Langmuir 1992, 8, 1861-1867 1861

Li+ Extraction/insertion with Spinel-Type Lithium

Manganese Oxides. Characterization of Redox-Type and
Ion-Exchange-Type Sites
Qi Feng,* Yoshitaka Miyai, Hirofumi Kanoh, and Kenta Ooi*
Government Industrial Research Institute, Shikoku, 2-3-3 Hananomiya-cho,
Takamatsu 761, Japan

Received October 22, 1991. In Final Form: April 1, 1992

Spinel-type lithium manganese oxides which can be expressed by a general formula Li„Mn2-,04 (1 <
< 1.33, 0 < x < 0.33, < 1 + x) were prepared by reacting MnCOg with LÍ2CO3 at 400 °C and 800 °C.
The extraction/insertion reactions of lithium ions with the spinel samples were investigated by chemical,
X-ray, and thermal analyses, FT-IR spectroscopy, and pH titration. Lithium ions were extracted/inserted
by two different mechanisms: redox type and ion exchange type. Therefore, the Li+ extraction/insertion
sites could be classified into redox type and ion exchange type. Li* ions were preferentially extracted/
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inserted from/into the ion-exchange sites. The spinel-type lithium manganese oxides could be divided
into two parts: those with trivalent Mn ions and those with only tetravsdent Mn ions (with Mn defects
in 16d octahedral sites). The numbers of redox-type and ion-exchange-type sites correlated well with the
amounts of trivalent Mn ions and the Mn defects, respectively. The proportions of the two types of sites
varied depending on preparation conditions (heat treatment temperature and Li/Mn mole ratio of starting
material) of the lithium manganese oxide spinels.

Introduction investigated the structures of the Li+ extracted and

Spinel-type lithium manganese oxides show excellent
selectivity for the adsorption of Li+ after topotactic
extraction of Li+ with an acid.1-10 The adsorptive prop-
erties make the material practicable as a Li+ adsorbent,1-7
a cathode material for lithium batteries,11-13 and an
electrode for selective electroinsertion of Li+.14 LiMn204
with lithium at the 8a tetrahedral sites and manganese-
(III) and manganese(IV) at the 16d octahedral sites of a
cubic closed-packed oxygen framework15 is a typical spinel-
type lithium manganese oxide. An acid treatment of
LiMn204 causes the removal of nearly all of the lithium
while maintaining the spinel structure. Hunter16 has
proposed a redox mechanism
4(Li) [ ] 04 + 8H+
—
3(D)[MnIV2]04 + 4Li+ + 2Mn2+ + 4H20 (1)
for the topotactic extraction of lithium and defined the
spinel-type manganese oxide obtained as - 02, where
(), [], and are 8a tetrahedral sites, 16d octahedral sites,
and vacant sites, respectively. Thackeray et al.u>12 ***have
(1) Vol’khin, V. V.; Leont'eva, G. V.; Onolin, S. A. Neorg. Mater. 1973,
6, 1041.
(2) Leont’eva, G. V.; Chirkova, L. G. Zh. Prikl. Khim. 1988, 61, 734.
(3) Shen, X. M.; Clearfield, A. J. Solid State Chem. 1986, 64, 270.
(4) Ooi, K.; Miyai, Y.; Katoh, S. Sep. Sci. Technol. 1986, 21, 755.
(5) Ooi, K.; Miyai, Y.; Katoh, S. Sep. Sci. Technol. 1987, 22, 1779.
(6) Ooi, K.; Miyai, Y.; Katoh, S. Solvent Extr. Ion Exch. 1987,5, 561.
(7) Ooi, K.; Miyai, Y.; Katoh, S.; Maeda, H.; Abe, M. Bull. Chem. Soc.
Jpn. 1988, 61, 407.
(8) Ooi, K.; Miyai, Y.; Katoh, S.; Maeda, H.; Abe, M. Chem. Lett. 1988,
989.
(9) Ooi, K.; Miyai, Y.; Katoh, S.; Maeda, H.; Abe, M. Langmuir 1989,
5, 150.
(10) Ooi, K.; Miyai, Y.; Katoh, S.; Maeda, H.; Abe, M. Langmuir 1990,
6, 289.
(11) Thackeray, . M.; David, W. I. F.; Bruce, P. G.; Goodenough, J.
B. Mater. Res. Bull. 1983,18, 461.
(12) Thackeray, . M.; Johnson, P. J.; Picciotto, L. A. De.; David, W.
I. F.; Bruce, P. G.; Goodenough, J. B. Mater. Res. Bull. 1984, 19, 179.
(13) Roesouw, . H.; Kock, A. De.; Picciotto, L. A. De.; Thackeray, M.
M.; David, W. I. F.; Ibberson, R. M. Mater. Res. Bull. 1990, 25, 173.
(14) Kanoh, H.; Ooi, K.; Miyai, Y.; Katoh, S. Langmuir 1991, 7,1841.
(15) Wickham, D. G.; Croft, W. J. Phys. Chem. Solid 1968, 7, 351.
(16) Hunter, J. C. J. Solid State Chem. 1981, 39, 142.
inserted manganese oxide in detail by X-ray and neutron
diffraction analyses.
We have studied the Li+ adsorptive properties of -
Mn02 in the aqueous phase. It shows a specific selectivity
for Li+ among alkali, alkaline-earth, and transition-metal
ions.6’7 *A stoichiometric investigation in the ( - 02 +
LiOH) system has shown that the insertion of Li4’ involves
an evolution of about a 90% equivalent amount of oxygen
gas, as well as a reduction of Mn(IV) to Mn(III) in the
solid phase.9 **But such reactions do not occur in the ( -
Mn02 + KOH) system. We have therefore proposed a
redox mechanism for the Li+ insertion
(ü)[MnIV2]04 + nLiOH —
(Li„D1_„)[MnIIInMnIV2_n]04 + (n/2)H20 + (n/4)02 (2)
After further study of the Li+ insertion reactions for the
spinel-type lithium manganese oxides prepared under
different conditions (Li/Mn mole ratio and temperature),
we have found that Li+-specific ion-exchange and non-
specific ion-exchange reactions also occur during lithium
insertion, in addition to the redox reaction of eq 2.17 We
have classified the insertion sites into three groups: redox-
type sites, Li+-specific ion-exchange sites, and nonspecific
ion-exchange sites. The proportion of each group varied
depending on the preparation conditions of the spinel-
type lithium manganese oxide precursors.
The present paper describes the origin of the two kinds
of sites (redox-type and ion-exchange-type) from the
chemical and structural standpoints. Lithium manganese
oxide spinels have distinct characteristics compared with
other oxide-type spinels, e.g. an easy conversion between
Mn(III) and Mn(IV) owing to the movement of electrons,
and an easy migration of Li4’ in the oxygen framework.
These characteristics enable the lithium manganese oxide
to have various kinds of spinels with different oxidation
states of Mn and with different Li/Mn mole ratios. For
example, Li1.33Mn1.e7CU or (Li) [Lio.ssMn^i.e?] 04 is a typical
(17) Ooi, K.; Miyai, Y.; Sakakihara, J. Langmuir 1991, 7, 1167.

0743-7463/92/2408-1861$03.00/0 &copy; 1992 American Chemical Society

1862 Langmuir, Vol. 8, No. 7, 1992 Feng et al.

spinel with Li/Mn = 0.8 and tetravalent Mn alone.1819 We

propose in the present paper that the spinel-type precursor
having trivalent Mn gives a redox-type site on the basis
of eq 1 while the precursor having only tetravalent Mn
gives an ion-exchange-type site by Li+/H+ ion exchange.

Experimental Section
Materials. Lithium manganese oxides were prepared by heat-
treating mixtures of MnCOa and Li2C03 with different Li/Mn
mole ratios for 4 h at 400 or 800 °C in air.
Li+ Extraction/Insertion Reactions. Li+ extraction/
insertion reactions were investigated at room temperature for
three kinds of lithium manganese oxides prepared under different
conditions (Li/Mn mole ratio, heating temperature): 0.5-800
(0.5,800 °C); 0.5-400 (0.5,400 °C); 0.8-400 (0.8,400 °C). In the
extraction study, lithium manganese oxide was immersed in a
0.2 (1 = 1 mol
dm'3) HC1 solution of varying volumes with
stirring for 2 days to obtain various kinds of lithium-extracted
samples. The samples were filtered, washed with water, and
air-dried at 70 °C. In the insertion study, 2 g of acid-treated
sample (0.5-800(H), 0.5-0.400(H), or 0.8-400(H) (Table II)) was
immersed in a LiOH solution (500 cm3) of varying concentration
with stirring for 4 days to obtain various kinds of lithium-inserted
samples. The inserted samples were filtered, washed with water,
and air-dried at 70 °C. The samples obtained from the highest
concentration (0.1 M) of LiOH were designated as 0.5-800(Li),
0. 5-400(Li), and 0.8-400(Li), respectively.
Figure 1. X-ray diffraction patterns of lithium manganese oxides
prepared at 400 °C with different Li/Mn mole ratios: O, peaks
Chemical Properties. The available oxygen of each sample
corresponding to spinel phase; , a-Mn203; , Li2Mn03.
was determined by the standard oxalic acid method.20 The mean
oxidation number (2m») of manganese was evaluated from the
value of available oxygen. The lithium and manganese contents
were determined after dissolving the sample with a mixed solution
of H2SO4 and H2O2. Lithium concentration was determined by
atomic absorption spectrometry and manganese by absorption
spectrometry at 523 nm after oxidizing Mn to Mn(VII) with
(NH4) 28203.
pH Titration. A 0.1-g portion of each acid-treated sample
was immersed in a mixed solution (10 mL) of MCI + MOH (M
Li, Na) in varying ratio with intermittent shaking at 25 °C. After
the sample was shaken for 7 days,14 the pH of the supernatant
solution was determined with a Horiba Model M8s pH meter.
Physical Analyses. An X-ray analysis was carried out using
a Rigaku type RAD-II X-ray diffractometer with graphite mono-
chromator. A mechanical deviation of diffraction angles was
corrected by scanning the whole range of angle with silicon
powder. Infrared spectra were obtained by the KBr method on
a JEOL infrared spectrometer, Model JTR-RFX3001. Differ-
ential thermal analysis and thermal gravimetric (DTA-TG)
curves were obtained on a MAC Science thermal analyzer (System
001, TG-DTA 2000) at a heating rate of 10 °C/min.

Results and Discussion

Preparation and Characterization of Spinel-Type
Lithium Manganese Oxides. X-ray diffraction patterns
of lithium manganese oxides prepared at 400 and 800 °C
with different Li/Mn mole ratios are shown in Figures 1
and 2, respectively. Pure spinel-type lithium manganese
oxides were obtained in a range of Li/Mn mole ratio from
0.5 to 0.8 at 400 °C, but only at 0.5 in the case of 800 °C
heating. A mixture of spinel-type lithium manganese oxide
and monoclinic LizMnOg was formed in the region Li/Mn
> 0.8 at 400 °C and Li/Mn > 0.5 at 800 °C; the proportion
of monoclinic LizMnOs increased with an increase in the
Li/Mn. In the region Li/Mn < 0.5, a-MnaOa phase (400
°C heating) and - ß phase (800 °C heating) were
formed in addition to the spinel-type phase. An analysis
of available oxygen showed that in the case of 400 °C
heating, the mean oxidation number of manganese (Zmd)
(18) Blasse, G. J. Inorg. Nucí. Chem. 1963, 25, 743.
(19) Blasse, G. Philips Res. Rep., Suppl. 1964, No. 3, 1.
(20) Japan Industrial Standard (JIS) Í969, M8233.
Figure 2. X-ray diffraction patterns of lithium manganese oxides
prepared at 800 °C with different Li/Mn mole ratios: O, peaks
corresponding to spinel phase; , - 203; , Li2Mn03.
of the lithium manganese oxide increases with the increase
of Li/Mn and reached 4 (tetravalence) at Li/Mn = 1, after
which it remained constant (Figure 3). The 2mh value is
lower for the sample 0.5-800 than for the sample 0.5-400.
Structure of Lithium Manganese Oxide Spinel.
The differences in the Li/Mn mole ratio and µ for these
spinels can be explained in terms of the distributions of
cations and vacant sites in the spinel. The spinel structure
has to satisfy the following conditions:
(3)
Li+ Extraction/Insertion Langmuir, Vol. 8, No. 7, 1992 1863

Table II. Cation Distributions and Values of z for

Spinel-Type Lithium Manganese Oxides
sample z cation distribution
0.5-800 0.78 (Lio.94-yDy+o.o6)[LiyOo.o4-yMnmo.78MnIvi.i8]04
0.5-400 0.57 I
(Lio,93-yOy+o.o7)[LiyOo.o9-yMn®o.57Mn* 2^i,34]04
0.65—400 0.33 (Lii.i3-yDy-o,i3)[LiyDo.2o-yMnmo.33MnIvi.47]04
0.8-400 0.18 (Lii.02) [Lio.2sMnII‘o.isMnrvi.54]04
LiMn204 1 (Li) [MnmMnIV] 04
Li1.33Mn1.e7O4 0 (Li)[Li0.33MnIvi.67]04

the spinels can be written as

(Lin-yD1_n+y) [LiyDx_yMnIIIzMnIV2_I_x] 04 (8)

Figure 3. Relation between mean oxidation number of Mn and
Li/Mn mole ratio for the lithium manganese oxides prepared at where y is number of Li+ distributed to 16d octahedral
400 °C (·) and 800 °C ( ).
sites (y < x) and z can be derived from
Table I. Compositional and Structural Parameters of
Spinel-Type Lithium Manganese Oxides z = n -

4x (9)
Since lithium is a very weak scatterer of X-rays, the position
sample 2ms Mn a0, A x n formula of Li+ (the value of y) cannot be determined from the
0.5—8Ó0 3.60 0.480 8.23 0.04 0.94 Li0.94D0.10Mn1.96O4 X-ray diffraction pattern. A neutron diffraction method
0.5-400 3.70 0.485 8.21 0.09 0.93 Lio.93Do.1eMm.91O4 may be the only method to determine the exact Li+
0.65-400 3.81 0.628 8.18 0.20 1.13 Li1.13D0.07Mn1.80O4 distribution. The neutron diffraction study on LÍ2Mn40g
0.8-400 3.89 0.754 8.14 0.28 1.30 Li1.30Mn1.72O4
spinel by Kock et al.21 has indicated that its cation
LiMn204 3.5 0.5 8.25° 0 1 LiMn204 distribution is (Lio.89Clo.11) [D0.22Mn1.7s] O4 with all Li+ in
Li1.33Mn1.67O4 4 0.8 8.19 0.33 1.33 Li1.33Mn1.67O4 8a tetrahedral sites. The other study by David et al.22 has
0
After ref 15. 6
After ref 19. indicated that Li+ occupy both 8a (tetrahedral) and 16c
(octahedral) sites in LÍ2Mn2(>4 and only 8a sites in Lio.2-
For the condition of electroneutrality, we have MnsCL.
The cation distributions and values of z for the present
= 8 (4) spinels are given in Table II. The proportions of Mn(III),
=
NqZ0
^NiZi Mn(IV), and Mn defects vary with the preparation
and for the spinel with tri- and tetravalent manganese conditions, in spite of the fact that they all have a spinel
phase. The number of Mn(III) increases with the increase
•^Mn(III) + ^Mn(IV) ^ 2 (5) of heat treatment temperature as well as with the decrease
where N¡ is the number of metal ion i, Nv the number of of Li/Mn ratio (Table II). The number of Mn defects
vacant sites of 8a and 16d, and No (=4) the number of varies in reverse order (Table I). The sample 0.5-800 is
oxygen anions in one structural unit. Z, and Zo (=2) are close to the normal spinel LiM^tX and 0.8-400 to the
valences of the metal ion i and oxygen anion, respectively. spinel Li1.33Mn1.67O4 in structure and composition, re-
The present spinels can be expressed by a general spectively.
formula Li„Mn2-x04 (1 < < 1.33, 0 < x < 0.33, < x + TG curves for the samples 0.5-400 and 0.8-400 show a
1) or LinGi-n+xMn2-x04 using eqs 3,4, and 5, by considering weight loss between 500 and 700 °C; this corresponds to
the conditions 3.5 < 2µ < 4(0 < Mandil) < 1) and 0.5 < the transformation from the Mn defect spinal to LiM^iX
Li/Mn < 0.8. The values of x and n can be evaluated from and Li2Mn03, accompanied by an evolution of oxygen gas.
Zmd and lithium-manganese mole ratio (Li/Mn) as This indicates that the Mn defect spinel is metastable
follows: and transforms to the stable state at temperatures higher
than 500 °C.
2Mn
-
(8 -

n)/( 2-x) =
8/(2 -

x) -

Li/Mn (6) Li+ Extraction Reaction. Three kinds of lithium

manganese oxide spinels (0.5-800,0.5-400, and 0.8-400)
x =
2-8/(Li/Mn + ZmJ were used as original samples to investigate the mecha-
nism of Li+ extraction/insertion reactions. The Li+
n¡ (Li/Mn) = 2-x (7) extraction was carried out using an HC1 solution. The
2mh vs Li/Mn curves showed different variation patterns
n =
Li/Mn(2 x) -

with each lithium manganese oxide system (Figure 4). The

2Mn value in the 0.5-800 system linearly increased with
The compositional and structural parameters for the a decrease of Li/Mn ratio, while that in the 0.8-400 system
spinel-type lithium manganese oxides are summarized in was almost constant, except for a slight increase in the
Table I.
The lithium manganese oxide spinel prepared here have region Li/Mn < 0.2. The 0.5-400 system showed a two-
a structure with Mn not at 8a tetrahedral sites but at 16d
stage process; Zmh is almost constant from starting Li/Mn
(0.485) to about 0.25, and then linearly increases with a
octahedral sites, since the (220) and (422) reflections are decrease of Li/Mn with the same slope as that of the 0.5-
not observed in the X-ray powder patterns (Figure 1 and 800 system. The increases of 2mh were attended by the
2) .1B Therefore, spinels have a framework (D)[DxMnmz- dissolution of Mn2+ ions in the extraction reactions.
MnIV2-x-z]04 (0 < z < 1) with Mn defects in 16d octahedral
sites; here x is the number of the Mn defect and z the
number of tirvalent Mn. Li+ can be distributed to both (21) Kock, A. De.; Rossouw, . H.; Picciotto, L. A.; Thackeray, . M.;
David, W. I. F.; Ibberson, R. M. Mater. Rea. Bull. 1990, 25, 667.
the 8a tetrahedral sites and the defects in 16d octahedral (22) David, W. I. F.; Thackeray, . M.; Picciotto, L. A. De.; Good-
sites of the framework. Thus the cation distribution of ennough, J. B. J. Solid State Chem. 1987, 67, 316.
1864 Langmuir, Vol. 8, No. 7, 1992 Feng et al.

Figure 4. Variations of mean oxidation number of Mn with the

extraction (solid marks) and insertion (open marks) of lithium
ions: ( , ) 0.5-800 system; (·, O) 0.5-400 system; (A, A) 0.8-
400 system.

Table III. Compositions of Li+-Extracted and -Inserted

Samples
sample H/Mn Li/Mn formula
Li+ extracted
0.5-800(H) 0.02 0.05 4.03 Li0.10H0.04D0.91Mn1.95O4
0.5-400(H) 0.27 0.03 3.95 Lio.O6Ho.50Do.66Mlll.88U4
0.8-400(H) 0.61 0.02 3.97 LlO.O3Hl.O7Do.l6Mni.74U4
Li* inserted 20 30 tú 50 60
0.5—800(Li) 0.02 0.42 3.63 LlO.83Ho.O4Do.l6Mni.97O4
2 /degree
0.5-400(Li) 0.07 0.38 3.77 Li0.73H0.13D0.24Mn1.90O4
0.8-400(Li) 0.22 0.46 3.87 Li0.8iH0.39D0.04Mn1.7eO4 Figure X-ray
5. diffraction patterns of the Li+-extracted (top)
and Li+-inserted (bottom) samples: (top) (Ai) 0.5-800(H); (Bi)
These results indicate the presence of two types of
0.5-400(H); (C,) 0.8-400(H); (bottom) (A2) 0.5-800(Li); (B2) 0.5-
extraction reaction; one is the redox-type reaction which 400(Li); (C2) 0.8-400(Li). The compositions of the samples are
is described aseql, and the other the Li+/H+ ion-exchange- given in Table III.
type reaction. The increase of 2md corresponds to the
oxidation of manganese from Mn(III) to Mn(IV) due to
a disproportionation reaction. The unchanged 2mo can
be explained by a Li+/H+ ion exchange reaction. The Li+
extraction with 0.5-800 is characterized by the redox-type
reaction, indicating the presence of a large number of re-
dox-type sites. The reaction with 0.8-400 can be char-
acterized as an ion-exchange-type reaction, indicating the
presence of a large number of ion-exchange-type sites. The
reaction with 0.5-400 contains both the redox- and ion-
exchange-type reactions. The 2mo vs Li/Mn curve for 0.5-
400 suggests that Li+ ions are preferentially extracted from
the ion-exchange sites.
X-ray, IR, and DTA-TG Analyses. X-ray diffraction
analyses were carried out for the Li+-extracted samples Li/Mn mole ratio
(0.5-800(H), 0.5-400(H), and 0.8-400(H)); their Li/Mn Figure 6. Plots of the lattice constant (o») of a spinel structure
ratio was less than 0.05 as shown in Table III. The against the Li/Mn mole ratio for the Li+ extraction (solid marks)
diffraction peaks of the spinel structure remained after and insertion (open marks): ( , ) 0.5-800 system; (·, O) 0.5-
Li+ extraction, but the peaks shifted to slightly higher 2 400 system; (A, A), 0.8-400 system.
values with the extraction of Li+ (Figure 5). This indicates
that the Li+ extraction reactions proceed topotactically, IR spectroscopic analysis was carried out for the original
involving a decrease of lattice constant (oo) of the spinel samples (0.5-800,0.5-400, and 0.8-400) and Li+-extracted
structure. The plots of oq against Li/Mn for the Li+ samples (0.5-800(H), 0.5-400(H), and 0.8-400(H)), as
extraction reaction are shown in Figure 6. By comparing shown in Figure 7. In the spectra of the original samples,
the absorption band at 3400 cm-1 and bands at 1530 and
Figure 6 with Figure 4, we can point out that the redox-
1640 cm-1 can be assigned to stretching and bending
type extraction brings a larger decrease of oq value than
the ion-exchange-type extraction. The larger decrease of vibrations of absorbed water, respectively. The bands in
oo in the redox-type reaction is caused by the decrease of
the region from 400 to 700 cm-1 can be assigned to Mn-0
the effective ionic radius of Mn due to the oxidation from stretching vibrations.1·3 A small band at 870 cm"1 shifts
Mn(III) to Mn(IV). Two spinel phases were observed in to 920 cm"1 and a new band at 3430 cm"1 appears following
the case of the 0.5-800 system in the region Li/Mn < 0.25. the extraction of Li+ in the cases of 0.8-400 and 0.5-400
These correspond to a X-MnOa phase having an oq value systems. But these bands are not found in the spectra of
of 0.803 nm and to a LiasM^O* phase having an oo value 0.5-800 and 0.5-800(H). The band at 3430 cm"1 can be
of 0.813 nm.9·22·23 Such a two-phase separation was not assigned to stretching vibration of the lattice -OH group
found in the 0.8-400 and 0.5-400 systems. and the band at 920 cm"1 to lattice coupling vibration of
the H+-form spinel.1 These results correlated well with
(23) Goodenough, J. B.; Thackeray, . M.; David, W. I. F.; Bruce, P. the fact that the Li+/H+ reaction occurs in the 0.8-400(H)
G. Rev. Chim. Miner. 1984, 21, 435. and 0.5-400(H) systems but rarely occurs in the 0.5-800
Li* Extraction/Insertion
Wavenumber/cm-1
Figure 7. IR spectra of original (top) and Li+-extracted (bottom)
samples: (top) (Ao) 0.5-800; (Bo) 0.5-400; (Co) 0.8-400; (bottom)
symbols are the same as those in Figure 5 (top).
system. The bands at 870 and 920 cm-1 may be useful for
the evaluation of the number of ion-exchange sites.
The DTA-TG curves for samples 0.5-400(H) and 0.8-
400(H) showed an endothermic peak at 70 0C with a weight
loss (Figure 8); this corresponds to the evaporation of
absorbed water. An exothermic peak at about 270 °C cor-
responds to a transformation from - 02 to /3-Mn02.9
A weight loss around 220 0C corresponds to the dissipation
of water by the condensation of the lattice-OH group of
the spinel structure, accompanied by a transformation
from H+-form spinel to /S-Mn02.17 The lattice proton
contents can be evaluated from the weight loss between
150 and 300 °C.
Composition of Li+-Extracted Samples. A general
formula for the Li+-extracted samples can be written as
follows:
LinHmD1+I_m.„Mn2.I04 (10)
The parameters n, m, and x can be evaluated from the
following equations using experimental values of proton-
manganese mole ratio (H/Mn), lithium-manganese mole
ratio (Li/Mn), and 2µ > with the condition of eletroneu-
trality. The compositions for Li+-extracted samples are
n + m + (2 -
x)ZMn
= 8
n/{ 2 x)- =
H/Mn
ml {2 -
x) =
Li/Mn (11)
shown in Table III. The increasing order (0.5-800(H) <
0.5-400(H) < 0.8-400(H)) of lattice proton content cor-
related well with the increasing order of the number of
ion-exchange-type sites. The presence of only trace
amounts of lattice proton in 0.5-800(H) indicates that
Langmuir, Vol. 8, No. 7, 1992 1865
Figure 8. DTA (top) and TG (bottom) curves for Li+-extracted
samples. Symbols are the same as those in Figure 5 (top).
most of the Li+ were extracted by the redox-type reaction
of eq 1 for this sample.
It is noteworthy that most of Mn are tetravalent in the
Li+-extracted samples. Shen et al. have proposed the
formation of ( ) [ ^ ™] O4 spinel by the Li+/H+ ion
exchange of (Li)[MnIIIMnrv]04.3 The present result,
however, does not show such an ion exchange reaction for
(Li) [MnmMnIV] O4 spinel. We think (H)[MnIIIMnIV]04
easily decomposes to - 02 and Mn(II) in an acid
solution, owing to a disproportionation reaction of Mn(III)
to Mn(II) and Mn(IV).
Model of Li+ Extraction. On the basis of the facts
that the redox-type extraction of one Li+ is attended by
a disproportion of one Mn(III) ion by the reaction Mn(III)
-*
72Mn(IV) + 72Mn(II) and most of the Mn are tet-
ravalent in the Li+-extracted samples, we can assume that
one Mn(III) ion corresponds to one redox-type site, and
one Mn defect in an octahedral site corresponds to four
ion-exchange-type sites. Thus in the general formula 8,
the number of redox-type sites and ion-exchange sites can
be evaluated to be z and 4x, respectively.
Formula 8 can be divided into two parts. One is the
redox-type part
(Liz)[MnmzMnIvz]04z (12)
where z is the number of redox-type sites in one spinel
structural unit, corresponding to the number of trivalent
Mn. The other is the ion-exchange type part
(kÍ4*-yni-z-4*+y)HiÍyD*-)MnIV2-x-2j04(1_z) (13)
where 4x is the number of ion-exchange-type sites, cor-
responding to 4 times the number of Mn defects. The
extraction of Li+ on the redox sites can be described by
reaction 14, and that on the ion-exchange sites by reaction
15
4(Liz) [MnmzMnIvz] 04z + 8zH+ — 3z(D)[MnIV2]04 +
4zLi+ + 2zMn2+ + 4zH20 (14)
(^JÍ4x-yai-z-4x+y)tLÍyD,-),MnIV2_;e_2z]04(1_z)
+ 4xH+ ^
4xLi
^4x-yai-z-4x+y)[HyDx_yMnIV2_I_2z]04(1_z) + (15)
A proton-free spinel manganese oxide (D)Mn204, which
1866 Langmuir, Vol. 8, No. 7, 1992 Feng et al.

Table IV. Contents and Proportions of the Redox-Type Site and Ion-Exchange-Type Site
redox site (/Mn) ion-exchange site (/Mn) /red, % /ion,.%

sample caled exptl caled exptl caled exptl caled exptl

0.5-800 0.40 0.44 0.08 0.02 83 96 17 4
0.5-400 0.30 0.27 0.19 0.27 61 50 39 50
0.65-400 0.19 0.44 30 70
0.8-400 0.10 0.07 0.65 0.61 14 10 86 90
LiMn204 0.5 0 100 0
Lil.33Mlll.e7O4 0 0.8 0 100

corresponds to - 02 as termed by Hunter,16 is obtained

by extracting Li+ from redox-type sites. A proton-form
spinel manganese oxide is formed by extracting Li+ from
ion-exchange-type sites.
Since we cannot distinguish between the redox-type and
the ion-exchange-type sites from the X-ray diffraction
pattern, it is reasonable to think that the redox-type and
ion-exchange-type sites are mixed with each other, sharing
the Mn-0 framework of a spinel, to form a one-phase
solid solution system.24 In such a case, electrons can move
almost freely over the Mn atoms of the framework.
Therefore, the extraction reaction of Li+ can be written
schematically as in Figure 9a. The lithium ions migrate
to the surface of the spinel powder and are transported
to the solution phase. The dissolution of Mn according
to eq 14 also proceeds at the surface of the powder owing
to the free movement of electrons. Therefore, the dis-
solution may proceed for the Mn atoms on the surface
regardless of whether it comprises a redox site or an ion-
exchange type site.
Evaluation of Site. The validity of the above model
regarding the formation of two kinds of sites can be
evaluated by comparing the calculated values of site
numbers with the experimental ones. According to the
model described above, the contents and proportions of
both the redox-type and ion-exchange-type sites do not
change following Li+ extraction although the total number
of sites per gram of inititial lithium manganese oxide spinel
decreases owing to the dissolution of Mn2+. Therefore,
the proportions of the sites can be calculated as follows

Aed
=
*ln (16)

Aon
=
4x/n
where /red from /¡on are proportions of the redox-type site
and ion-exchange-type site, respectively. These values
can be estimated from the chemical compositions of the
original lithium manganese oxide spinel (Table IV).
The experimental value for the number of ion-exchange-
type sites can be directly determined from a lattice proton
content (Table III) of the Li+-extracted sample. On the
other hand, the number of redox-type sites cannot be
directly determined from the chemical composition of the
Li+-extracted sample. But it can be evaluated on the basis
of eq 14 by using the amount (riMn) of Mn dissolved, the
amount (nu) of Li+ extracted, and the difference (ALi/
Mn) of Li/Mn ratio from the original lithium manganese
oxide
redox site content (/Mn) =
2(nMn/nLi)(ALi/Mn) (18)
The experimental values of the contents and proportions
of the two kinds of site are given in Table IV.
The agreement between the calculated and experimental
values is comparatively good for both the redox-type and
ion-exchange-type sites. This agreement justifies our
model (Figure 9a) for the formation of different kinds of
sites. This indicates that the contents and proportions of
(24) Kozawa, A.; Powers, R. A. Electrochem. Technol. 1967, 5 535.
(17)
Figure 9. Schematic representations of (a) Li+ extraction
reactions and (b) Li+ insertion reactions: O, redox-type sites; ,
ion-exchange-type sites.
the redox-type and ion-exchange-type sites can be pre-
dicted by using Li/Mn and 2mb values of the lithium
manganese oxide spinels, without a direct study on the
extraction/insertion reactions. The calculation for the
model materials suggests that all sites in the normal spinel
LiMn204 are redox-type sites and in the Li1.33Mn1.67O4
spinel are ion-exchange sites.
The content and proportion of each site depend on the
preparation conditions of the original lithium manganese
samples. The number of ion-exchange-type sites increases
with an increase in the starting Li/Mn mole ratio at 400
°C. The ion-exchange-type sites (Mn defects in the
octahedral site) are unstable above 500 °C; they tend to
transform to redox-type sites (LiMn2(>4) and virtually only
Li+ Extraction/Insertion
redox-type sites are formed at 800 °C. This tendency has
been generally observed. The redox-type mechanism eqs
1 and 2 has been proposed for the samples prepared
between 800 and 850 °C.9-16 Leont’eva et al.1·2 and Shen
et al.3 have proposed an ion-exchange mechanism for the
samples which are prepared below 520 °C, where ion-
exchange sites form easily.
Li"1" Insertion Reaction. The Li"1" insertion reaction
was studied using the Li+-extracted samples (0.5-800(H),
0.5-400(H), and 0.8-400(H). Redox-type and ion-exchange-
type reactions also take place in a LiOH solution. A linear
relationship between 2mh and Li/Mn is observed with the
0.5-800 system (Figure 4). On the other hand, a two-
stage process is observed with the 0.5-400 and 0.8-400
systems. The 2md values are constant in the first stage
of Li+ insertion, corresponding to the ion-exchange-type
Li+ insertion, while they decrease in the second stage owing
to the redox-type reaction. These 2µ vs Li/Mn curves
indicate that Li+ ions are preferentially inserted in the
ion-exchange-type sites.
The chemical compositions of Li+-inserted samples (0.5-
800(Li), 0.5-400(Li), and 0.8-400(Li)) from a 0.1 M LiOH
solution are given in Table III. The decrease of the lattice
proton content with the progress of Li+ insertion indicates
the presence of the ion-exchange-type insertion reaction
in the 0.8-400 and 0.5-400 systems. However, the com-
positional data indicate that the lattice protons in 0.8-
400(Li) and 0.5-400(Li) cannot be fully exchanged by Li+
even in a 0.1 M LiOH solution. This suggests the presence
of two types of ion-exchange sites with different acidities.
According to the model described as eq 15, there are two
types of lattice protons in the acid-treated samples: the
protons at 8a tetrahedral sites and those at Mn defects in
16d octahedral sites. These two kinds of lattice protons
may have different acidities and may correspond to two
types of ion-exchange sites in the Li+-extracted sample.
The amount of redox-type insertion, (Li/Mn)red, can be
evaluated by subtracting the amount of ion-exchange-type
insertion from the total amount of inserted Li+ as follows,
(Li/Mn)red = ((Li/Mn)n (Li/Mn)i)
-
((H/Mn)i (H/
- -
Mn)n), where subscripts I and II refer to the mole ratio
before and after the Li+ insertion, respectively. The (Li/
Mn),ed values are given as 0.37,0.15, and 0.05 for the system
of 0.5-800, 0.5-400, and 0.8-400, respectively, using the
data in Table III. Comparing these values with the
numbers of redox sites in Table IV, we can conclude that
most of the redox type sites are filled with Li+ by the
treatment with a 0.1 M LiOH solution. It also indicates
that a further lithium insertion into LiM^O* is difficult
in aqueous phase.
The X-ray diffraction patterns of the Li+-inserted
samples showed that the spinel structures remained after
Li+ insertion with a shift of the diffraction peaks to slightly
lower 2 values (Figure 5(bottom)>. This indicates that
the Li+ insertion reactions proceed topotactically, involving
an increase in the lattice constant of the spinel structure.
The oq vs Li/Mn curve for the insertion reaction is in
agreement with that for the extraction reaction in the 0.5-
800 system (Figure 6). On the other hand, the oq vs Li/Mn
curve for the insertion reaction shows an upward deviation
from that for the extraction reaction in the case of the
0.8-400 system. The upward deviation may be caused by
the reduction of Mn(IV) to Mn(III) in the region Li/Mn
> 0.3.
The Li"1" insertion reaction can also be regarded as a
Langmuir, Vol. 8, No. 7, 1992 1867
Figure 10. pH titration curves for Li+-extracted samples:
sample, 0.100 g; soln, 0.1 M MCI + MOH ( = Li (solid marks)
or Na (open marks)); total volume of solution, 10 mL; temper-
ature, 20 °C; ( , ) 0.5-800(H), (·, O) 0.5-400(H), ( , ) 0.8-
400(H); (---) blank titration, (---) Li+-specific sites.
one-phase solid solution reaction which is schematically
represented as in Figure 9b. The redox-type insertion
reaction attends a reduction of Mn(IV) to Mn(III) at solid
surface. The diffusion of Li+ from the surface to the redox-
type site in the bulk attends a diffusion of electrons over
Mn atoms.
pH Titration. The pH titration curves of Li+-extracted
samples in a (0.1 M LiCl + LiOH) and a (0.1 M NaCl +
NaOH) solution are shown in Figure 10. The apparent
capacities for Li+ were remarkably larger than those for
Na+ over the pH range studied, indicating that all the
samples showed lithium-ion-sieve properties. The high
selectivity for Li+ is due to the steric effect of the insertion
site. The Na+ ion uptake can be regarded as the number
of nonspecific ion-exchange sites on the surfaces of the
powder.17 The net titration curves (dotted lines in Figure
10) for the Li+-specific sites can be obtained by subtracting
Na+ uptake from total Li+ uptake, assuming that the
number of nonspecific sites is equal to Na+ uptake.17 Li+-
specific sites of the ion-exchange-type sample 0.8-400(H)
show a stronger acidity than those of the redox-type sample
0.5-800(H). This indicates that Li+-specific ion-exchange
sites have a stronger acidity than those of redox-type sites.
Sample 0.5-400(H), which is classified as a mixed type,
shows a dibasic acid behavior. A stronger acidic site,
dissociating below pH 4, can be ascribed to Li+-specific
ion-exchange sites, and weaker acidic sites, dissociating
above pH 5, can be ascribed to redox-type sites.
Conclusions
The spinel-type lithium manganese oxides can be
described by the general formula (Lin-yDi-n+y) [Liy^-y-
* 2-*-*]04 (1 < < 1.33,0<x< 0.33,0 < z < 1,
y < x, < 1 + x). These spinels have two types of sites
for Li+ extraction/insertion reactions: redox-type and the
ion-exchange-type sites. The proportions of each site can
be predicted from the values of Li/Mn mole ratio and 2µ
of the spinels. The ion-exchange-type sites predominantly
form below 500 0C while the redox-type sites form at higher
temperatures. The Li+ extraction/insertion reactions
occur preferentially with the ion-exchange-type sites.