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New O2/P2-type Li-Excess Layered Manganese Oxides
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as Promising Multi-Functional Electrode Materials for
Rechargeable Li/Na Batteries
Naoaki Yabuuchi, Ryo Hara, Masataka Kajiyama, Kei Kubota, Toru Ishigaki,
Akinori Hoshikawa, and Shinichi Komaba*
sustainable energy development. This

A new and promising P2-type layered oxide, Na5/6[Li1/4Mn3/4]O2 is prepared movement necessarily leads to the replace-
using a solid-state method. Detailed crystal structures of the sample are ment of internal combustion engines
with alternative power sources. An energy
analyzed by synchrotron X-ray diffraction combined with high-resolution
storage system based on electrochemical
neutron diffraction. P2-type Na5/6[Li1/4Mn3/4]O2 consists of two MeO2 layers methods, such as rechargeable lithium
with partial in-plane √3a × √3a-type Li/Mn ordering. Na/Li ion-exchange batteries (lithium-ion batteries, LIB),
in a molten salt results in a phase transition accompanied with glide of potentially provides the solution to meet
[Li1/4Mn3/4]O2 layers without the destruction of in-plane cation ordering. these tough challenges. Although LIB
P2-type Na5/6[Li1/4Mn3/4]O2 translates into an O2-type layered structure with technology has become considerably more
sophisticated since its first appearance
staking faults as the result of ion-exchange. Electrode performance of P2-type
as a power source for portable electronic
Na5/6[Li1/4Mn3/4]O2 and O2-type Lix[Li1/4Mn3/4]O2 is examined and compared devices in 1991, demands for further
in Na and Li cells, respectively. Both samples show large reversible capacity, increase in energy density and reduction
ca. 200 mA h g−1, after charge to high voltage regardless of the difference in in material costs are still growing. As
charge carriers. Structural analysis suggests that in-plane structural rear- positive electrode materials for LIB, many
oxide- and phosphate-based materials have
rangements, presumably associated with partial oxygen loss, occur in both
been extensively studied in the past three
samples after charge to a high-voltage region. Such structural activation pro- decades.[1] Recently, lithium-excess man-
cess significantly influences electrode performance of the P2/O2-type phases, ganese layered oxides, Li2MnO3-based
similar to O3-type Li2MnO3-based materials. Crystal structures, phase-tran- materials, have been especially attractive to
sition mechanisms, and the possibility of the P2/O2-type phases as high- researches as high-capacity positive elec-
capacity and long-cycle-life electrode materials with the multi-functionality for trode materials for LIBs.[2–5] Li2MnO3 with
a monoclinic lattice (space group; C2/m)[6]
both rechargeable Li/Na batteries are discussed in detail.
can be reformulated as Li[Li1/3Mn2/3]O2,
which is classified as a slightly distorted
O3-type layered structure by using the
1. Introduction notation proposed by Delmas et al.[7] Based on LiMeO2 layered
structures, lithium ions are substituted for one-third of metal
It is now widely admitted that the substitution of energy ions, forming [Li1/3Mn2/3]O2 layers (slabs) with lithium/manga-
sources for fossil fuels must be considered to achieve nese in-plane cation ordering, and therefore called “Li-excess”
or “Li-rich” layered materials.
Prof. N. Yabuuchi, R. Hara, M. Kajiyama,
For a long time Li2MnO3 was considered to be electrochemi-
Prof. K. Kubota, Prof. S. Komaba cally inactive and was not attracted to researchers as an elec-
Department of Applied Chemistry trode material because it was thought that oxidation of manga-
Tokyo University of Science nese ions beyond a tetravalent state was difficult at octahedral
1–3 Kagurazaka, Shinjuku, Tokyo 162–8601, Japan environment for oxides.[8] However, it has been demonstrated
E-mail: komaba@rs.kagu.tus.ac.jp
that Li2MnO3 is electrochemically active in Li cells.[3,9] Revers-
Prof. N. Yabuuchi, Prof. S. Komaba
Elements Strategy Initiative for Catalysts and Batteries ible capacity of Li2MnO3 reaches ca. 250 mA h g−1 using nano-
Kyoto University sized particles, even though its reversibility is insufficient for
Katsura, Kyoto 615–8520, Japan practical applications.[10] Since Li2MnO3 (Li[Li1/3Mn2/3]O2) and
Prof. T. Ishigaki, Prof. A. Hoshikawa LiMeO2 (Me = Co, Ni, Mn etc.) have the compatibility of crystal
Frontier Research Center for Applied Atomic Sciences structures as layered materials consisting of a CCP lattice
Ibaraki University
Tokai, Ibaraki, Japan
(O3-type phase), the formation of a complete solid solution is
achieved over the entire range between both phases. Although
DOI: 10.1002/aenm.201301453 the cyclability of pure Li2MnO3 is unacceptable for an electrode
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Figure 1. Schematic illustrations of crystal structures for P2-, O2-, and O3-type layered oxides. O2-type layered oxides are prepared from P2-type layered
oxides by ion-exchange. Half of MeO2 layers in the P2-phase glides toward the direction of (2/3, 1/3, z), forming the O2-phase. Na ions are located at
trigonal prismatic sites (P-site) for the P2-phase whereas Li ions are located at octahedral sites (O-site) for the O2- or O3-phase. Li ions (LiO6 octa-
hedra) share a face (denoted as “F”) with metal ions (MeO6 octahedra) for one side after ion-exchange. In contrast, LiO6 octahedra for the O3-phase
(or O3-domains for the O2-phase) share edges (denoted as “E”) with MeO6 octahedra.
material,[10] electrode reversibility is effectively improved by is utilized as “O’3-type” when the crystal lattice has in-plane
the utilization of solid solution phases between Li2MnO3 distortion, such as Li[Li1/3Mn2/3]O2 and LiMnO2 with a mono-
(Li[Li1/3Mn2/3]O2) and LiMeO2.[2,5,11–16] For instance, solid solu- clinic lattice.[30] Although Li ions are similarly accommodated
tion systems of Li2MnO3 (Li[Li1/3Mn2/3]O2) with Li[Ni1/2Mn1/2]O2 at octahedral sites for O3- and O2-phases, local environment on
and Li[Co1/3Ni1/3Mn1/3]O2 show anomalously large reversible LiO6 octahedra is different for both phases. LiO6 octahedra for
capacity of over 250 mA h g−1 with relatively good capacity the O3-phase share only edges with MeO6 octahedra, whereas
retention. The origin of large reversible capacity has been LiO6 octahedra for the O2-phase share edge and face with MeO6
studied and many different reaction mechanisms have been octahedra, as shown in Figure 1. When a certain amount of
proposed by many authors. Although reaction mechanisms of lithium ions are extracted, vacant face-shared tetrahedral sites
Li2MnO3-based electrode materials depend on chemical com- with MnO6 octahedra are formed in the lithium layer. Triva-
position,[5,11] surface coating,[17] particle morphology,[10] cycling lent manganese ions are energetically stabilized at the tetrahe-
conditions[18,19] etc., it has been suggested that charge com- dral sites, resulting in the migration of manganese ions to the
pensation is achieved by oxidation of oxide ions,[16,20] which face-shared tetrahedral sites in the lithium layer, presumably
partly results in the oxygen loss as oxygen molecules (with CO/ accompanied with disproportionation reaction.[31] From layered
CO2 gas)[10,13,17,21] from the crystal lattice on an initial charge to spinel phase transition is completed by further migration of
process. Following partial oxygen loss on charge, the distri- manganese ions from the tetrahedral to vacant and adjacent
bution of cations is re-arranged in the crystal lattice.[13,14,21,22] octahedral sites in the lithium layer. Since vacant octahedral
Meanwhile, originally tetravalent manganese ions in the CCP sites formed in the lithium layer share only edges with MnO6
lattice are partly reduced to a trivalent state on discharge.[13] octahedra for the O3-phase, manganese ions can easily migrate
Although large reversible capacity is achieved with “activated” from tetrahedral to the adjacent octahedral sites. Indeed, the lay-
manganese ions, lowering operating voltage (and change in the ered to spinel phase transition for the O3-phase is the energeti-
voltage profile) during continuous electrochemical cycling is cally favorable process.[31] In contrast to the O3-phase, for the
known to be a disadvantage in electrode materials.[23,24] Such a O2-type phase, such phase transition induced by manganese
failure mode reminds us a phase transition to spinel reported migration is expected to be energetically unfavorable because
in Li-Mn oxides consisting of trivalent manganese ions, such of large repulsive interaction with face-shared manganese ions.
as orthorhombic zigzag-layered LiMnO2[8,25,26] and monoclinic O2-type Li2/3[Li1/6Mn5/6]O2 as a metastable phase was prepared
layered LiMnO2.[4,8,27,28] These Li-Mn oxides are composed of by an ion-exchange method from P2-type Na2/3[Li1/6Mn5/6]O2,
the common CCP oxygen lattice. Therefore, two polymorphs in which Na+ occupies trigonal prismatic sites (Figure 1). Sche-
of LiMnO2 easily transform into spinel as the energetically matic illustrations in Figure 1 were drawn using the program
favorable phase during electrochemical cycles. VESTA.[32] Although O2-type Li2/3[Li1/6Mn5/6]O2 shows relatively
To overcome the phase transition issue of LiMnO2 as an elec- good capacity retention without the phase transition into spinel,
trode material, Paulsen et al. reported a layered Li-Mn oxide, available reversible capacity is smaller than that of O3-type
O2-type Li2/3[Li1/6Mn5/6]O2, with a distinct oxygen lattice from Li2MnO3-based electrode materials. From these pieces of exper-
CCP, which does not convert to spinel.[29] For the description imental evidence, lithium-enriched O2-type manganese-based
of O3-type and O2-type phases, symbols of “O” and “3” or “2” layered materials, ultimately O2-type Li[Li1/3Mn2/3]O2 and/or its
denote the octahedral environment for Li sites between MeO2 solid solution with other O2-type LixMeO2, are expected to be
layers and the minimum number of MeO2 layers needed to a promising candidate for high-capacity manganese-based elec-
describe its unit cell, respectively. Additionally, a prime symbol trode materials without the phase transition issue.
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Here, we describe a new P2-type Li-excess manganese oxide, Time-of-flight neutron diffraction (TOF-ND) measurements
from which a new O2-type Li-excess manganese oxide as a were conducted at iMATERIA,[38] BL20 of Materials and Life
metastable phase is prepared by Na/Li ion-exchange. Detailed Science Experimental Facility (MLF), J-PARC in Japan. The
structural characterization of the samples and electrochemical samples were sealed in vanadium tubes (6.0 mm in diameter)
properties as electrode materials are also provided. Similar in an inert atmosphere. TOF-ND data was collected at room
to the O2-type phase in Li cells, the P2-type Li-excess sample temperature using a high-resolution bank (Δd/d = 0.16%),
used as a precursor is potentially utilized as high-capacity which covers the d-range of 0.18 < d (Å) < 5. The collected data
positive electrode materials in Na cells. Reversible capacity of was analyzed using the program of Z-Rietveld.[39]
the P2-type Li-excess manganese oxide in Na cells reaches ca. Simulation of stacking faults of the samples was performed
200 mA h g−1 with relatively good capacity retention, which is with the DIFFaX program.[40] See the text for detailed conditions
slightly larger reversible capacity compared with that of P2-type for the simulation. Morphological features of the samples were
Na2/3[Fe1/2Mn1/2]O2 as high-capacity positive electrode materials observed using a scanning electron microscope (Carl Zeiss,
reported so far for rechargeable sodium batteries.[33] From these SUPRA40) operated at 15 keV of acceleration voltage. Surface
results, we further discuss similarities and differences between area of the sample was measured by the Brunauer, Emmett,
O2/P2-type Li-excess layered oxides as the multi-functional and Teller (BET) surface area measurement (BEL Japan, Inc.,
electrode material utilized for rechargeable Li/Na batteries. BELSORP-miniII).
2. Experimental Section 2.3. Electrochemical Characterization
2.1. Synthesis of Samples Coin-type cells (R2032-type) were assembled to evaluate the elec-
trode performance of Na5/6[Li1/4Mn3/4]O2 and its ion-exchanged
Na5/6[Li1/4Mn3/4]O2 was prepared by a solid-state reaction of sample. Positive electrodes consisted of 80 wt% active materials,
Na2CO3 (Kanto Chem. Co., Ltd. purity: 99.5%), Li2CO3 (Kanto 10 wt% acetylene black, and 10 wt% poly(vinylidene fluoride),
Chem. Co., Ltd. purity: 99%), and MnCO3 (Kishida Chem. Co., which were mixed with N-methylpyrrolidone and pasted on Al
Ltd., 44% as the Mn content). These starting materials were foil, and then dried at 80 °C in vacuum. Typical mass loading of
mixed using a mortar and pestle, and then pressed into a pellet. the composite electrodes used in this study ranges from 2.0 to
The pellet was heated at 700 °C for 10 h in air. The pellet was 3.5 mg cm−2. Metallic lithium and sodium foil were used as a
taken out from the furnace without a cooling process, and then negative electrode. Electrolyte solution used was 1.0 mol dm−3
immediately transferred into an argon-filled glove box. The LiPF6 dissolved in ethylene carbonate/dimethyl carbonate (1:1
pellet was cooled to room temperature in the glove box and was by volume) (Kishida Chem. Co., Ltd.) for Li cells with polyolefin
kept inside it to avoid the contact with moisture in air. microporous film as a separator, and 1.0 mol dm−3 NaClO4 dis-
A well-characterized Na5/6[Li1/4Mn3/4]O2 sample was ion- solved in propylene carbonate (Kishida Chem. Co., Ltd.) with
exchanged in a molten salt of LiNO3:LiCl (88:12 mol%) at 2 vol% of fluoroethylene carbonate (FEC, Kanto Denka Kogyo
280 °C for 2 h, according to the method described in the lit- Co., Ltd.) as an electrolyte additive[41] for Na cells with glass
erature.[29,34] Chemical compositions of Li, Na, and Mn were fiber filter (GB-100R, ADVANTEC Co., Japan) as a separator.
determined by ICP analysis after dissolving the samples in HCl
solutions.
3. Results and Discussion
2.2. Materials Characterization 3.1. Synthesis and Structural Characterization of P2-type
Na5/6[Li1/4Mn3/4]O2
Crystal structures of Na5/6[Li1/4Mn3/4]O2 and its ion-exchanged
sample were examined by using an XRD diffractometer Phase stability of P2-type sodium-lithium-manganese ternary
(MultiFlex, Rigaku Co., Ltd.) equipped with a high-speed, one- oxides was first studied. Since no study has examined whether
dimensional X-ray detector (D/teX Ultra, Rigaku Co., Ltd.). or not P2-type Na[Li1/3Mn2/3]O2 only consisting of tetra-
Nonmonochromatized Cu Kα radiation was utilized as an X-ray valent manganese ions, similar to O’3-type Li[Li1/3Mn2/3]O2,
source with a nickel filter. The samples were covered with a would be prepared, we have tried the synthesis of P2-type
laboratory-made attachment during the data collection to avoid Na[Li1/3Mn2/3]O2 by a conventional solid-state method. All our
air exposure. trials to prepare P2-type Na[Li1/3Mn2/3]O2 as a precursor for
Synchrotron X-ray diffraction patterns of the samples were O2-type Li[Li1/3Mn2/3]O2 were, however, unsuccessful because
also collected at beam line BL02B2, SPring-8 in Japan, equipped the P2-type phase is empirically known to be stabilized with a
with a large Debye-Scherrer camera.[35] To minimize the effect Na+-deficient condition (in general, x = 2/3 in NaxMeO2). A typ-
of X-ray absorption by samples, a wavelength of incident X-ray ical X-ray diffraction (XRD) pattern of a reaction product with a
beam was set to 0.5 Å using a silicon monochromator, which ratio of Na/Li/Mn = 3: 1: 2 in the starting material is shown in
was calibrated with a CeO2 standard. Structural analysis by the Figure 2a. Although a major phase is assigned to be the P2-type
Rietveld method was carried out using the program of RIETAN- layered phase, some diffraction lines from impurity phases are
FP.[36] Electron density distribution was optimized by a max- observed. These impurity phases are assigned into Na3MnO4,
imum entropy method (MEM) using the PRIMA program.[37] Li2MnO3, and Na2CO3. Therefore, Na and Li contents in the
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and Mn ions are located at octahedral sites in

MeO2 layers because the size is similar each
other (Li+ = 0.76, Mn3+ = 0.645, and Mn4+ =
0.53 Å).[42] In contrast, relatively large Na ions
(Na+ = 1.02 Å) are located at trigonal pris-
matic sites sandwiched between [Li, Mn]O2
layers. Detailed structural analysis was car-
ried out by the Rietveld/MEM method.
First, in-plane cation ordering between
lithium and manganese ions in [Li1/4Mn3/4]
O2 layers is analyzed. A small diffrac-
tion line is observed at 22 degrees in two
theta in Figure 2. This diffraction line can
be indexed as “1/3 1/3 1” based on fun-
damental diffraction lines for P2-type
NaxMeO2 with a space group of P63/mmc,
indicating the existence of long range in-
plane ordering between Li and Mn ions.
Therefore, a larger unit cell with a
√3a × √3a-type supercell is utilized as a
structural model (Figure 4). Paulsen et al.
have extensively studied the in-plane cation
ordering for P2-type layered structures.[43] Two
different stacking types for the √3a × √3a-type
Figure 2. a) An XRD pattern of the sample prepared with the chemical composition of Na/Li/ supercell in P2-type layered phases are
Mn = 3:1:2 (molar ratio), which was intended to synthesize Na[Li1/3Mn2/3]O2. Some impurity known so far, Na2/3[Mg1/4Mn3/4]O2 (AA-
phases are found with a P2-type layered oxide in (a). b) An XRD pattern of the sample with type, ideally as Na2/3[Mg1/3Mn2/3]O2) and
the optimized chemical composition of Na/Li/Mn = 10:3:9. No impurity phase is found in (b). Na2/3[Ni1/3Mn2/3]O2 (AB-type). Both phases
composed of the same √3a × √3a-type super-
P2-phase were slightly reduced relative to the Mn content. Syn- cell, but stacking sequences of the superlattice along the c-axis
thesis of P2-type Na5/6[Li1/4Mn3/4]O2 without any impurities direction is different. The difference in two types, AA-type
was successful once the synthesis conditions were optimized and AB-type, is also described in Figure 4. Since the stacking
as shown in Figure 2b. Lithium ion contents were successfully sequence of supercells for P2-Na2/3[Li1/6Mn5/6]O2 was not
enriched (approximately 8%) compared to P2-Na2/3[Li1/6Mn5/6]O2 described in the literature,[29] we optimized synthesis condi-
reported by Paulsen et al.[29] The chemical composition of the tions to analyze the stacking sequence. Three clear superlattice
sample was measured by ICP method, and the composition lines are observed for the well-crystallized P2-Na2/3[Li1/6Mn5/6]
(Na/Li/Mn = 0.83:0.24:0.76 molar basis) found to be quite close O2 sample whose stacking sequence of supercells is classi-
to that expected from Na5/6[Li1/4Mn3/4]O2. fied as the AB-type (Figure 4). P2-Na2/3[Li1/6Mn5/6]O2 is com-
Detailed structural analysis for P2-type Na5/6[Li1/4Mn3/4]O2 posed of 1/6 of Li+, 1/6 of Mn3+, and 2/3 of Mn4+ based on
was carried out by synchrotron X-ray diffraction (SXRD) and the simple consideration of charge neutrality. Ionic radius of
neutron diffraction (ND) methods. Figure 3a compares SXRD Mn4+ (0.53 Å) is smaller than radii of Li+ (0.76 Å) and Mn3+
and ND patterns of P2-type Na5/6[Li1/4Mn3/4]O2. Diffraction data (0.645 Å), and Li+ and Mn3+ with similar ionic radii can be
with an extremely high S/N ratio was obtained within several located together at the same crystallographic sites. Therefore,
minutes by using high flux synchrotron X-ray from only a few 1:2 ordering with the √3a × √3a-type supercell is expected to
milligram samples. A higher S/N ratio and narrower full-width be energetically stable in a triangular lattice. Although in-
at half-maximum (FWHM) than those of SXRD are obtained plane cation ordering is still observed in P2-Na5/6[Li1/4Mn3/4]
by ND by using a high-resolution bank (Δd/d = 0.16%) in iMA- O2 as shown in Figures 2, 3 and 4, only a single superlattice
TERIA[38] at J-PARC even though higher sample loading (a few line “1/3 1/3 1” is visible in P2-Na5/6[Li1/4Mn3/4]O2. Super-
grams) and relatively longer measurement time a few hours) are lattice lines of “1/3 1/3 0” and “1/3 1/3 2” are not observed,
required. FWHM of 110 line at d = 1.43 Å is measured to be d = which is different from P2-Na2/3[Li1/6Mn5/6]O2. Both sodium
0.004 and 0.003 Å for SXRD and ND, respectively. In addition, and lithium contents are enriched in P2-Na5/6[Li1/4Mn3/4]O2
intensity of ND lines in a shorter d-spacing region (d < 1.0 Å) based on P2-Na2/3[Li1/6Mn5/6]O2, and its chemical composi-
is much higher than that of SXRD as shown in Figure 3a inset. tion is designed to have the same total amount of Li+ (25%)
For the SXRD pattern, peak intensity is reduced as decrease in and Mn3+ (8.3%), i.e., 1/3 as the sum of Li+ and Mn3+, to
d-values. The Rietveld analysis was first conducted on the SXRD avoid “frustration” to fill triangular sites with √3a × √3a-type
pattern, and the refined data was further validated with analysis superlattice ordering. It was originally expected, therefore,
on the TOFND pattern. Lattice parameters of the sample are that superlattice ordering in the triangular lattice was not
calculated to be a = 2.8678(2) and c = 11.039(1) Å, which are disturbed. The results of the Rietveld analysis further
slightly smaller than those for P2-Na2/3[Li1/6Mn5/6]O2. Both Li support this observation. P2-Na2/3[Ni1/3Mn2/3]O2 with the
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Figure 3. a) Comparison of SXRD and ND patterns of Na5/6[Li1/4Mn3/4]O2. b) The result of the Rietveld analysis on the SXRD pattern of Na5/6[Li1/4Mn3/4]O2.
Refined crystallographic parameters are summarized in Table 1.
superlattice (AB-type, space group of P63) reported by Lu cation ordering is formed in P2-Na5/6[Li1/4Mn3/4]O2. It is found
et al.[44] was employed as an initial structural model for the Riet- that, however, cation ordering between two different sites, 2a
veld analysis on P2-Na5/6[Li1/4Mn3/4]O2. In the unit cell used for and 2b sites, is not perfect from the analysis. Lithium ions in
the Rietveld analysis, lithium and manganese ions are located Na5/6[Li1/4Mn3/4]O2 were found in both sites even though a
at three different octahedral sites, one 2a and two 2b sites. Ide- site occupation number of lithium ions is relatively higher
ally, Li+ and Mn3+ with similar ionic radii can occupy the 2a for the 2a site than the 2b sites, 0.48 and 0.12 for 2a and 2b
site and Mn4+ can occupy the 2b sites when perfect in-plane sites, respectively, as shown in Table 1. This result indicates
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Figure 4. Comparison of stacking sequences of the MeO2 layers with in-plane √3a × √3a-type superlattice ordering in the P2-type phase. Simulated
XRD patterns of Na5/6[Li1/4Mn3/4]O2 with AA-type (Na2/3[Mg1/4Mn3/4]O2-type) and AB-type (Na2/3[Ni1/3Mn2/3]O2-type) stacking manners are compared
with those of the observed XRD patterns of P2-Na2/3[Li1/6Mn5/6]O2 and Na5/6[Li1/4Mn3/4]O2.
that 2/3 and 1/3 of lithium ions are located at 2a and 2b sites, superlattice diffraction lines (Figure 4). Note that a diffraction
respectively, and partial cation disordering (anti-site defect) in line of “1/3 1/3 1” is still clearly observed, and a stacking
P2-Na5/6[Li1/4Mn3/4]O2. Electron density in metal layers opti- manner of superlattice layers along c-axis direction is clearly
mized by the maximum entropy method (MEM) is also shown dominated by the AB-type sequence rather than the AA-type
in Figure 5b. Some extent of contrast for electron density at 2a sequence as expected from the simulated patterns in Figure 4.
(Li-rich) and 2b (Mn-rich) sites is observed in the electron den- Second, the distribution of sodium ions in prismatic sites was
sity shown in Figure 5b associated with partial cation ordering further refined by the Rietveld/MEM analysis. Na ions are poten-
in the triangular lattice. However, its contrast is not clear what tially located at two different prismatic sites in P2-type layered
is expected from the perfect cation ordering without the anti- materials; edge-shared and face-shared sites with Mn(Li)O6 octa-
site defect. This anti-site defect (or potentially stacking faults hedra. Edge-shared sites are generally expected to be energetically
of ideal superlattice layers as discussed in the later section) stable for sodium ions if no interaction from neighboring sodium
reduces the contrast for the electron density between 2a and ions is assumed. Two prismatic sites with different environment
2b sites, and also resulting in the reduction of the intensity of for P2-type oxides, however, result in the complex nature of
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Figure 5. a) A schematic illustration of P2-type Na5/6[Li1/4Mn3/4]O2. b) Electron density calculated by the MEM along [110]. Cross-sectional planes for
Na and Me layers are also shown in (b). The existence of two distinct crystallographic sites, Li-rich and Mn-rich sites, are found in the Me layer. Na
ions are widely distributed in Na layers at splitting edge- and face-shared sites, as shown in (c).
in-plane distribution of Na ions depending on Na contents.[45–47] localized at the two prismatic sites, and found to be widely distrib-
Structural analysis for P2-Na5/6[Li1/4Mn3/4]O2 also suggests that uted in the Na layers. The trend is clearly different from that of
sodium ions are located not only at edge-shared sites but also at P2-type Na1/2VO2 that has perfectly ordered Na ions to minimize
face-shared sites. Site-occupation factors are refined to be approxi- Na+/Na+ electrostatic repulsions between edge and face-shared
mately 50% at edge-shared and 30% at face-shared sites when sites.[47] Therefore, off-centered site positions (or site splitting)
fixed isotropic displacement parameters (0.7 Å2) are used for the for face-shared sodium sites, which are often utilized as a meth-
analysis, as shown in Figure S1a (see the Supporting Information). odology to explain fast self-diffusion of alkaline ions in solid elec-
A goodness of fit is effectively improved by assuming the existence trolyte, such as perovskite-type La0.62Li0.16TiO3[51] and garnet-type
of sodium ions at face-shared sites. Furthermore, a much better Li7La3Zr2O12,[52,53] are employed to rationalize the anomalously
fitting result is obtained by the refinement of isotropic displace- large displacement parameters. This method was also applied for
ment parameters for prismatic sites (Figure S1b in the Supporting the P2-type NaxCoO2.[45] Sodium ions, for P2-Na5/6[Li1/4Mn3/4]
Information). Isotropic displacement parameters are refined to be O2 with the space group P63, are originally located at different
4–5 Å2. The values are anomalously large as isotropic displacement four prismatic sites, (0, 0, z) as 2a, (1/3, 2/3, z) as 2b, (1/3, 2/3,
parameters. Similar trends are also found for P2-Na0.63CoO2[45] z) as 2b, and (1/3, 0, z) as 6c sites as shown in Figure S1a,b (see
and other P2-[48] and OP4-phases.[49,50] The data were, therefore, the Supporting Information). The positions of sodium ions are
further analyzed by the maximum entropy method to understand slightly off-centered based on these ideal positions for each site.
the origin of large displacement parameters. Electron density dis- Site symmetry is reduced from 2a and 2b to 6c sites, leading to
tribution of sodium layers in P2-Na5/6[Li1/4Mn3/4]O2 optimized a split in the sites as shown in Figure 5c. As shown in Table 1
by MEM is shown in Figure 5b. The MEM analysis also supports and Figure 3b, site splitting drastically improves the goodness of
that electrons in Na layers are widely distributed in the both edge- fit with conventional isotropic displacement parameters (0.7 Å2).
and face-shared prismatic sites. Moreover, electron density is not From these results, sodium ions for P2-Na5/6[Li1/4Mn3/4]O2 in
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Table 1. Crystallographic parameters refined by the Rietveld method on a synchrotron X-ray diffraction pattern of P2-type Na5/6[Li1/4Mn3/4]O2.
Atom Site g x y z B [Å2]

Naf (1) 6c 0.104(1) 0.730(2) 0.397(2) ¼ 0.7
Naf (2) 6c 0.104(1) 0.064(2) 0.064(2) ¼ 0.7
Naf (3) 6c 0.104(1) 0.397(2) 0.730(2) ¼ 0.7
Nae (4) 6c 0.172(1) 0.606(1) 0.606(1) ¼ 0.7
Nae (5) 6c 0.172(1) 0.728(1) 2/3 ¼ 0.7
Nae (6) 6c 0.172(1) 2/3 0.728(1) ¼ 0.7
Li (1) 2b 0.121(3) 2/3 1/3 0 0.55(2)
Mn (1) 2b 0.879(3) 2/3 1/3 0 0.55(2)
Li (2) 2b 0.121(3) 1/3 2/3 0 0.55(2)
Mn (2) 2b 0.879(3) 1/3 2/3 0 0.55(2)
Li (3) 2a 0.478(3) 0 0 0 0.55(2)
Mn (3) 2a 0.522(3) 0 0 0 0.55(2)
O (1) 6c 1.0 0.009(3) 0.676(3) 0.087(1) 1.1(1)
O (2) 6c 1.0 0.325(3) 0.992(3) 0.913(1) 1.1(1)
P2-Na5/6[Li1/4Mn3/4]O2, S.G.: P63; a = 4.9672(3) Å, c = 11.039(1) Å, Rwp = 8.26%, RB = 8.28%, and RF = 6.59%.
Na layers are speculated to be not immobilized at prismatic sites ion-exchange of P2-type Na5/6[Li1/4Mn3/4]O2 sample in a molten
between [Li1/4Mn3/4]O2 layers composed of MnO6/LiO6 octahedra, salt medium and its crystal structure of the ion-exchanged
and widely distributed in layers similar to alkaline ions conduc- product are described. Bragg diffraction lines of the sample
tors[51–53] and dissimilar to P2-type Na1/2VO2.[47] Therefore, it is after Na+/Li+-exchange in the molten salt completely changed
hypothesized that such wider distribution of the electron density as shown in Figure 6. The chemical composition is found to
originates from fast self-diffusion of Na+ over edge- and face- be Li/Mn = 0.94:0.76 (molar ratio) in the ion-exchanged sample
shared prismatic sites, instead of stabilization by ordering. Self- with a trace of sodium. Decrease in alkali metal ion contents
diffusion of Na+ is further enhanced at elevated temperatures. after ion-exchange suggests partial oxidation of manganese ions
A SXRD pattern of P2-Na5/6[Li1/4Mn3/4]O2 collected at 470 °C is during ion-exchange in molten salts, presumably oxidation by
shown in Figure S2 (see the Supporting Information). Lattice nitrate ions, NO3− and/or moist air. Since the ionic radius of Li+
parameters are expanded at 470 °C because of thermal expansion. is smaller than that of Na+, Li+ cannot occupy trigonal prismatic
Isotropic displacement parameters for all sites are also increased, sites. The ion-exchange process, therefore, results in translation
especially for the sites of Na ions (5.6–7.1 Å2). Although displace- of [Li1/4Mn3/4]O2 layers toward either way (2/3, 1/3, z) or (1/3,
ment parameters are generally increased at elevated temperatures, 2/3, z) direction.[54,55] Note that selective profile broadening for
displacement parameters observed for Na sites are anomalously 10l lines is clearly observed while the diffraction line profile
large, which could be indicative of further accelerated self-diffu- for 00l and 11l remains sharp. A ND pattern was also collected
sion of Na ions. (Figure 6c) to further analyze the crystal structure of the ion-
Finally, on the basis of the results obtained by the Rietveld/ exchange sample. Since Li and Mn ions have similar neutron
MEM analysis on the SXRD pattern, isotropic displacement scattering length, 002 diffraction line was not observed. Neutron
parameters and site occupation factors were further validated with diffraction line profile is mainly contributed by oxide ions as
the analysis on a ND pattern. Note that Li and Mn ions are very the framework structure. Similar to SXRD pattern, line profile
difficult to distinguish from each other by the ND method. There- broadening is clearly observed in the ND pattern. The profile
fore, the P2-phase with a primitive unit lattice with a space group of 110 diffraction line remains sharp with narrow full-width-at-
of P63/mmc (not supercell) was utilized as the structural model for half-maximum after ion exchange. These results clearly suggest
analysis. A general trend observed is slightly smaller isotropic dis- that in-plane crystallinity of the sample was not damaged by ion
placement parameters for ND, as shown in Figure S3, compared exchange. Additionally, superlattice lines are still observed as
with SXRD in Figure S1b (see the Supporting Information). The discussed in the later section. From these results, its chemical
existence of oxygen vacancy etc. was not evidenced. From these composition and cation arrangement of [Li1/4Mn3/4]O2 layers
results, it is concluded that refined results by SXRD are reason- are expected to be not changed by ion exchange. Therefore, the
able as the structural model of P2-Na5/6[Li1/4Mn3/4]O2. possibility of stacking faults for [Li1/4Mn3/4]O2 layers along
c-axis direction was analyzed with the DIFFaX program.
The MeO2 layers (slabs) for the P2-phase can glide toward
3.2. Na+/Li+-Exchange in a Molten Salt and Analysis of Stacking either (1/3, 2/3, z) or (2/3, 1/3, z) direction by Na+/Li+ ion-
Faults exchange because smaller Li ions in comparison to Na ions
cannot be stabilized at large trigonal prismatic sites. Gliding
In the previous section, the crystal structure of P2-type of MeO2 layers often results in stacking faults, depending
Na5/6[Li1/4Mn3/4]O2 was analyzed in detail. In this section, Na/Li on the kinetics of “formation of ion-exchange centers” vs.
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process with different models for stacking
002
faults are summarized in Figure 7. MeO2

layers are numbered from 1 to 7 for the
(a) P2-phase in Figure 7. MeO2 layers (slabs)
with odd numbers, 1, 3, 5 and 7, do not
move and the layers stay at its original posi-
014
tion, whereas layers with even numbers,
012
2, 4, and 6 move toward (2/3, 1/3, z) direc-
tion, forming the ideal O2-phase. Similar to
110
013 this phase, when the even-numbered layers
016
glide toward the direction of (1/3, 2/3, z),
010
O2′-phase is formed as shown in Figure 7.

1/3 1/3 1
112
004
The difference between O2- and O2’-phases

is the position of face- and edge-shared
011
planes between MeO6 and LiO6 octahedra.

Both phases are crystallographically iden-
(b) tical. When the O2′-phase is rotated by 180°
110
(the rotation axis is directed perpendicular

002
to the page), the O2′-phase is superimposed

1/3 1/3 0
to the O2-phase. Both phases are formed

011
1/3 1/3 1
112
004
013
with the minimum numbers in layer gliding

012
015
(50%). The formation of these phases should

*
* be achieved if growth of O2-domains is the
dominant process, such as O2-LiCoO2.[56]
114
Here, the formation rate of ion-exchange

(c) centers is assumed to dominate the growth
rate, higher percentage of layers (>50%)
moves from its original position. If a number
of gliding layers increases to 66.7% (two out
of three MeO2 layers), the formation of a dif-
ferent phase is expected, i.e., a O6-type phase,
5 10 15 20 25 30 which is an intergrowth phase between O2-
and O2’-phases, as shown in Figure 7. An
2θ / deg. (λ = 0.5 Å) ideal sequence for layer gliding is described
as follows; MeO2 layers, numbered as 1 and
Figure 6. Comparison of synchrotron X-ray diffraction patterns: a) P2-type Na5/6[Li1/4Mn3/4]O2
4, stay at their original position, layers 2 and
(S.G. P63/mmc; a = 2.8679(2) Å and c = 11.038(6) Å), and, b) O2-type Lix[Li1/4Mn3/4]O2 (S.G.
P63mc; a = 2.842 Å and c = 9.778 Å) as the ion-exchanged sample of (a). c) A neutron diffraction 5 move towards (1/3, 2/3, z), and layers 3
pattern of O2-type Lix[Li1/4Mn3/4]O2. Asterisks in (b) suggest the existence of an unknown impu- and 6 move towards (2/3, 1/3, z), resulting
rity phase. Dotted lines in the figure are guides for eyes. Particle morphology observed by SEM in the formation of the O6-phase. The
of the samples is shown in the inset. Particle size of P2-type Na5/6[Li1/4Mn3/4]O2 ranges from 0.7 sequence of face- and edge-shared sites for
to 1.5 µm, and no clear change in the particle morphology by the Na+/Li+ ion-exchange is found. LiO6 octahedra alternately changes along the
The surface area of P2-type Na5/6[Li1/4Mn3/4]O2 is observed to be approximately 1.0 m2 g–1 by c-axis direction in the O6-phase because the
the BET measurement.
O6-phase is the intergrowth phase between
O2- and O2’-phases. A simulated XRD pat-
“growth of O2-domains”. O2-LiCoO2 has a nearly ideal phase tern of the O6-phase is shown in Figure 8. The XRD pattern of
as O2-phase without stacking faults[56] whereas clear evidence the O6-phase is completely different from that of the O2(O2′)-
of stacking faults was found for O2-Li2/3[CoxNi1/3-xMn2/3]O2.[57] phase, except 110 and 00l lines. Therefore, the XRD pattern is
Small amount of metal substitution also highly influences the expected to change drastically by assuming the formation of
formation of stacking faults.[58] Models of O2/T2 and O2/O6 the intergrowth between O2/O6-phases, as proposed by Lu and
intergrowth have been proposed by Lu and Dahn to analyze the Dahn.[57] Simulated XRD patterns of the O2/O6 intergrowth
stacking faults induced by ion exchange.[57] Recently, we have phase with different fractions are also shown in Figure 8. In
extended this model to an OP4-phase, which is an intergrowth this simulation, O6-domains are randomly inserted based on
phase between O3- and P2-phases. A model of O4/O12 inter- the ideal O2-phase. As shown in Figure 8, a line profile is dras-
growth has been proposed for the analysis of stacking faults.[59] tically broadened as increase in the fractions of stacking faults,
In this study, the O2/O6 intergrowth model is extended to elu- except for the 110 and 00l lines. The maximum line broadening
cidate the cation ordering in MeO2 layers based on the AB-type is observed for 1:1 random intergrowth structure between O2-
model (Figure 4) which was utilized as the structural model of and O6-phases, and this phase also corresponds the layered
P2-type Na5/6[Li1/4Mn3/4]O2 for the Rietveld analysis (Figure 3b structure with complete random sequence for the stacking of
and Table 1). Schematic illustrations of the ion-exchange MeO2 layers (each block glides towards either (1/3, 2/3, z) or
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Figure 7. Schematic illustrations of crystal structures for the P2-type phase, and for O2-, O2’-, and O6-type phases that are potentially prepared from the
P2-phase by Na/Li ion-exchange. “E” and “F” denote edge- and face-sharing planes of LiO6−MeO6, respectively. Numbers of layers and corresponding
glide vector to obtain the three different phases derived from the P2-phase are also shown. See the text for more details.
(2/3, 1/3, z) without any restrictions). From the simulated XRD both profiles and intensity of superlattice lines are influenced
patterns shown in Figure 8, approximately 30% of O6-domains by faults of through-plane sequences of superlattice layers with
are expected to exist in the experimentally prepared O2-phase Li/Mn ordering, by which line profiles and intensity for funda-
from P2-type Na5/6[Li1/4Mn3/4]O2. The relatively large extent of mental diffraction lines are not affected. One example is shown
stacking faults is found in the ion-exchange sample of P2-type in Figure 9 as B and B’ layers, which are two different superlat-
Na5/6[Li1/4Mn3/4]O2. These results clearly suggest that the tice layers, but positions of oxygen and metal sites are crystallo-
nucleation rate for ion exchange is kinetically fast. Relatively graphically the same each other. As a result, line profiles of fun-
higher temperature for the ion exchange with molten salt damental diffraction lines is only little changed by intergrowth
(280 °C) could accelerate the nucleation rate. between B and B’. In-plane arrangements of lithium and metal
Note that superlattice lines are still observed after ion ions are, however, clearly different in both layers. The intensity
exchange, indicating that in-plane cation ordering was not of superlattice diffractions lines is, therefore, reduced by this
lost by ion-exchange. However, some lines related to cation type of intergrowth, except for the “1/3 1/3 0” line which is per-
ordering are not found in the experimental pattern (see the pendicular to (001), as shown in Figure 9. Note that superlattice
inset in Figure 8). Relatively sharp “1/3 1/3 0” and broad “1/3 line profiles in simulated patterns are still sharp compared with
1/3 1” superlattice lines are observed in the experimental pat- the observed patterns, especially for “1/3 1/3 1”. This observa-
tern in Figure 6. As shown in the inset of Figure 8, superlat- tion suggests the existence of additional stacking faults; e.g.,
tice lines of “1/3 1/3 2” and “1/3 1/3 3” must be also observed insertion of B and/or B’ layers into the A layer, etc., which fur-
for the ideal O2-type phase derived from the P2-type phase with ther reduce the intensity of superlattice layers. Indeed, when
the AB-type superlattice stacking. This fact could be explained three superlattice layers, A, B, and B’, are randomly stacked in
by the existence of additional stacking faults related to supre- the O2-type phase, only the “1/3 1/3 0” superlattice line with
rlattice layers, as shown in Figure 9. The intensity of the “1/3 a tail is observed as shown in Figure 9, similar to O3-type
1/3 1” superlattice line is the maximum among all superlattice Li2MnO3-based materials.[60] This fact also suggests that the in-
lines for the ideal O2-type layered structure. When the stacking plane anti-site defect observed in P2-Na5/6[Li1/4Mn3/4]O2 could
faults with O2/O6 intergrowth are induced, the line profile originate from this type of the stacking fault. The Rietveld
broadening is observed, not only for fundamental diffraction method can deal with an averaged crystal structure and cannot
lines (Figure 8), but also for superlattice lines, except for the deal with real local structures. If the B and B’ superlattice
“1/3 1/3 0” superlattice line, as shown in Figure 9. Additionally, layers are in part inserted into the A layer as stacking faults,
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Figure 8. Simulated SXRD patterns of O2/O6 intergrowth phases with in-plane superlattice ordering using the DIFFaX program. Peak broadening
observed for the O2-type phase is nicely reproduced by assuming the presence of stacking faults with approximately 30% O6-domains. The highlighted
pattern in relation to the superlattice diffraction lines is shown in the inset. Also see Figure 9 for further detail.
site-occupation factors could be easily changed, as shown for Li layers is the same with the ideal O2-phase. LiO6 octa-
in Table 1. From superlattice line profiles observed for the hedra share a face with a MeO6 octahedron at least either side
O2-phase, it is hypothesized that anti-site defects found in even in the ideal O6-phase; therefore, it is expected that man-
P2-Na5/6[Li1/4Mn3/4]O2 could originate from stacking faults ganese migration could be suppressed during electrochemical
related to superlattice layers. Additionally, the fact also seems to cycling regardless of the existence of stacking faults. Figure 10
imply that each superlattice layer could have nearly ideal cation shows the electrode performance of O2-Lix[Li1/4Mn3/4]O2 in a
arrangement as expected from the chemical compositions, 25% Li cell in a voltage range of 2.0 and 4.8 V. The electrode per-
Li+, 8.3% Mn3+ (total 33%), and 66% Mn4+, and have locally formance of O2- Li2/3[Li1/6Mn5/6]O2 that is the original sample
less anti-site defects. To test this hypothesis, studies on X-ray reported by Dahn’s group[29] is also shown for comparison. The
absorption and nuclear magnetic resonance spectroscopy are maximum reversible capacity of ca. 150 mA h g−1 is observed
currently under way in our group to examine the local struc- for O2-Li2/3[Li1/6Mn5/6]O2, which is consistent with the lit-
tures of Li and Mn ions. erature.[29] Different electrochemical behavior is observed for
O2-Lix[Li1/4Mn3/4]O2. On initial charge to 4.8 V, a voltage plateau
at 4.6 V is observed, especially clearly for O2-Lix[Li1/4Mn3/4]O2.
3.3. Electrode Performance of O2-Lix[Li1/4Mn3/4]O2 Similar voltage plateaus are generally observed as a specific
and P2-Na5/6[Li1/4Mn3/4]O2 character for O3-type Li2MnO3-based electrode materials. In
addition, the reversible capacity of O2-Lix[Li1/4Mn3/4]O2 is sig-
In the previous section, the crystal structures of Na/Li ion- nificantly increased by charge beyond the voltage plateau as
exchanged samples of P2-type Na5/6[Li1/4Mn3/4]O2 were ana- shown in Figure S4 (see the Supporting Information). The
lyzed in detail. Although stacking faults with O6-domains are reversible capacity increases from 100 mA h g−1 (2.0–4.4 V cycle)
not negligible in the ion-exchanged sample, the local structure to 200 mA h g−1 (2.0–4.8 V cycle). These facts probably suggest
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Figure 9. Comparison of simulated XRD patterns of O2-type Lix[Li1/4Mn3/4]O2 with different stacking sequences. Through-plane stacking faults highly
influence the intensity of the superlattice lines in relation to the difference in the position of Li and Mn ions. See the text for more details.
that oxide ions could be partly extracted from the crystal lattice, reversible capacity observed is less than 60 mA h g−1. These
resulting in in-plane cation rearrangements, similar to O3-type results suggest that P2-type Na5/6[Li1/4Mn3/4]O2 also shows
Li2MnO3-based electrode materials.[5,10,13,14,21,61] The reversible irreversible structural transition in Na cells, presumably
capacity is successfully increased by enrichment of Li ions in associated with the partial oxygen loss from P2-type frame-
the O2-type framework structure as manganese-based elec- work upon charge to high voltage, similar to the O2-phase
trode materials. Discharge capacity retention for two different in Li cells. Such structural phase transition during first and
O2-phases, O2-Lix[Li1/4Mn3/4]O2 and O2-Li2/3[Li1/6Mn5/6]O2, continuous cycles in the Na/Li cells will be further discussed
is also compared in Figure 10d. Both samples show similar in the later section.
capacity retention and changes in voltage profiles, which origi- Rate-capability of the O2- and P2-phases in Li and Na cells,
nate from the unfavorable phase transition into spinel, are not respectively, is compared in Figure 11. The P2-type phase in
observed. the Na cell seems to show better rate-capability compared
As shown in Figure 10a, O2-Lix[Li1/4Mn3/4]O2 can deliver to the O2-type phase in the Li cell. The O2- and P2-phases
large reversible capacity (ca. 200 mA h g−1) in the Li cell. deliver approximately 190 and 185 mA h g−1 of reversible
Additionally, note that this electrode material has multi- capacity, respectively, at a low rate of 10 mA g−1. Estimated
functionality in both Li and Na cells. Similar to the Li cell, energy density reaches 620 mW h g−1 based on emf vs. Li
P2-type Na5/6[Li1/4Mn3/4]O2 can deliver ca. 200 mA h g−1 of metal for the O2-phase and 500 mW h g−1 based on emf vs.
reversible capacity in a Na cell (Figure 10c) with relatively Na metal for the P2-phase. P2-Na5/6[Li1/4Mn3/4]O2 can still
good capacity retention for 20 cycles. A voltage plateau deliver more than 150 mA h g−1 of reversible capacity at 1 C
is observed at 4.1 V for initial charge in the Na cell. Large rate (236 mA g−1). According to the first-principles calcula-
reversible capacity of ca. 200 mA h g−1 is also obtained after tion on the layered oxides, a diffusion barrier of Na+ in the
charge to 4.5 V (corresponding to approximately 4.8 V vs. Li) O3-type layered oxides is comparable to Li+ even though the
in the Na cell (see Figure S5 in the Supporting Information). ionic radius of Na+ is much larger than that of Li+.[62] Since
When the cut-off voltage is limited to 3.6 V in the Na cell, the the P2-type layered phase provides an open Na+-diffusion
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ions, similar to O3-phase (note that O2/O3-phases could have
slightly different migration characters because of the differ-
ence in interstitial tetrahedral sites; only face-shared sites
for the O3-phase and either face or edge-shared sites for the
O2-phase). Instead, Li ions migrate to octahedral sites via
adjacent face-shared tetrahedral sites to reduce the activation
energy for site hopping.[62–64] Therefore, it is expected better
diffusivity of Na ions in the P2-type framework structures.
Good rate-capability of P2-Na5/6[Li1/4Mn3/4]O2 in the Na cell
could be also consistent with the results of these studies by
first-principles calculation,[62,63] and the structural analysis
provided in this study in Figure 5. Site splitting for Na ions
found by the Rietveld analysis is suggested to be indicative of
low migration barriers of sodium ions in P2-type framework
structures. Open framework structures without a bottleneck
for Na migration, such as P2-type phase, which are stabilized
by large Na ions, have an advantage as insertion hosts.
3.4. Changes in Crystal Structures of O2-Lix[Li1/4Mn3/4]O2

and P2-Na5/6[Li1/4Mn3/4]O2
In the previous section, we demonstrated that O2-type

Lix[Li1/4Mn3/4]O2 and P2-Na5/6[Li1/4Mn3/4]O2 show good elec-
trode performance in Li and Na cells, respectively. In this
section, changes in crystal structures during initial charge/
discharge processes are discussed. Synchrotron X-ray diffrac-
tion (SXRD) patterns of the samples after charge/discharge
in Li or Na cells are shown in Figure 12. Changes in lattice
parameters are summarized in Figure 13. For the O2-phase,
the 002 line is found to be separated into two peaks after
charge to 4.8 V. This fact indicates that the coexistence of two
phases, which are two O2-type layered phases with different
interlayer distances (approximately 4.8 and 4.6 Å). Volume
shrinkage after the formation of this second phase is calcu-
lated to be 4% when both phases are assumed to have similar
a-axis values (because peak splitting and/or clear broadening
was not observed for the 110 line.). A single phase of the
O2-type phase with a relatively large a-axis value (2.86 Å, and
2.84 Å for the as-prepared sample) is found after discharge to
2.0 V. When the XRD patterns of the fully discharged sam-
ples in Li and Na cells are compared, a clear difference is
noted. The diffraction line profile of the sample in the Na cell
Figure 10. Comparison of charge/discharge curves: a) Li/Lix[Li1/4Mn3/4] is clearly broadened, especially for the 110 line. In contrast,
O2, b) Li/Lix[Li1/6Mn5/6]O2, and, c) Na/Na5/6[Li1/4Mn3/4]O2 cells cycled at peak profiles for 00l lines remain sharp. This result suggests
a rate of 10 mA g−1 in voltage ranges of 2.0–4.8 V in Li cells and 1.5–4.4 V in-plane distortion in the crystal lattice. Therefore, the fully
in Na cells. d) Capacity retention of the three electrochemical cells. discharged sample was analyzed using an orthorhombic lat-
tice (S.G. Cmcm). Enriched high-spin trivalent manganese
ions, which are typically known as Jahn-Teller ions, induce in-
path compared with the O3-phase, lowering the diffusion plane distortion in the crystal lattice. Such distortion of the lat-
barrier is expected. Sodium ions in the P2-type framework tice is much more evident for the P2-phase with sodium ions
structure can directly hop between edge- and face-shared compared with the O2-phase with lithium ions, even though
trigonal prismatic sites (with MeO6 octahedron), which are it is expected that similar amount of trivalent manganese
adjacent sites at a distance range of 1.6–1.7 Å. Results of ions could exist in both phases simply based on the observed
the first-principles calculation indicate that lower activation reversible capacity. The formation of a new phase is found as
energy for Na diffusion in the P2-phase with the direct path a minor phase after fully charging to high voltage in the Na
compared with that of the O2-phase.[63] For the O2-phase, Li cell for P2-type Nay[Li1/4Mn3/4]O2. The minor phase can be
migration with a direct path is expected to be energetically assigned into the P2-phase with relatively shorter interlayer
unfavorable because of large repulsive interaction with oxide distance because of Na extraction. However, phase transition
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FULL PAPER
in Li cells and P2-type Nay[LixMn1-x]O2 in Na

cells. Very recently, it has been reported that
(a) Li/Lix[Li1/4Mn3/4]O2 high reversible capacity of 200 mA h g−1 was
4.0 observed for P2-type Na0.85[Li0.17Ni0.21Mn0.64]
1/10 C 1/28 C O2 after charge to 4.8 V in a Na cell.[66] How-
(10 mA g-1) ever, its origin for high capacity has not
3.0 been provided and discussed. As shown in
A Figure 12, superlattice lines disappeared
2.0 B
after charge to high voltage for O2-type
Liy[LixMn1-x]O2 and P2-type Nay[LixMn1-x]O2.
Edge-share
Face-share
x It is proposed that large reversible capacity
1/2 C 1/5 C
1.0 A 2C for both phases originates from the in-plane
cation rearrangements induced by partial
Voltage / V
C 1C (275 mA g-1)
edge-share lithium extraction from transition metal
0.0 layers and partial oxygen loss. As a result,
originally inactive tetravalent manganese
5.0 ions are activated in Li and Na cells, regard-
less of the difference in oxygen packing,
(b) Na/Nay[Li1/4Mn3/4]O2
4.0 O2, O3, and P2. It is also hypothesized that
charge compensation is partly achieved by
the contribution of oxide ions in the crystal
1/24 C
3.0 1/10 C lattice as solid-state reactions without oxygen
(10 mA g-1) loss.[13,16,67,68] Large hysteresis for charge/dis-
A charge cycles, which is an inherent character
2.0 B of “activated” Li2MnO3-based materials,[69]
could also support this hypothesis (see Figure
Edge-share Face-share
S6 in the Supporting Information). Note
1.0 B 2C
that, historically, such charge compensation
1/2 C 1/5 C
A 1C (236 mA g-1) by anions has been already evidenced in
0.0 sulfides,[70] and the possibility of charge com-
0 50 100 150 200 pensation by oxide ions has been also dis-
cussed for late transition metal oxides before
Capacity / mAh g -1 2000.[71,72] From these results, it is concluded
that high-reversible capacity as electrode
Figure 11. Rate-capability of: a) Li/Lix[Li1/4Mn3/4]O2, and, b) Na/Na5/6[Li1/4Mn3/4]O2 cells. The materials in O2-type Lix[Li1/4Mn3/4]O2 and
cells were charged at a rate of 10 mA g−1 to 4.8 V for the Li cell and 4.4 V for the Na cell, and
then discharged at different current density. The sample loading of the electrodes used was:
P2-type Na5/6[Li1/4Mn3/4]O2 originates from
a) 2.5, and, b) 2.1 mg cm−2. Schematic illustrations of Li and Na migration processes in similar charge compensation mechanisms to
O2- and P2-type layered structures are also compared in the insets (see the detailed explana- O3-type Li2MnO3-based electrode materials.
tions in the text).
into other phases, e.g., the P2-O2 phase transition observed 3.5. Changes in Crystal Structures and Phase Transition
for Nay[Ni1/3Mn2/3]O2[63,65] and the P2-OP4 phase transition of O2-Lix[Li1/4Mn3/4]O2 during “Continuous” Cycles
observed for Nay[Fe1/2Mn1/2]O2[33], are not evidenced even in
the fully charged state. In this section, since it is expected that O2-Lix[Li1/4Mn3/4]O2
Large reversible capacity is obtained only after charge beyond can suppress the spinel-like phase transition and thus good
voltage plateaus, as shown in Figures S4 and S5 in the Sup- cyclability without nickel and cobalt substitution, similar
porting Information. A clear change in the SXRD patterns after to O2-Lix[Li1/6Mn5/6]O2,[29] reaction mechanisms and long-
charge to high voltage is found for the superlattice lines; “1/3 term phase stability were further examined. Herein, O3-type
1/3 0” at 2θ of 6.7° for the O2-phase and “1/3 1/3 1” at 7.1° Lix[Li1/4Mn3/4]O2, which has nearly the same amount of lithium
for the P2-phase. A similar trend, the maintenance of superlat- ions in transition metal layers (25%), was also prepared from
tice lines before charge to high voltage and disappearance of P3-Nax[Li1/4Mn3/4]O2 by the same ion-exchange process as that
the superlattice lines after charge to high voltage, is found in for O2-Lix[Li1/4Mn3/4]O2. The importance of oxygen packing,
both Li and Na cells. These facts clearly suggest in-plane cation which affects cyclability and phase transition during continuous
rearrangement after charge to high voltage, which is presum- cycles, is also discussed through a comparative study on the O2-
ably induced by partial oxygen loss from the crystal lattice, and O3-type Li-excess manganese layered oxides. Note that it is
similar to Li2MnO3-based electrode materials.[13,14,21,22] To the difficult to directly synthesize O3-type Lix[Li1/4Mn3/4]O2 under
best of our knowledge, this is the first experimental evidence an equilibrium condition. Therefore, a Na-based layered com-
of cation rearrangements, presumably associated with partial pound was prepared and utilized as a precursor for Na/Li ion-
oxygen loss from the crystal lattice, in O2-type Liy[LixMn1-x]O2 exchange. Our all trials to synthesize O3-type Nax[Li1/4Mn3/4]O2
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Figure 12. Changes in SXRD patterns of: a) Lix[Li1/4Mn3/4]O2, and, b) Na5/6[Li1/4Mn3/4]O2 in Li and Na cells, respectively, on initial charge/discharge.
Highlighted SXRD patterns (marked by dotted squares) are also shown in the insets. Changes in lattice parameters calculated from the SXRD patterns
and charge/discharge curves with the points, where SXRD patterns were collected, are shown in Figure 13.
failed whereas P3-type Nax[Li1/4Mn3/4]O2 was successfully syn- LiMnO2 and Li2MnO3 even though the sample could have an
thesized, as shown in Figure 14. P3-type Nax[Li1/4Mn3/4]O2 was off-stoichiomteric composition associated with the formation
prepared by heat treatment of a mixture of Na2CO3, Li2CO3, and of Li vacancies in lithium layers. Charge/discharge curves of
MnCO3 at 600 °C for 10 h in air. The starting materials were the O2- and O3-type Lix[Li1/4Mn3/4]O2 are compared in Figure 15.
same as those for P2-type Na5/6[Li1/4Mn3/4]O2 and the synthesis Voltage plateaus at approximately 4.5 V are observed in both
temperature was lowered to 600 °C. After Na/Li ion-exchange samples on initial charge regardless of the difference in oxygen
for P3-type Nax[Li1/4Mn3/4]O2, lithium ions cannot be stabilized packing manners. Large initial discharge capacities of more
at trigonal prismatic sites, resulting in gliding of layers and thus than 200 mA h g−1 are observed for O3-type Lix[Li1/4Mn3/4]O2.
the formation of O3-type Lix[Li1/4Mn3/4]O2. Herein, O3-type The initial discharge capacity for the O3-phase is slightly larger
Lix[Li1/4Mn3/4]O2 is regarded as a solid solution between O3-type than that of the O2-phase. Since the size of primary particles for
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Figure 13. Changes in lattice parameters calculated from the SXRD patterns for: a) O2-Lix[Li1/4Mn3/4]O2, and, b) P2- Na5/6[Li1/4Mn3/4]O2 in Figure 12.
The points, where SXRD patterns were collected, are shown in the right-hand side. Estimated Na and Li contents from the oxidation/reduction capacity
in both phases are also shown in the right graphs, in which lithium ions in the transition metal layers and oxide ions are assumed to be non-extractable
for simplicity.
both samples is different (O3: ca. 100 nm, Figure 14, and O2: ca. (Figure 16b). Both diffraction lines merge into a single broad
1.0 µm, Figure 6b inset), this could contribute to a larger initial diffraction line, indicating that the ratio of lattice parameters,
discharge capacity for the O3-phase. The most important differ- chex./ahex., is decreased to 4.90. This change can be explained
ence is found to appear in changes in voltage profiles during by phase transition from a rhombohedral to cubic lattice.[73]
continuous cycles in Figure 15. Voltage profiles of the O3-phase Structural anisotropy of layered materials is easily lost after
in the Li cell continuously change while almost no change in electrochemical cycle tests for the O3-phase, similar to other lay-
the profile is found for the O2-phase. The discharge voltage is ered LiMnO2 with trivalent manganese ions.[25,26,28] This result
lowered in continuous cycles for the O3-phase, which resembles directly supports unavoidable phase transition into the cubic
the character of nickel- and cobalt-substituted Li2MnO3-based phase (probably a spinel-like phase) for O3-type layered manga-
electrode materials.[15,23,24] Additionally, after several cycles, a nese oxides with a CCP oxygen array. This cubic phase seems to
new redox couple appears at 3.8–4.0 V in a differential capacity have grown further in electrochemical cycles because the peak
plot in Figure 15d. The appearance of this redox couple is con- profile became sharp after 15 cycles. This result is consistent
sidered to be a sign of spinel phase formation. In contrast, with the fact that a new redox couple at near 4 V becomes more
such voltage profile changes are not observed for the O2-phase, clearly visible after 15 cycles. In contrast to the O3-phase, no
except the initial activation cycle, as shown in Figure 15c. change in the SXRD profile during continuous cycles is observed
Changes in crystal structures of the O2- and O3-phase in for the O2-phase, except the activation process for the first cycle.
Li cells during continuous cycles were further examined by The SXRD pattern of the O2-phase after the first cycle is super-
SXRD. Figure 16 compares SXRD patterns of O2- and O3-type imposed into that of the 20th cycle. This result is also consistent
Lix[Li1/4Mn3/4]O2 before and after cycle tests. It is noted that with the fact that no clear change is found in dQ/dV plots for the
clear changes in diffraction patterns of the O3-phase is found O2-phase (Figure 15c) in continuous cycles. The results are dem-
after cycle tests. A clear separation of Bragg diffraction lines for onstrated that O2-type Lix[Li1/4Mn3/4]O2 does not convert into
108 and 110 is originally observed for the as-prepared O3-phase spinel because of the incompatibility of oxygen packing.
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Figure 14. XRD patterns of: a) P3-type Nax[Li1/4Mn3/4]O2, and, b) its ion-exchanged sample in a molten salt. Unreacted Na2CO3 is also found as a minor
impurity phase with the P3-phase as a major phase. Since non-reacted Na2CO3 was found in P3-type Nax[Li1/4Mn3/4]O2, the value of x is expected to be
smaller than that used in the starting material (x = 5/6). Lattice parameters of the O3-Nax[Li1/4Mn3/4]O2 were calculated to be ahex. = 2.852 and chex. =
14.44 Å. The crystal structure of the ion-exchanged sample is assigned to an O3-type layered phase with a space group R-3m. c) Particle morphology
of the O3-phase as observed by SEM. d) A schematic illustration of the O3-type layered structure.
3.6. Impact of Pre-Cycle on Electrode Performance of O2-type large reversible capacity, 220 mA h g−1, as lithium manganese
Lix[Li1/4Mn3/4]O2 binary oxides without nickel and cobalt ions. Moreover, its
cyclability is acceptable as electrode materials. Capacity reten-
Recently, it was reported that stepwise pre-cycling treatment is tion reaches 80% after the 50 cycles test at a rate of 15 mA g−1
an effective method to improve cyclability of Li2MnO3-based (Figure 17b). Clear changes in the dQ/dV profile are not found,
electrode materials.[18,19] Samples are charged with a gradual as shown in the inset of Figure 17a.
increase of cut-off voltage in Li cells, and thus a regulated From these results, it is concluded that oxygen packing of
amount of lithium/oxygen is extracted from the samples. Unfa- manganese-based layered materials is the important factor to
vorable surface modifications of samples are, therefore, effec- suppress phase transition into the cubic spinel phase, which
tively suppressed by the stepwise pre-cycling treatment. This originates from trivalent manganese ions with a highly mobile
treatment is also highly effective for O2-type Lix[Li1/4Mn3/4]O2. character in the framework structure consisting of oxide ions.
Experimental conditions used are described in Figure S7 (see As first proposed by Dahn and coworkers,[29] the O2-type phase
the Supporting Information). The reversible capacity increases with face-shared octahedral sites effectively suppresses the
to more than 220 mA h g−1 after the stepwise pre-cycling treat- migration of trivalent manganese ions, presumably because of
ment (Figure 17a). This reversible capacity is comparable to that the large repulsive interaction between manganese and lithium
reported for the nickel substituted O2-type Li-rich phase, which ions at face-shared sites. In addition, further enrichment of
was prepared from P2-type Na0.9Li0.3Ni0.25Mn0.75Oδ by ion lithium ions in the transition metal layers is the highly effective
exchange.[74] It is demonstrated that the possibility to achieve method to increase reversible capacity of O2-type layered oxides
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Figure 15. Comparison of charge/discharge curves for two layered polymorphs: a) O2-, and, b) O3-type Lix[Li1/4Mn3/4]O2 at a rate of 15 mA g−1 in the
voltage range 2.0–4.8 V in Li cells. The evolution of differential capacity (dQ/dV) curves during continuous cycles in: c) O2-, and, d) O3-type polymorphs
is also compared.
as electrode materials. The design of oxygen packing and fur- has enough sodium ions to compensate on the negative elec-
ther enrichment of Li contents will be the important strategy to trode side, and therefore can be utilized as a high-capacity elec-
realize high capacity and long cycle life manganese-based posi- trode material.[33] Approximately 60 mA h g−1 (0.23 mol of Na+)
tive electrode materials for rechargeable lithium batteries in the of capacity is needed to compensate in advance (for example,
future. by pre-discharge in Na half-cells, pre-doping of sodium ions
with metallic sodium, etc.) to achieve a high reversible capacity
of 190 mA h g−1 as a full cell. The deficiency of sodium ions
3.7. The Possibility of Rechargeable Sodium Batteries becomes a disadvantage of P2-type phases when it is intended
(Na-Ion Batteries) with P2-type Layered Materials to design practical Na-ion batteries combined with conven-
tional negative electrodes, such as hard carbon[75,76] or titanium
As shown in previous sections, O2-Lix[Li1/4Mn3/4]O2 could have oxides,[77] which have no sodium ions to compensate. This
potential for application as a high capacity and long cycle life leads to a disadvantage compared to Na2/3[Fe1/2Mn1/2]O2 as
manganese-based electrode material for rechargeable Li bat- the cost-effective electrode materials for rechargeable sodium
teries. In addition, P2-Na5/6[Li1/4Mn3/4]O2 shows 190 mA h g−1 batteries. In contrast, P2-Na5/6[Li1/4Mn3/4]O2 as the new
of reversible capacity in Na cells, similar to Li cells. Moreover, P2-type layered material reported in this article has relatively
the reversible capacity observed is comparable or slightly larger a higher sodium content for P2-type layered oxides. There-
than that of P2-type Na2/3[Fe1/2Mn1/2]O2, which is known as a fore, the deficiency of sodium ions is also reduced compared
sodium insertion material showing very high reversible capacity with P2-Na2/3[Fe1/2Mn1/2]O2. Indeed, the difference in capacity
in Na cells with acceptable cyclability.[33] In general, P2-type between initial charge/discharge processes is observed to be
layered materials are thermodynamically stabilized under a 20 mA h g−1 (Figure 10c), which is clearly reduced in compar-
sodium-deficient condition,[7] such as Na2/3[Fe1/2Mn1/2]O2, in ison to that of P2-Na2/3[Fe1/2Mn1/2]O2 (60 mA h g−1). Direct syn-
which 1/3 of sodium sites exists as vacancies. Therefore, large thesis of Na-enriched P2-phase is one of the potential strategies
capacity (190 mA h g−1, corresponding to 0.73 mol of Na+) for to reduce sodium-ion deficiency in P2-type layered oxides.
P2-Na2/3[Fe1/2Mn1/2]O2 is only achieved after the compensation P2-type Na2/3MnO2 also shows high reversible capacity,
of deficient sodium ions in the structure. For instance, a half- as shown in Figure S6 (see the Supporting Information),
cell with metallic sodium (i.e., a Na/Na2/3[Fe1/2Mn1/2]O2 cell) when a suitable electrolyte additive (such as FEC) is utilized.
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Figure 16. Changes in SXRD patterns of two layered polymorphs: a) O2-, and, b) O3-type Lix[Li1/4Mn3/4]O2 during continuous cycles in Li cells. Sche-
matic illustrations of phase transition for O2 and O3-phases are also compared in the insets. The O2-phase is stable after the continuous cycle test
whereas the O3-phase easily changes into the spinel phase having the same CCP oxygen array associated with the migration of Mn3+.
However, P2-type Na2/3MnO2 has disadvantages as the elec- The substitution of Fe3+ for Mn3+ in P2-type Na2/3MnO2, i.e.,
trode materials for rechargeable batteries: i) lower operating Na2/3[Fe1/2Mn1/2]O2, increases operating voltage, as reported
voltage (energy density) with a Mn3+/Mn4+ redox couple in our previous paper,[33] because a Fe3+/Fe4+ redox couple has
(3.5 V vs. Na metal as the maximum) in oxide-ion frame- higher potential than the Mn3+/Mn4+ redox couple. Although
work structures, and, ii) complicated phase transition associ- a Ni2+/Ni4+ redox couple is also a good candidate to increase
ated with large repulsive interaction between Na ions (elec- the operating voltage, e.g., P2-Na2/3[Ni1/3Mn2/3]O2[65] and
tronic and atomic size effects) because in-plane ordering of P2- Na0.85[Li0.17Ni0.21Mn0.64]O2[79], the utilization of nickel
Na ions shows a deteriorating tendency in rate-capability.[78] ions as a less-abundant element is preferably minimized for
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Figure 17. The impact of “pre-cycles” on electrode performance of O2-type Lix[Li1/4Mn3/4]O2 in the Li cell. The Li cell was cycled at a rate of 15 mA g−1
in the voltage range 2.0–4.8 V: a) charge/discharge curves with differential capacity plots, and, b) reversible capacity retention. Electrode performance
is highly improved by “pre-cycles” in the Li cell. Also see Figure S7 in the Supporting Information for detailed conditions used for “pre-cycles”.
large-scale batteries. The substitution of Li+ and enrichment element, being classified as a minor metal. However, the
of Mn4+ in the P2-type framework structures also raises oper- concept of utilization of oxide ions in redox reactions could be
ating voltage of manganese-based layered oxides. Discharge extended to other abundant elements to substitute for manga-
starts from over 4.0 V, as shown in Figures 10c and 11b. It is nese ions.
believed that the contribution of oxide ions in redox reactions, The substitution of lithium for manganese ions also influ-
similar to Li2MnO3-based electrode materials,[13,16,28,67] could ences phase transition in relation to a miscibility gap, single-
be responsible for the increase in average operating voltage. phase reaction (as solid solution) or two-phase separation,
Similar to nickel, lithium is also known as a less-abundant which is another advantage as an electrode material. Several
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sets of voltage plateaus are observed for P2-NaxMnO2, but such 4. Conclusions
plateaus are not seen in P2-Nax[Li1/4Mn3/4]O2. The voltage
profile of P2-Nax[Li1/4Mn3/4]O2 in the Na cell almost linearly Na ions provide greater structural diversity as layered mate-
changes from 4.0 to 1.5 V on discharge. Since phase bounda- rials compared with Li ions, and thus P2-type layered struc-
ries are always required to move across the inside particles for tures with open channels for solid-state Na diffusion are
the samples with two-phase reactions, its rate-capability is also energetically stabilized. The P2-type Li-excess manganese
limited as an electrode material.[78] Non-stoichiometry with Li- oxide Na5/6[Li1/4Mn3/4]O2 was first prepared by a conventional
substitution and/or oxygen vacancies induced in the crystal solid-state method. The O2-type Li-excess manganese oxide
lattice after the activation process could influence such phase Lix[Li1/4Mn3/4]O2, with unusual oxygen packing, was prepared
transition behavior during electrochemical Na insertion/extrac- from the P2-type precursor by Na/Li ion-exchange in a molten
tion processes. In fact, good rate-capability has been dem- salt. Detailed structural analysis on P2-type Na5/6[Li1/4Mn3/4]O2
onstrated for P2-Nax[Li1/4Mn3/4]O2 in the Na cell with small reveals that the sample consists of two MeO2 layers with partial
polarization in Figure 11b. Micrometer-sized samples without in-plane √3a × √3a-type cation ordering, and Na ions located at
carbon coating can deliver high-reversible capacity at higher splitting edge-/face-shared sites between the superlattice layers.
rates. The partial in-plane √3a × √3a-type cation ordering still exists
Additionally, small volume changes on charge/discharge after ion exchange even though Na/Li ion exchange results
are found for Nax[Li1/4Mn3/4]O2 as P2-type sodium insertion in gliding of MeO2 layers to form O2-phases. This study also
materials. Framework structures of the P2-type phase are gen- focused on how Li ions in MeO2 layers influence the electrode
erally stabilized by the existence of sodium ions. Therefore, performance of P2/O2-type Li-excess manganese oxides in Na/
sodium extraction from P2-type phases tends toward phase Li cells. Electrode performance in both Na/Li cells is signifi-
transition into O2-phaes. As shown in Figure 1, the interlayer cantly improved after the appearance of voltage plateaus. Since
distance of P2-type (and P3-type) layered oxides is increased by in-plane cation ordering is not observed after charge beyond
large repulsive interaction between negatively charged oxide the voltage plateaus, structural reorganization processes are
ions. Phase transition to the O2-phase is accompanied with proposed to take place, which are expected to be accompa-
drastic shrinkage for the interlayer distance because of reduced nied by partial oxygen loss similar to O3-type Li-excess layered
repulsive interaction between MeO2 layers. For instance, oxides. The O2-type phase in Li cells delivers high reversible
P2-Na2/3[Ni1/3Mn2/3]O2 transforms into O2-䊐[Ni1/3Mn2/3]O2 capacity, more than 200 mA h g−1, without nickel and cobalt
(“䊐” denotes vacant octahedral sites left between [Ni1/3Mn2/3]O2 substitution. Moreover, unfavorable phase transitions, such as
layers after sodium extraction),[65] and the percentage of volume the spinel-like phase transition during electrochemical cycles,
shrinkage is calculated to be 30% (average interlayer distances; are effectively suppressed because of unusual oxygen packing
5.6 Å for the P2-phase to 4.4 Å for the O2-phase). Cyclability is, in the O2-phase. Li substitution for manganese also effectively
therefore, insufficient as an electrode material.[63] The volume suppresses the complicated phase transition for the P2-phase
change is reduced for P2-Na2/3[Fe1/2Mn1/2]O2 because OP4-type in Na cells, presumably because of non-stoichiometric charac-
Nax[Fe1/2Mn1/2]O2, which is an intergrowth phase between P2- ters induced by structural rearrangement on charge. It is con-
and O2-phases, is formed in the fully charged state,[33] and the cluded that Li substitution for Mn ions in the P2-type phase
percentage of volume change is calculated to be 13% (average is highly beneficial to enhance its electrode performance, and
interlayer distances; 5.61 Å for the P2-phase to 5.15 Å for the P2/O2-type Li-excess manganese-based electrode materials are
OP4-phase); note that phase transition with volume change is a promising system as multi-functional electrode materials for
drastically reduced for Nax[Li1/4Mn3/4]O2. The formation of O2- rechargeable Na/Li batteries.
or OP4-phase is not evidenced for Nax[Li1/4Mn3/4]O2 even in the
fully-charged state (Figures 12b and 12b). It is found to form
the minor P2-phase that has slightly shorter interlayer distance Supporting Information
(5.4 Å) than that of the main phase (5.6 Å). The percentage of
volume change is calculated to be only 3% with the minor phase, Supporting Information is available from the Wiley Online Library or
which has smaller unit-cell volume than the major phase. Such from the author.
small volume change on electrochemical cycles without the for-
mation of O2-domains could be highly beneficial to achieve long
cycle life. Acknowledgements
In this article, we have demonstrated that lithium-substi- This study was in part granted by JSPS through the “Funding for NEXT
tuted manganese oxides with P2-type layered structures have Program,” and the MEXT program “Elements Strategy Initiative to
attractive characteristics as positive electrode materials for Form Core Research Center” (since 2012), MEXT; Ministry of Education
rechargeable sodium batteries. These characteristics are useful Culture, Sports, Science and Technology, Japan. The SXRD experiments
to compensate for the disadvantages of P2-type layered mate- were made possible through the support of the Japanese Ministry
rials, such as sodium deficiency, complicated phase transition, of Education, Science, Sports and Culture, and the Nanotechnology
and large volume change. We believe that the optimal design of Support Project (Proposal No. 2012B1777 and 2013A1681), with the
approval of the Japan Synchrotron Radiation Research Institute (JASRI).
P2-type layered oxides through these methodologies can further
The neutron-scattering experiment was approved by the Neutron
improve electrode properties, leading to cost-effective and high- Science Proposal Review Committee of J-PARC/MLF (Proposal No.
energy rechargeable batteries systems based on sodium and 2011A0023 and 2012B0046) and supported by the Inter-University
manganese ions in the future. Research Program on Neutron Scattering of IMSS, KEK. N.Y. gratefully
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acknowledges the support of a Grant-in-Aid for Young Scientists (B) [30] C. Delmas, J.-J. Braconnier, C. Fouassier, P. Hagenmuller, Solid
(No. 24750186) from MEXT. State Ionics 1981, 3–4, 165.
[31] J. Reed, G. Ceder, Chem. Rev. 2004, 104, 4513.
Received: September 23, 2013 [32] K. Momma, F. Izumi, J. Appl. Crystallogr. 2008, 41, 653.
Revised: February 17, 2014 [33] N. Yabuuchi, M. Kajiyama, J. Iwatate, H. Nishikawa, S. Hitomi,
Published online: R. Okuyama, R. Usui, Y. Yamada, S. Komaba, Nat. Mater. 2012, 11,
512.
[34] S. Komaba, L. Croguennec, F. Tournadre, P. Willmann, C. Delmas,
J. Phys. Chem. C 2013, 117, 3264.
[1] M. S. Whittingham, Chem. Rev. 2004, 104, 4271. [35] E. Nishibori, M. Takata, K. Kato, M. Sakata, Y. Kubota, S. Aoyagi,
[2] Z. H. Lu, L. Y. Beaulieu, R. A. Donaberger, C. L. Thomas, J. R. Dahn, Y. Kuroiwa, M. Yamakata, N. Ikeda, Nucl. Instrum. Methods Phys.
J. Electrochem. Soc. 2002, 149, A778. Res. 2001, 467, 1045.
[3] A. D. Robertson, P. G. Bruce, Chem. Mater. 2003, 15, 1984. [36] F. Izumi, K. Momma, Solid State Phenom. 2007, 130, 15.
[4] A. R. Armstrong, N. Dupre, A. J. Paterson, C. P. Grey, P. G. Bruce, [37] F. A. Izumi, R. A. Dilanian, Recent Res. Dev. Phys. 2002, 3, 699.
Chem. Mater. 2004, 16, 3106. [38] T. Ishigaki, A. Hoshikawa, M. Yonemura, T. Morishima,
[5] C. S. Johnson, J. S. Kim, C. Lefief, N. Li, J. T. Vaughey, T. Kamiyama, R. Oishi, K. Aizawa, T. Sakuma, Y. Tomota, M. Arai,
M. M. Thackeray, Electrochem. Commun. 2004, 6, 1085. M. Hayashi, K. Ebata, Y. Takano, K. Komatsuzaki, H. Asano,
[6] P. Strobel, B. Lambertandron, J. Solid State Chem. 1988, 75, 90. Y. Takano, T. Kasao, Nucl. Instrum. Methods Phys. Res. 2009, 600,
[7] C. Delmas, C. Fouassier, P. Hagenmuller, Physica B & C 1980, 99, 189.
81. [39] R. Oishi, M. Yonemura, Y. Nishimaki, S. Torii, A. Hoshikawa,
[8] B. Ammundsen, J. Paulsen, Adv. Mater. 2001, 13, 943. T. Ishigaki, T. Morishima, K. Mori, T. Kamiyama, Nucl. Instrum.
[9] P. Kalyani, S. Chitra, T. Mohan, S. Gopukumar, J. Power Sources Methods Phys. Res. 2009, 600, 94.
1999, 80, 103. [40] M. M. J. Treacy, J. M. Newsam, M. W. Deem, Proc. R. Soc. London A
[10] D. Y. W. Yu, K. Yanagida, Y. Kato, H. Nakamura, J. Electrochem. Soc. 1991, 433, 499.
2009, 156, A417. [41] S. Komaba, T. Ishikawa, N. Yabuuchi, W. Murata, A. Ito, Y. Ohsawa,
[11] Z. H. Lu, D. D. MacNeil, J. R. Dahn, Electrochem. Solid State Lett. ACS Appl. Mater. Interfaces 2011, 3, 4165.
2001, 4, A191. [42] R. D. Shannon, Acta Crystallogr. Sect. A 1976, 32, 751.
[12] J. H. Lim, H. Bang, K. S. Lee, K. Amine, Y. K. Sun, J. Power Sources [43] J. M. Paulsen, R. A. Donaberger, J. R. Dahn, Chem. Mater. 2000, 12,
2009, 189, 571. 2257.
[13] N. Yabuuchi, K. Yoshii, S.-T. Myung, I. Nakai, S. Komaba, J. Am. [44] Z. Lu, R. A. Donaberger, J. R. Dahn, Chem. Mater. 2000, 12, 3583.
Chem. Soc. 2011, 133, 4404. [45] Q. Huang, M. L. Foo, R. A. Pascal Jr., J. W. Lynn, B. H. Toby, T. He,
[14] H. Koga, L. Croguennec, P. Mannessiez, M. Menetrier, F. Weill, H. W. Zandbergen, R. J. Cava, Phys. Rev. B 2004, 70, 184110.
L. Bourgeois, M. Duttine, E. Suard, C. Delmas, J. Phys. Chem. C [46] R. Berthelot, D. Carlier, C. Delmas, Nat. Mater. 2011, 10, 74.
2012, 116, 13497. [47] M. Guignard, C. Didier, J. Darriet, P. Bordet, E. Elkaïm, C. Delmas,
[15] Y. Li, M. Bettge, B. Polzin, Y. Zhu, M. Balasubramanian, Nat. Mater. 2013, 12, 74.
D. P. Abraham, J. Electrochem. Soc. 2013, 160, A3006. [48] D. Carlier, J. H. Cheng, R. Berthelot, M. Guignard, M. Yoncheva,
[16] T. Ohzuku, M. Nagayama, K. Tsuji, K. Ariyoshi, J. Mater. Chem. R. Stoyanova, B. J. Hwang, C. Delmas, Dalton Trans. 2011, 40,
2011, 21, 10179. 9306.
[17] J. M. Zheng, Z. R. Zhang, X. B. Wu, Z. X. Dong, Z. Zhu, Y. Yang, J. [49] R. J. Balsys, R. Lindsay Davis, Solid State Ionics 1994, 69, 69.
Electrochem. Soc. 2008, 155, A775. [50] R. Berthelot, M. Pollet, D. Carlier, C. Delmas, Inorg. Chem. 2011, 50,
[18] A. Ito, D. Li, Y. Sato, M. Arao, M. Watanabe, M. Hatano, H. Horie, 2420.
Y. Ohsawa, J. Power Sources 2010, 195, 567. [51] M. Yashima, M. Itoh, Y. Inaguma, Y. Morii, J. Am. Chem. Soc. 2005,
[19] A. Ito, D. Li, Y. Ohsawa, Y. Sato, J. Power Sources 2008, 183, 344. 127, 3491.
[20] Y. Koyama, I. Tanaka, M. Nagao, R. Kanno, J. Power Sources 2009, [52] C. A. Geiger, E. Alekseev, B. Lazic, M. Fisch, T. Armbruster,
189, 798. R. Langner, M. Fechtelkord, N. Kim, T. Pettke, W. Weppner, Inorg.
[21] A. R. Armstrong, M. Holzapfel, P. Novak, C. S. Johnson, S. H. Kang, Chem. 2010, 50, 1089.
M. M. Thackeray, P. G. Bruce, J. Am. Chem. Soc. 2006, 128, [53] R. Jalem, Y. Yamamoto, H. Shiiba, M. Nakayama, H. Munakata,
8694. T. Kasuga, K. Kanamura, Chem. Mater. 2013, 25, 425.
[22] M. Jiang, B. Key, Y. S. Meng, C. P. Grey, Chem. Mater. 2009, 21, [54] C. Delmas, J.-J. Braconnier, P. Hagenmuller, Mater. Res. Bull. 1982,
2733. 17, 117.
[23] M. Gu, I. Belharouak, J. Zheng, H. Wu, J. Xiao, A. Genc, K. Amine, [55] D. Carlier, I. Saadoune, L. Croguennec, M. Ménétrier, E. Suard,
S. Thevuthasan, D. R. Baer, J.-G. Zhang, N. D. Browning, J. Liu, C. Delmas, Solid State Ionics 2001, 144, 263.
C. Wang, ACS Nano 2013, 7, 760. [56] F. Tournadre, L. Croguennec, I. Saadoune, D. Carlier, Y. Shao-Horn,
[24] J. R. Croy, D. Kim, M. Balasubramanian, K. Gallagher, S. H. Kang, P. Willmann, C. Delmas, J. Solid State Chem. 2004, 177, 2790.
M. M. Thackeray, J. Electrochem. Soc. 2012, 159, A781. [57] Z. H. Lu, J. R. Dahn, Chem. Mater. 2001, 13, 2078.
[25] T. Ohzuku, S. Kitano, M. Iwanaga, H. Matsuno, R. Ueda, J. Power [58] S. Komaba, K. Yoshii, A. Ogata, I. Nakai, Electrochim. Acta 2009, 54,
Sources 1997, 68, 646. 2353.
[26] Y. I. Jang, B. Y. Huang, H. F. Wang, D. R. Sadoway, Y. M. Chiang, J. [59] N. Yabuuchi, Y. Kawamoto, R. Hara, T. Ishigaki, A. Hoshikawa,
Electrochem. Soc. 1999, 146, 3217. M. Yonemura, T. Kamiyama, S. Komaba, Inorg. Chem. 2013, 52,
[27] M. Tabuchi, K. Ado, H. Kobayashi, H. Kageyama, C. Masquelier, 9131.
A. Kondo, R. Kanno, J. Electrochem. Soc. 1998, 145, L49. [60] J. Bréger, M. Jiang, N. Dupré, Y. S. Meng, Y. Shao-Horn, G. Ceder,
[28] Y. I. Jang, B. Y. Huang, Y. M. Chiang, D. R. Sadoway, Electrochem. C. P. Grey, J. Solid State Chem. 2005, 178, 2575.
Solid State Lett. 1998, 1, 13. [61] N. Yabuuchi, K. Yamamoto, K. Yoshii, I. Nakai, T. Nishizawa,
[29] J. M. Paulsen, C. L. Thomas, J. R. Dahn, J. Electrochem. Soc. 1999, A. Omaru, T. Toyooka, S. Komaba, J. Electrochem. Soc. 2013, 160,
146, 3560. A39.
www.advenergymat.de
FULL PAPER
[62] S. P. Ong, V. L. Chevrier, G. Hautier, A. Jain, C. Moore, S. Kim, [71] M. K. Aydinol, A. F. Kohan, G. Ceder, K. Cho, J. Joannopoulos, Phys.
X. Ma, G. Ceder, Energy Environ. Sci. 2011, 4, 3680. Rev. B 1997, 56, 1354.
[63] D. H. Lee, J. Xu, Y. S. Meng, Phys. Chem. Chem. Phys. 2013, 15, 3304. [72] J. M. Tarascon, G. Vaughan, Y. Chabre, L. Seguin, M. Anne,
[64] A. Van der Ven, G. Ceder, M. Asta, P. D. Tepesch, Phys. Rev. B 2001, P. Strobel, G. Amatucci, J. Solid State Chem. 1999, 147, 410.
64, 184307. [73] N. Yabuuchi, Y.-T. Kim, H. H. Li, Y. Shao-Horn, Chem. Mater. 2008,
[65] Z. Lu, J. R. Dahn, J. Electrochem. Soc. 2001, 148, A1225. 20, 4936.
[66] M. D. Slater, D. Kim, E. Lee, C. S. Johnson, Adv. Funct. Mater. 2013, [74] D. Kim, S.-H. Kang, M. Balasubramanian, C. S. Johnson, Electro-
23, 947. chem. Commun. 2010, 12, 1618.
[67] H. Koga, L. Croguennec, M. Ménétrier, K. Douhil, S. Belin, [75] D. A. Stevens, J. R. Dahn, J. Electrochem. Soc. 2000, 147,
L. Bourgeois, E. Suard, F. Weill, C. Delmas, J. Electrochem. Soc. 1271.
2013, 160, A786. [76] S. Komaba, W. Murata, T. Ishikawa, N. Yabuuchi, T. Ozeki,
[68] M. Sathiya, G. Rousse, K. Ramesha, C. P. Laisa, H. Vezin, T. Nakayama, A. Ogata, K. Gotoh, K. Fujiwara, Adv. Funct. Mater.
M. T. Sougrati, M. L. Doublet, D. Foix, D. Gonbeau, W. Walker, 2011, 21, 3859.
A. S. Prakash, M. Ben Hassine, L. Dupont, J. M. Tarascon, Nat. [77] P. Senguttuvan, G. Rousse l., V. Seznec, J.-M. Tarascon,
Mater. 2013, 12, 827. M. R. Palacín, Chem. Mater. 2011, 32, 4109.
[69] J. R. Croy, K. G. Gallagher, M. Balasubramanian, Z. Chen, Y. Ren, [78] H. Yoshida, N. Yabuuchi, S. Komaba, Electrochem. Commun. 2013,
D. Kim, S.-H. Kang, D. W. Dees, M. M. Thackeray, J. Phys. Chem. C 34, 60.
2013, 117, 6525. [79] D. Kim, S.-H. Kang, M. Slater, S. Rood, J. T. Vaughey, N. Karan,
[70] L. Blandeau, G. Ouvrard, Y. Calage, R. Brec, J. Rouxel, J. Phys. C: M. Balasubramanian, C. S. Johnson, Adv. Energy Mater. 2011, 1,
Solid State Phys. 1987, 20, 4271. 333.
Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany, 2014.
Supporting Information
for Adv. Energy Mater., DOI: 10.1002/aenm.201301453
New O2/P2-type Li-Excess Layered Manganese Oxides

as Promising Multi-Functional Electrode Materials for
Rechargeable Li/Na Batteries
Naoaki Yabuuchi, Ryo Hara, Masataka Kajiyama, Kei
Kubota, Toru Ishigaki, Akinori Hoshikawa, and Shinichi
Komaba*
Supporting Information for
New O2/P2-type Li-Excess Layered Manganese Oxides as Promising
Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries
Naoaki Yabuuchi1,2, Ryo Hara1, Masataka Kajiyama1, Kei Kubota1, Toru Ishigaki3,
Akinori Hoshikawa3, and Shinichi Komaba1,2*
1
Department of Applied Chemistry, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku,
Tokyo 162-8601, Japan
2
Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Katsura, Kyoto, 615-8520, Japan
3 Frontier Research Center for Applied Atomic Sciences, Ibaraki University, Tokai, Ibaraki, Japan
*corresponding author; komaba@rs.kagu.tus.ac.jp

P2‐Na5/6[Li1/4Mn3/4]O2
S.G. : P63 ; a = 4.9671(3) Å, c = 11.039(1) Å
Rwp = 9.62% RB = 10.82% RF = 7.59%
atom site g x y z B (Å2)

Naf (1) 2a 0.312(3) 0 0 1/4 0.7
Naf (2) 2b 0.312(3) 1/3 2/3 1/4 0.7
Naf (3) 2b 0.312(3) 2/3 1/3 1/4 0.7
Nae (4) 6c 0.518(3) 1/3 0 1/4 0.7
Li (1) 2a 0.121(3) 0 0 0 0.47(3)
Mn (1) 2a 0.879(3) 0 0 0 0.47(3)
Li (2) 2b 0.121(3) 2/3 1/3 0 0.47(3)
Mn (2) 2b 0.879(3) 2/3 1/3 0 0.47(3)
Li (3) 2b 0.478(3) 1/3 2/3 0 0.47(3)
Mn (3) 2b 0.522(3) 1/3 2/3 0 0.47(3)
O (1) 6c 1.0 0.346(3) 0.346(3) 0.087(1) 1.2(1)
O (2) 6c 1.0 0.662(4) 0.662(4) 0.913(1) 1.2(1)
obs.
cal.
delta
bragg position
5 10 15 20 25 30
2 / deg. ( = 0.5 Å)
Figure S1a. A result of the Rietveld analysis and refined crystallographic parameters on the SXRD pattern of
P2-type Na5/6[Li1/4Mn3/4]O2 with the restriction on isotropic displacement parameters, B, for Na sites. The values
2
of B for Na sites were fixed to be 0.7 Å . The criteria of fit are not satisfactory under this restriction.
P2‐Na5/6[Li1/4Mn3/4]O2
S.G. : P63 ; a = 4.9672(2) Å, c = 11.039(1) Å
Rwp = 7.75% RB = 7.24% RF = 6.21%

Naf (1) 2a 0.327(3) 0 0 1/4 5.3(2)
Naf (2) 2b 0.327(3) 1/3 2/3 1/4 5.3(2)
Naf (3) 2b 0.327(3) 2/3 1/3 1/4 5.3(2)
Nae (4) 6c 0.503(3) 1/3 0 1/4 3.9(2)
Li (1) 2a 0.121(3) 0 0 0 0.55(2)
Mn (1) 2a 0.879(3) 0 0 0 0.55(2)
Li (2) 2b 0.121(3) 2/3 1/3 0 0.55(2)
Mn (2) 2b 0.879(3) 2/3 1/3 0 0.55(2)
Li (3) 2b 0.478(3) 1/3 2/3 0 0.55(2)
Mn (3) 2b 0.522(3) 1/3 2/3 0 0.55(2)
O (1) 6c 1.0 0.343(3) 0.343(3) 0.087(1) 1.2(1)
O (2) 6c 1.0 0.661(3) 0.661(3) 0.913(1) 1.2(1)
obs.
cal.
delta
bragg position
5 10 15 20 25 30
2 / deg. ( = 0.5 Å)
Figure S1b. A result of the Rietveld analysis without the restriction on isotropic displacement parameters, B, for
Na sites. Although the criteria of fit are sufficiently improved without the restriction, the B values are found to be
anomalously large (> 3.0 Å2).
P2‐Na5/6[Li1/4Mn3/4]O2
S.G. : P63 ; a = 4.9860(2) Å, c = 11.103(1) Å
Rwp = 7.80% RB = 6.80% RF = 6.30%

Naf (1) 2a 0.332(3) 0 0 1/4 7.1(3)
Naf (2) 2b 0.332(3) 1/3 2/3 1/4 7.1(3)
Naf (3) 2b 0.332(3) 2/3 1/3 1/4 7.1(3)
Nae (4) 6c 0.499(3) 1/3 0 1/4 5.6(2)
Li (1) 2a 0.121(3) 0 0 0 0.83(2)
Mn (1) 2a 0.879(3) 0 0 0 0.83(2)
Li (2) 2b 0.121(3) 2/3 1/3 0 0.83(2)
Mn (2) 2b 0.879(3) 2/3 1/3 0 0.83(2)
Li (3) 2b 0.478(3) 1/3 2/3 0 0.83(2)
Mn (3) 2b 0.522(3) 1/3 2/3 0 0.83(2)
O (1) 6c 1.0 0.343(3) 0.343(3) 0.086(1) 1.5(1)
O (2) 6c 1.0 0.660(3) 0.660(3) 0.914(1) 1.5(1)
obs.
cal.
delta
bragg position
5 10 15 20 25 30
2 / deg. ( = 0.5 Å)
Figure S2. The result of the Rietveld analysis and refined crystallographic parameters on the XRD pattern of
P2-type Na5/6[Li1/4Mn3/4]O2 collected at 470 oC. Clear increase in B-values is noted at elevated temperature.
P2‐Na5/6[Li1/4Mn3/4]O2
S.G. : P63/mmc; a = 2.8711(1) Å, c = 11.028(1) Å
Rwp = 8.12% RB = 5.07% RF = 6.15%

Naf 2b 0.320(1) 0 0 1/4 3.7(1)
Nae 2d 0.510(1) 1/3 2/3 3/4 2.3(1)
Li 2a 0.24 0 0 0 0.12(1)
Mn 2a 0.76 0 0 0 0.12(1)
O 4f 1.000(1) 1/3 2/3 0.094(1) 0.56(1)
010
013
012
006
011
004
114
obs.
110
cal.
017
0.5 1.0 1.5 2.0 2.5 3.0

d/Å
Figure S3. The result of the Rietveld analysis and crystallographic parameters refined on the ND pattern of
P2-type Na5/6[Li1/4Mn3/4]O2.
Li / Lix[Li1/4Mn3/4]O2
6
5 2.0 – 4.8 V
4
200 mAh g‐1
3
Voltage / V
2
1
6
5 2.0 – 4.4 V
4
3 100 mAh g‐1 1st
2nd
2 5th
1
0 50 100 150 200 250
-1
Capacity / mAh g
Figure S4. Galvanostatic charge and discharge curves of Li/O2-Lix[Li1/4Mn3/4]O2 cells with different cut-off
voltage; 4.4 and 4.8 V. Reversible capacity is significantly increased by charge to high voltage of 4.8 V.
Na/ Na5/6[Li1/4Mn3/4]O2
5
1.5 – 4.4 V
Voltage / V
4
1st
3 2nd
190 mAh g-1 10th
1
5
1.5 – 3.6 V
Voltage / V
4
1st
2nd
3
3rd
60 mAh g-1
2
1
0 50 100 150 200 250
-1
Capacity / mAh g
Figure S5 Galvanostatic charge and discharge curves of Na/P2-Na5/6[Li1/4Mn3/4]O2 cells with different cut-off
voltage; 3.6 and 4.4 V. Reversible capacity is significantly increased by charge to high voltage of 4.4 V similar to
the O2-phase in Li cells.
5 5
(a) Hex. P2-type Na0.7MnO2 (b) P2-type Na5/6[Li1/4Mn3/4]O2
4 4
Voltage / V
Voltage / V
3 3
2 2
5th cycle 5th cycle

1 1
0 50 100 150 200 0 50 100 150 200
-1 -1
Capacity / mAh g Capacity / mAh g
Figure S6. Comparison of charge/discharge curves for Na/P2-NaxMnO2 and Na/P2-Na5/6[Li1/4Mn3/4]O2 cells at
the 5th cycle at a rate of 15 mA g-1. Large polarization is a characteristic feature of Na5/6[Li1/4Mn3/4]O2 as
electrode materials in Na cells, similar to Li2MnO3-based materials in Li cells. Many voltage plateaus are
observed in P2-NaxMnO2 that is indicative of phase transitions associated with Na ions ordering.
Pre-cycle condition
2.0 – 4.5 V at 55 mA/g (2 cycles)

2.0 – 4.6 V at 55 mA/g (2 cycles)
2.0 – 4.7 V at 55 mA/g (2 cycles)
2.0 – 4.8 V at 15 mA/g (1st cycle in Figure 13)
5 1st 6th
Voltage / V
2
1st 6th
1
0
0 50 100 150 200 250
-1
Capacity / mAhg
Figure S7. Experimental conditions used for the “pre-cycles” on Li/O2-Lix[Li1/4Mn3/4]O2 cells. After these
pre-cycles, the Li cell was further cycled for 50 cycles in Figure 17.

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New O2/P2-type Li-Excess Layered Manganese Oxides

sustainable energy development. This

2. Experimental Section 2.3. Electrochemical Characterization

and Mn ions are located at octahedral sites in

Atom Site g x y z B [Å2]

faults are summarized in Figure 7. MeO2

O2′-phase is formed as shown in Figure 7.

The difference between O2- and O2’-phases

planes between MeO6 and LiO6 octahedra.

(the rotation axis is directed perpendicular

to the page), the O2′-phase is superimposed

to the O2-phase. Both phases are formed

with the minimum numbers in layer gliding

(50%). The formation of these phases should

Here, the formation rate of ion-exchange

3.4. Changes in Crystal Structures of O2-Lix[Li1/4Mn3/4]O2

In the previous section, we demonstrated that O2-type

in Li cells and P2-type Nay[LixMn1-x]O2 in Na

New O2/P2-type Li-Excess Layered Manganese Oxides

New O2/P2-type Li-Excess Layered Manganese Oxides as Promising

Multi-Functional Electrode Materials for Rechargeable Li/Na Batteries

Akinori Hoshikawa3, and Shinichi Komaba1,2*

Tokyo 162-8601, Japan

*corresponding author; komaba@rs.kagu.tus.ac.jp

atom site g x y z B (Å2)

atom site g x y z B (Å2)

atom site g x y z B (Å2)

atom site g x y z B (Å2)

0.5 1.0 1.5 2.0 2.5 3.0

5th cycle 5th cycle

2.0 – 4.5 V at 55 mA/g (2 cycles)

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