4 .
partial substitution of Mn for Fe does not affect the electronic As the lithiation process, the intensity of the two peaks gradu-
structure of Fe 3d orbital, indicating robust localization of Fe 3d ally decreases, suggesting the entry of electrons into the O 2p
state in the Lix Mn0.5 Fe0.5 PO4 /C system. However, in the XAS and orbital, causing the loss of intensity in the two peaks. Therefore,
PES analysis of the Mn L-edge, the Mn 3d state remained nearly compared to Lix MnPO4 , a more significant proportion of charge
unchanged throughout the charging process, and a significant compensation occurs at the Fe and O sites in LiMn0.9 Fe0.1 PO4 .
amount of Mn2+ still existed after charging. It is therefore spec- For LiMn0.6 Fe0.4 PO4 nanowire material, the involvement of
ulated that, in the Mn2+ /Mn3+ reaction region, a small portion oxygen in charge compensation has also been observed.[102] Dur-
of the electrons are provided by Mn2+ , while the majority may be ing lithiation, samples with different SOC were subjected to XAS
supplied by polyanions (although this assumption is not proven measurement in total fluorescence yield (TFY) and TEY modes
in the study). (with probing depths of TEY and TFY ≈<3 and <100 nm, respec-
In another study on Mn-rich LiMn0.9 Fe0.1 PO4 material, XAS tively). The peak shapes obtained from both measurement modes
was employed to analyze the Fe and Mn L-edges and O K-edge in are similar, indicating that the Fe2+ /Fe3+ redox reaction occurred
the total electron yield (TEY) mode.[86] It was found that through- uniformly in bulk, at the surface, and only at low voltage regions.
out the lithium extraction process, the Mn L-edge exhibits sim- However, at 2.8 V, 33% of the Fe site still remained as Fe3+ .[102]
ilar characteristic peaks to those of Lix MnPO4 , while the spec- The incomplete reduction behavior of Fe2+ /Fe3+ is not explained
tral features of LiMnPO4 and Li0.2 MnPO4 are almost identical to in the literature. In contrast, the actual discharge-specific capacity
MnO (Mn2+ ), as shown in Figure 20a–c. Therefore, it was specu- of the material was only 98 mAh g−1 , which is much lower than
lated that the primary charge compensation in Lix Mn0.9 Fe0.1 PO4 the theoretical capacity. Therefore, it is highly likely that a por-
occurs at the Fe and O sites. Because Fe2+ still accounted for tion of the particles became deactivated during the electrochem-
60% of the total Fe content at x = 0.9, and particularly in the ical reaction and remained in a discharged or charged state, no
range of 0.4 ≤x≤0.6, the valence state of Fe changes rapidly, with longer participating in the lithiation/delithiation process, result-
the characteristic peak of Fe3+ becoming most pronounced at ing in a non-uniform reaction. Similarly, analysis of Mn L-edge
x = 0.2, as shown in Figure 20d. However, at the end of dis- in TFY and TEY modes revealed that the electronic structure of
charge, Fe3+ was still not fully reduced to Fe2+ . Furthermore, as Mn 3d remained almost unchanged between the surface and bulk
shown in Figure 20e,f, the analysis of the O K-edge indicated that throughout the delithiation process, indicating that Mn2+ hardly

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Figure 21. Schematic diagram of LMFP delithiation/lithiation mechanism. Region I, the single-phase or two-phase region of Fe2+ /Fe3+ redox (m≤x≤1);
Region II, a single-phase region, where significant interaction between the Fe2+ /Fe3+ and Mn2+ /Mn3+ reactions (n≤x≤m); Region III, the two-phase or
single-phase region of Mn2+ /Mn3+ redox (0≤x≤n). From the third quadrant to the first quadrant (light blue arrow direction), it is the dilithiation process
of LMFP→Lx MFP→MFP, where Mn2+ and Mn3+ coexist in Lx MFP at the end of the charge due to the hysteresis kinetics of Mn2+/ Mn3+ reaction.

participated in the oxidation reaction, the 4.0 V voltage plateau by in situ/operando XRD. By comparing the results with other
could not be attributed to the Mn2+ /Mn3+ oxidation/reduction. in situ/operando characterizations and analyzing various factors
By analyzing the pre-edge peaks of O K-edge and combining that influence the phase transition pathways in electrochemical
them with configuration-interaction full-multiplet calculations delithiation/lithiation processes, discrepancies in reported mech-
and FTIR spectroscopy, it is found that the 4.0 V voltage plateau anisms are explained, and suggestions for systematic research
could be attributed to the electron gain/loss in O 2p orbital with on LMFP’s phase transition mechanism are proposed. Regarding
a strong charge transfer effect.[102] the electronic structure changes, existing studies suggest signif-
It should be noted that the presence of deactivated particles icant interactions between Fe and Mn ions, and the sluggish ki-
and the potential interference they may cause in the analysis of netics of the Mn2+ /Mn3 reaction is mainly attributed to the Jahn-
element charge states and chemical environments can compli- Teller effect. Additionally, it is proposed that some oxygen ions
cate the interpretation of experimental results. However, the in- may participate in charge compensation.
formation on electrochemical performance provided in the above The delithiation/lithiation mechanism of LMFP can be sum-
literature is insufficient for quantitatively determining the con- marized as shown in Figure 21. Region I (m≤x≤1) corresponds
tributions of the Fe2+ /Fe3+ and Mn2+ /Mn3+ reactions to the ca- to the Fe2+ /Fe3+ reaction, which can exhibit either a pure solid
pacity. Therefore, discussions regarding the extent of the reac- solution mechanism or a sequential occurrence of phase tran-
tions and polyanion charge compensation may lack rigor. Fur- sition mechanism and solid solution mechanism depending
thermore, the voltage plateaus provided by all the aforemen- on the Fe content. Compared to the Mn2+ /Mn3+ reaction, the
tioned polyanionic reactions align with the voltage plateau of the Fe2+ /Fe3+ reaction has a higher proportion in the single-phase re-
Mn2+ /Mn3+ reaction remains unexplained. Understandably, the gion. Region II (n≤x≤m) represents a solid solution mechanism,
Mn2+ /Mn3+ redox reaction in LMFP during electrochemical lithi- where significant interactions occur between the Fe2+ /Fe3+ and
ation/delithiation is incomplete due to sluggish kinetics. How- Mn2+ /Mn3+ reactions. Region III (0≤x≤n) corresponds to the
ever, some unexpected phenomena, such as polyanion participa- pure Mn2+ /Mn3+ reaction, primarily in the two-phase region, but
tion in charge compensation and the occurrence of the Fe2+ /Fe3+ there is also a possibility of a single-phase region when the Mn
reaction at Mn2+ /Mn3+ voltage platform, require further inves- content is very low. Most studies indicated that the Mn2+ /Mn3+
tigation and explanation, despite the characterization data pro- reaction follows a phase transition mechanism, even when the
vided in the article. Fe content exceeds that of Mn. However, individual studies have
reported that LMFP even exhibits a complete solid solution mech-
5. Conclusion and Perspectives anism with equal Mn and Fe contents. This could be attributed to
the uniform distribution of Mn and Fe in the crystal, leading to
LMFP holds promise as a cathode material for LIBs, and under- continuous interaction between the Fe2+ /Fe3+ and Mn2+ /Mn3+
standing its complex delithiation/lithiation mechanism is cru- reactions. Under similar conditions of particle size, rate, etc., the
cial for optimizing its electrochemical performance. In terms specific ranges of the three regions are primarily influenced by
of crystal structure transition, this article provides an overview the Mn/Fe ratio and the distribution of Mn and Fe in the crystal.
of the common mechanism and influencing factors of crystal Additionally, the yellow dashed line with a red diagonal short line
structure transition in LMFP during delithiation/lithiation pro- indicates a certain degree of irreversibility for the Mn2+ /Mn3+ re-
cess. It points out that the crystal structure transition in LMFP action. On the other hand, from the third quadrant to the first
exhibit significant relaxation property and thus emphasizes the quadrant (light blue arrow direction), it is the dilithiation pro-
need for the structure transition mechanism to be characterized cess of LMFP→Lx MFP→MFP, where Mn2+ and Mn3+ coexist in

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Lx MFP at the end of the charge due to the hysteresis kinetics of We believe this review can provide new insights into the
Mn2+ /Mn3+ reaction. delithiation/lithiation mechanism of LMFP and offer potential
In most studies, it cannot be guaranteed that LMFP samples guidance for producing and developing future olivine-type cath-
exhibit a microscopically homogeneous distribution of Fe and ode materials. It aims to stimulate creative design in the research
Mn, as well as synchronous reactions in all particles. XRD and of such materials, which is significant for improving material per-
most spectroscopic analyses are performed on multi-particle sys- formance, extending battery life, and promoting the development
tems, but such compositional and reactive heterogeneity can sig- of high-performance, environmentally friendly, and cost-effective
nificantly interfere with the statistical state and behavior of the LIB cathode materials.
particles, leading to biased conclusions. For instance, if LMFP
particles exhibit a composite structure consisting of multiple mi-
crocrystalline domains, the types, sizes, and spatial homogene- Acknowledgements
ity of these domains would influence the apparent phase tran- The authors would like to show gratitude to the National Natural Science
sition behavior of the LMFP materials. Similarly, through the Foundation of China (No. 22279070 [L.W.] and U21A20170 [X.H.]), and the
analysis of electronic structure changes, the significant varia- Ministry of Science and Technology of China (No. 2019YFA0705703[L.W.]).
tions in the chemical environment of LMFP also depend mainly The authors also would like to thank the “Explorer 100” cluster system of
on the compositional uniformity. If LMFP consists entirely of Tsinghua National Laboratory for Information Science and Technology for
facility support.
a homogeneous solid solution, the mutual interaction between
different ions during the electrochemical cycling process be-
comes more pronounced. Therefore, determining the micro-
Conflict of Interest
scopic structural composition of LMFP is paramount in studying
the crystal structure and electronic structure changes during the The authors declare no conflict of interest.
delithiation/lithiation processes. In addition, it has been argued
that the sluggish dynamics of the Mn2+ /Mn3+ reaction, attributed
to low electronic conductivity, slow Li+ diffusion rate, and Jahn- Keywords
Teller distortion, may result in partial capacity through charge crystal structures, delithiation/lithiation mechanisms, electronic struc-
compensation from other ions during the Mn2+ /Mn3+ reaction tures, LiMny Fe1−y PO4, olivine cathode materials
stage.
Therefore, the studies of LMFP delithiation/lithiation mecha- Received: August 23, 2023
nism are not comprehensive and systematic, and many aspects Revised: October 6, 2023
require attention and further investigation: 1) Regarding the re- Published online: October 20, 2023
laxation property of LMFP during lithium insertion/extraction, it
is crucial to employ advanced in situ characterization techniques
that can more accurately reflect its delithiation/lithiation mecha-
[1] a) I. M. Nwachukwu, A. C. Nwanya, A. B. C. Ekwealor, F. I. Ezema,
nism. The influence of factors such as Mn/Fe ratios and temper-
J. Energy Storage 2022, 54, 105248; b) J. Cabana, L. Monconduit, D.
ature on the relaxation effect should also be considered to com- Larcher, M. R. Palacín, Adv. Energy Mater. 2010, 22, E170.
prehensively account for the factors influencing crystal structure [2] M. R. Palacín, A. De Guibert, Science 2016, 351, 1253292.
transition. 2) Effective characterization methods should be devel- [3] a) J. Cheng, B. Ouyang, K. A. Persson, ACS Energy Lett. 2023, 8, 2401;
oped to assess the compositional uniformity of LMFP at the mi- b) C. Geng, D. Rathore, D. Heino, N. Zhang, I. Hamam, N. Zaker,
croscopic level and the synchronicity of particle reactions. Based G. A. Botton, R. Omessi, N. Phattharasupakun, T. Bond, C. Yang, J.
on this, the synthesis methods can be evaluated and optimized, R. Dahn, Adv. Energy Mater. 2021, 12, 2103067; c) K. Ding, Y. Zhao,
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Shuzhen Li is currently a Ph.D. candidate with Prof. Yong Liu (College of Materials Science and En-
gineering, Beijing University of Chemical Technology, China) and Prof. Xiangming He (Institute of
Nuclear and New Energy Technology, Tsinghua University, China). Her research focuses on synthesis
and (de)lithiation mechanism of lithium manganese iron phosphates for lithium ion batteries.

Hao Zhang is a professor of Beijing Key Lab of Advanced Chemical Energy Storage Materials and Tech-
nology. His research interest includes energy storage materials and machine learning for energy sci-
ence. Dr. Zhang has published more than 110 peer-reviewed research articles.

Yong Liu, head of the Polymeric Nano Composite Lab and faculty at Beijing University of Chemical
Technology. His research focuses on preparing ultrafine nanofibers by electrospinning. He has pub-
lished 180 articles, 5 books and 4 chapters; 66 patents were authorized. Dr. Liu is a member of the
Royal Society of Chemistry, a senior member of the Chinese Society for Composite Materials, a mem-
ber of the American Chemical Society, and a member of the Chinese Chemical Society. The State Coun-
cil awarded him the National Award for Science and Technology Progress for his contribution to poly-
mer materials.

Li Wang is an associate professor at the Institute of Nuclear and New Energy Technology, Tsinghua
University, China. She received his B.S. in 1999 and Ph.D. in analytical chemistry in 2004 from the Ts-
inghua University. Her research expertise includes new electrode material preparation technology,
failure mechanism of lithium-ion battery, safety power-battery technology and fundamental under-
standing of related electrochemical processes.

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www.advancedsciencenews.com www.afm-journal.de

Xiangming He is a professor and the group leader of the Lithium-ion battery Laboratory in the Institute
of Nuclear and New Energy Technology, Tsinghua University. He received his bachelor’s and master’s
degrees from the School of Chemical Engineering and Ph.D. from Institute of Nuclear and New Energy
Technology, Tsinghua University. His research focuses on the design and application of functional ma-
terials for energy storage and conversion and fundamental understanding of related electrochemical
processes.

Adv. Funct. Mater. 2024, 34, 2310057 2310057 (27 of 27) © 2023 Wiley-VCH GmbH