Synthesis and Electrochemistry of LiNiMn2_O4

Qiming Zhong,*a Arman Bonakclarpour, Meijie Zhang,0b Yuan 01s,b,c and J. R. Dahn'
aMoli Energy (1990) Limited, Maple Ridge, British Columbia V2X 9E7, Canada
6Department of Physics, Simon Fraser University, Burnaby, British Columbia V5A 1S6, Canada
ABSTRACT

LiNiMn2_104 has been synthesized using sol-gel and solid-state methods for 0 <x c 0.5. The electrochemical behavior of the samples was studied in Li/LiNiMn5_O4 coin-type cells. When x =0, the capacity of Li/LiMn2O4 cells appears
at 4.1 V. As x increases, the capacity of the 4.1 V plateau decreases as 1-2x Li per formula unit, and a new plateau at4.7
V appears. The capacity of the 4.7 V plateau increases as 2x Li per formula unit, so that the total capacity of the samples
(both the 4.1 and 4.7 V plateaus) is constant. This is taken as evidence that the oxidation state of Ni in these samples is
+2, and therefore they can be written as
The 4.1 V plateau is related to the oxidation of Mn" to
Mn" and the 4.7 V plateau to the oxidation of Ni" to Ni". The effect of synthesis temperature, atmosphere, and cooling
rate on the structure and electrochemical properties of LiNi55Mn15O4 is also studied on samples made by the sol-gel
method. LiNi05Mn,504 samples made by heating gels at temperatures below 600C in air are generally oxygen deficient,
leading to Mn oxidation states significantly less than 4. LiNi55Mn,504 samples heated above 650C suffer due to dispro-

portionation into LiNiMn2_O4 with x <

0.5

and Li2Ni1_0 with z

0.2, which occurs above about 650C. Pure

LiNi55Mn, 504 materials can be made by extended heatings near 600C or by slowly cooling materials heated at higher
temperatures. LiNi9 5Mn1504 made at 600C has demonstrated good reversible capacity at 4.7 V in excess of 100 mAh/g for
tens of cycles.
Infroduction
Cathode materials for Li-ion cells are generally selected

from LiCoO2,' LiNiO2,2 and spinel LiMn2O4.35 Cells containing LiCoO2 are now the state-of-the-art power sources
for portable electronic devices.6'7 LiMn2O4 is currently a
very promising cathode material due to its economical and
environmental advantages compared to LiCoO5. However,

stoichiometric LiMn3O4 has been shown to exhibit poor

cycling behavior. To overcome these problems Tarascon
et at.5 and Thackeray and co-workers9 added excess lithium to the material to make Li15Mn2_504 with y about
equal to 0.1. Unfortunately, the addition of excess lithium

reduces the capacity of the spinel approximately as

148(1 3y)

niAh/g ' so that users must make a trade-off

between cycle life and capacity.

An alternative approach for improving the cycling

behavior has been the substitution of other transition metals for Mn to make LiMMn2_04 (M = Co, Mg, Cr, Ni, Fe,

Ti, and n).SOl9 However, all these show a decreased

capacity in the 4.1 V plateau (depending on the amount of

the doped transition metal), but improved cycle life was
reported for Co- and Ni-doped spinels.11 Recently, Sigala

et at. ,12 showed that much of the reduced capacity of

LiCrMn204 materials appears in a 4.9 V plateau which

increases in size with Cr content. This plateau was missed

in the previous works because cells were not charged to
sufficiently high cutoffs. With this in mind it is probably
appropriate to reinvestigate all the LiMMn2_04 materials
in electrochemical cells charged to above 5.0 V. This paper
reports our studies of LiNirMn2x04 charged to these high
potentials.
Recently LiNi05Mn, 504, prepared by a low-temperature
sol-gel method has been reported and studied on the 3 V
plateau.'3 Amine et at. showed using x-ray photoelectron

spectroscopy (XPS) measurements that the oxidation

states of Ni and Mn in LiNi55Mn15O4 were +2 and +4,

respectively. Charging cells containing LiNi5 5Mn5 504 to
4.5 V showed that the 4.1 V plateau was virtually eliminated and that the lithium incorporated during synthesis
could not be removed. This was attributed to the absence
of Mn" in the sample. Here, we report that the lithium can
be removed, but at about 4.7 V vs. Li metal. In addition,

we discuss the structure and electrochemistry of

LiNiMn2..04 samples with 0 <x < 0.5.
* Electrochemical Society Active Member.

Present

Address: FMC Corporation, Lithium Division, Bes-

semer City, North Carolina 28106, USA.

d Present Address: Department of Physics, Daihousie Uni-

versity, Halifaz, Nova Scotia B3H 3J5, Canada.

Experimental

LiNi1Mn204 samples were prepared by solid-state and

sol-gel methods. The solid-state samples were prepared
from stoichiometric mixtures of LiOH (FMC Corporation),

Ni(N0j2 6H20 (Aldrich) and electrolytic manganese

dioxide (Mitsui TAD I grade). Samples with 0 <x 0.4

were heated in air first at 750C for 4 h, then ground and

reheated again for a further 12 h at 750C. These samples
were single phase. The sample with x = 0.5 was heated
three times at 750C, followed by a single heating at 800C.

All solid-state samples were cooled by switching off the

furnace power. We call this "furnace cooling." The sample
with x = 0.5 contained a small LiNi5..0 impurity as is discussed later. These samples are listed in Table I.
Based on the difficulty of preparing pure LiNi05Mn15O4
samples by the solid-state method, we adopted the sol-gel
method proposed in Ref. 13 as an alternative. This gives
the further advantage of studying the products prepared at
a variety (250 to 800C) of temperatures. Stoichiometric
amounts of Mn(CH3COO)5 4H20 (Sigma) and Ni(N05)2
6H20 (BDH) were dissolved in distilled water. Enough
reagents to make 0.1 M of product were dissolved in 150
ml of distilled water. This solution was then mixed with
LiOH (Anachemia) solution. Sufficient LiOH was used to
yield a (2 x):x:1 mole ratio of manganese to nickel to

lithium. The LiOH was dissolved in 20 ml of distilled

water and this solution was added slowly with vigorous
stirring to the solution containing the Mn and Ni ions. A
small amount of carbon black was then added as a stabilizing agent. The resulting mixture was stirred for at least
1 h. The obtained gel was then fired either in air or in oxygen at the desired temperature for 24 h and cooled to room
temperature by the methods listed in Table I. All the samples made are described in Table I.

Some of the LiNiMn204 samples were analyzed after

dissolving in dilute HC1 by flame atomic absorption spectroscopy (AAS) for Li and Ni contents. The Mn content
and its average oxidation state in the same samples were
determined by a redox titration with KMnO4 as the titrant
based on the procedure described by Rousseau. 14 Powder
x-ray diffraction (XRD) measurements were made with a
Siemens D5000 diffractometer equipped with a Cu target
tube and a diffracted beam monoch,romator. Rietveld refinement was then performed on the XRD data to obtain
lattice information using Hill and Howard's program.15
Thermal gravimetric analyses of the samples was made
with a TA Instruments TGA 51 analyzer. A platinum boat
was used as the sample holder. The samples were heated at
2C/mm and cooled at 3C/mm in a constant flow of extra

dry air (Linde). The surface area of the products was

J. Electrochem. Soc., Vol. 144, No. 1, January 1997 The Electrochemical Society, Inc.

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206

J. Electrochem. Soc., Vol. 144, No. 1, January 1997 The Electrochemical Society, Inc.
Table I. Summary of the samples studied.

Sample
1
2
3
4
5
6
7
8
9
10
11
12
13

14
15
16
17

18
19

20
21
22
23
24
25
26
27
28
29
30

x in
LiNiMn,O4

Preparation
method

Temp.

0.0

S-S

0.1
0.15
0.2
0.3

S-S
S-S
S-S

750
750
750
750
750
750
750
800
250
300
400
500
600

5-5

0.05

0.4
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.1
0.2
0.3
0.4
0.5
0.2
0.3
0.4
0.5
0.5

0.5
0.5

S-S

S-S
S-S
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel
sol-gel

(C)

700

800
250
800
800
600
600
600
600
600
850
850
850
850
850
850

850

Cooling

Mn oxidation

method

a (A)

Atmosphere

Furnace
Furnace
Furnace
Furnace
Furnace
Furnace
Furnace
Furnace

8.243

air
air
air
air
air
air
air
air
air
air
air
air
air
air
air

3C/mm
3C/mm
3C/mm
3C/mm
3C/mm
3C/mm
3C/mm
3C/mm
3C/mm
0.8C/mm
0.8C/mm
0.8C/mm

--0.8C/mm
0.8C/mm
0.8C/mm
0.8C/mm
0.8C/mm
0.8C/mm
0.8C/mm

650q
750q
BSOq

8.234
8.228
8.222
8.215
8.200
8.187
8.176
8.1886
8.1840
8.1805
8.1772
8.1716
8.1780
8.1857
8.1806
8.1759
8.1744
8.2196
8.2080
8.1915
8.1730
8.1678
8.2176
8.2034
8.1818
8.1722
8.1745
8.1840
8.2183

oxygen
oxygen
oxygen

air
air
air
air
air
air
air
air
air
air
air
air

state

3.869
3.927
3.935
3.962
3.967
3.919
3.855
3.891

3.663

3.771
3.907
3.987

s-s means solid-state synthesis.

determined by the single-point nitrogen sorption Bru-

nauer-Emmett-Teller (BET) method using a Micromeritics

Flowsorb 112300 surface area analyzer.

The electrochemical properties of the LiNirMfl2_x04

samples were evaluated using coin-type cells (size 2320)

containing a lithium metal foil anode, a Celgard 2502

microporous polypropylene separator, together with an

electrolyte of 1 M LiBF4 dissolved in a 30/70 volume per-

centage mixture of ethylene carbonate and diethyl carbonate (EC/DEC). Composite cathode electrodes were
made from the spmnel sample powders, Super S carbon
black (10% by weight) (Chemetals Incorporated), and
polyvmnylidene fluoride (PVDF) binder, uniformly coated

on aluminum foil. The sample powder and carbon black

were added to a solution of 9.4% PVDF in n-methyl pyrrolidinone (NMP) such that 5% of the final electrode mass is

PVDF. Excess NMP was then added until the slurry

reached a syrupy viscosity, and then the slurry was spread
on the Al foil with a doctor blade spreader, and dried at

110C in air. Dried electrodes were then compressed

between two flat plates at about 60 bar pressure. Test electrodes 1.2 >( 1.2 cm were then cut using a precision cutting

jig. Electrode squares were weighed, and the combined

weight of foil, carbon black, and PVDF was subtracted to
obtain the active electrode mass. Fabrication of the coin
cells was carried out in an argon-filled glove box.
The electrochemical measurements were conducted
under thermostatic conditions at 3 0C. Cells were cycled
galvanostatically in a potential range of 3.0 to 4.9 V using
a Moli cycler [Moli Energy (1990) Limited, Maple Ridge,

BC, Canada] with 1% current stability. Currents were

adjusted to be either 14.7, 3.7, or 3.0 mA/g of active electrode material, which corresponds to a discharge or charge
time of 10, 40, or 50 h, respectively, assuming that one Li
atom per formula unit can be extracted.
Results and Discussion
1
shows
diffraction profiles for samples 19, 21,
Figure
and 23 which have x = 0.1, 0.3, and 0.5, respectively These
samples were made at 600C and are single-phase spinel
samples. The insets in the figures show an expanded view
of the spinel (400) peak. When LiNi1O is present as an
impurity, an impurity peak appears to the left of the (400)

peak, as we see later. Figure 2 shows the variation of the

lattice constant with nickel content for the samples prepared by both the solid-state and sol-gel methods. Data
for all samples, except samples 9-18 and 28-30, are included in the figure. The linear variation of the lattice constants coupled with the single-phase patterns in Fig. 1
show that a solid-solution series has been prepared.
Figure 3 shows potential profiles of representative solgel and solid-state materials. The solid-state materials
were cycled two times to 4.3 V before they were charged to
4.9 V. The currents used were 3.7 mA/g. The sol-gel materials were cycled directly to 4.9 V, and the data shown are

for the third cycle of these materials. The currents used

were 3.0 mA/g for these samples. It is clear that the 4.1 V
plateau moves upward to 4.7 V as the Ni content increases. There is a sharp step between the plateaus. We have
recently shown that the cause of potential step stems from
the position of the Ni 3d e5 levels with respect to the Mn 3d

e5 levels. The former have an electron binding energy

which is about 0.5 eV larger than the latter.

As Li is removed from the solid, the Li and a corre-

sponding electron are removed. The electron comes from

the top of the valence band, which is shown in Ref. 16 to
be made up of metal 3d levels. In LiMn2O4 (high-spin configuration) there is one electron per formula unit in the
lowest e5 level and three electrons in the lowest tig level. Ni

in this compound has an exchange splitting which is

smaller than the crystal field splitting and is in the low

spin configuration. There are six electrons in the nearly

degenerate t2g levels. The lowest eg level, which can hold
two electrons, is about 0.5 eV below the filled Mn e5 level.
Since the other exchange split Ni e5 level is above the filied
Mn e5 level, it remains empty Thus, as Ni is added to the
compound, d electrons from Mn e5 "dump" into the lowest
Ni eg level, which can hold two electrons, giving a total of
eight on the Ni. Thus, the Ni in this compound takes oxi-

dation state + 2 (as experimentally confirmed by Amine

et al.ii) and there are 1 2x Mn atoms in oxidation state

+3 and 1 + x Mn atoms in oxidation state +4 in

LiNiMn2O4 per formula uhit. Therefore we write the oxi-

dation state of this compound as LiNit2MntMnixO_.

Since there are 1 2x Mn eg electrons per LiNiMn2_O4
formula unit, the length of the 4.1 V plateau should vary

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207

J. Electrochem. Soc., Vol. 144, No. 1, January 1997 The Electrochemical Society, Inc.

Fig. 1. Powder x-ray diffraction patterns for LiNi,Mn1_,04

samples 19, 21, and 23, with
= 0.1 (a), 0.3 (b), and 0.5 (c)

prepared by the sal-gel methad

at 600C. The inset shows the

region near the spinel (400)

peak.

10

20

40

30

50

60

70

80

90

SCA I I tRING ANGLE (deg.)

as 1 2x Li per formula unit. Once all the Mn 3d e5 elec-

trons are removed, the next electrons available are from Ni

3d e5, which has a 0.5 eV higher binding energy. Thus, the
potential of the cell steps up by about 0.5 V. The length of
the 4.7 V plateau should be 2x Li per formula unit because

there are two electrons per nickel atom in the lowest eg

level. Thus, in the fully charged state (4.9 V), the Ni should

be in oxidation state +4.

When x = 0, the capacity of Li/LiMn2O4 cells appears at
4.1 V. Figure 4 shows that as x increases, the discharge

capacity of the 4.1 V plateau decreases approximately as

1 2x Li per formula unit (1 Li per formula unit is about
148 mAh/g). The discharge capacity of the 4.7 V plateau
increases approximately as 2x Li per formula unit, so that
the total capacity of the samples (both the 4.1 and 4.7 V
plateaus) is constant. This agrees well with the arguments
above and proves that the electron energy level locations
proposed in Ref. 16 are correct. In simple terms, the 4.1 V
plateau is related to the oxidation of Mn3 to Mn" and the
4.7 V plateau to the oxidation of Ni2 to Ni".
The cells made from the sol-gel materials described in
Fig. 3 suffered from parallel electrolyte decomposition aL

these high potentials. The net effect of this is that the

effective current used to deintercalate lithium during

600 Sol-Gel

850 Sol-Gel

'

charge is smaller than the set current, because some frac-

tion of the current is used to decompose electrolyte.

During discharge, the effective current is higher than the

set current. This leads to a charge imbalance between

charge and discharge which is particularly severe for the
x = 0.5 sample in Fig. 3a. Since the capacities used in Fig.
4a are the discharge capacities from Fig. 3, these are systematically lower than would be attained in the absence of
electrolyte decomposition. On the other hand, electrolyte
decomposition is much less severe for the solid-state materials as shown in Fig. 3f-j, and hence Fig. 4b is more reliable than Fig. 4a. The sol-gel materials made at 600C
have specific surface areas near 10 m2/g as we see later,

750 Solid State

'

8.24d

C 8.220CD

while the solid-state materials have surface areas near

1 m2/g. This is a possible explanation why electrolyte
decomposition is more severe for the sol-gel materials.

0
C-)

8.200 -

CD

-J

Alternatively, differences in surface chemistry between the

.+

A
8.180 -

A
8.160

0.00

0.10

0.20

0.30

0.40

x in LiNiMn2O4

0.50

Fig. 2. Lattice constant vs. x for LiNiMn1_O4 samples as indicated in the legend. All the samples in Table I, except samples 9-18
and 28-30 are included in the figure.

sol-gel and solid-state materials could be responsible for

the difference.
According to our model for the length of the plateau
capacities, materials with x = 0.5 should show no 4.1 V
plateau. This is true for the sol-gel material (sample 23)
shown in Fig. 3a, but not for the solid-state material (sample 8) shown in Fig. 3f. The presence of the 4.1 V plateau
in Fig. 3f, suggests that this sample may be nickel deficient. Figure 2 shows that sample 8 has a larger lattice
constant than sample 23, again consistent with less nickel
in the spinel phase. AAS analysis shows that both specimens have the same desired overall Ni composition of x =
0.5. In order to understand the origin of the 4.1 V plateau
in sample 8, we noted that it had been prepared at higher

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208

J. Electrochem. Soc., Vol. 144, No. 1, January 1997 The Electrochemical Society, Inc.

temperature than sample 23. We now consider the effect of

an increase to the synthesis temperature.
Figure 5 shows the TGA curve for sample 10 (sol-gel, x =
0.5, 300C) heated and cooled in air. There is a reversible

weight loss associated with oxygen loss during heating

and weight gain due to reincorporation during cooling. In

a recent paper of ours, we identified the reactions which
occurred during similar weight loss events in the beatings
of Li1Mn2_O4. ' There we used diffraction studies of
samples quenched from temperatures above the onset of

SOLID-STATE

SOL-GEL

Fig. 3. Potential vs. capacity

for Li/LiNi,,Mn1_O4 cells. The
samples presented are: (a) sampie 23, (b) sample 22, (c) sample

>

21, (d) sample 20, (e) sample

19, (f) sample 8, (gJ no data
available, (h) sample 6, Ci) sample 5, (j) sample 3.

0.

40

80

120

Capacity (mA.hr/g)

160 0

40

120

160

Capacity (mA.hr/g)

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209

J. Electrochem. Soc., Vol. 144, No. 1, January 1997 The Electrochemical Society, Inc.
!rap-,t

a) SOL-GEL

b) SOLID-STATE

I low V plateau

high V plateau

D total
117 mAhr/g.2x

140.0.

Fig. 4. Discharge capacity of

the 4.1 V plateau, 4.7 V

117 mAhr/g.(1-2x)

plateau, and total discharge

capacity between 3.0 and 4.9 V

for Li/LiNiMn1.O4 cells. (a)

120.0 -

Samples 19-23 prepared by solgel methods; (b) samples 2, 3, 5,

0) 100.0 -

6, and 8 prepared by solid-state

methods. A demarcation line at
43 V was used to partition the

E
>.
C)

80.0 60.0

capacity into the two regions.

The solid and dashed lines in the

figures are linear fits as indicated in the legends.

40.0 -

20.0 -

I
0.1

S.

0.2

0.3

I _._I

0.4

0.5

0.0

0.1

weight loss to determine the reaction occurring during

weight loss. We use the same strategy here.

Figure 6 shows the diffraction patterns of samples 28,

29, and 30 (all x = 0.5), quenched from 650, 750, and
850C. The latter two samples have been quenched well
above the onset of weight loss in Fig. 5. An extra set of diffraction lines appears in samples 29 and 30. Peaks from a
rock-salt related structure near 37.5, 43.8 (see inset in the
figure), and 63.8 are clearly visible. In addition, the lattice

constant of the spinel phase itself increases with quench-

ing temperature, as shown in Fig. 7. The peaks of the

impurity phase can be indexed on a rock-salt structure,
and a cubic lattice constant of 4.140 A was found for this
phase from two-phase Rietveld refinement. Since the lattice constants of NiO and MnO are 4.18 and 4.44 A, respectively,'8 it is unlikely that this phase contains Mn. The lattice constant of LiNi50 decreases with z, and is 4.140 A

at z

0.18. We propose that the impurity phase is

LiNi1_0 with z near 0.18. The increase of the lattice constant of the spinel phase with quenching temperature is
due to the removal of Ni from it (see Fig. 2).
We propose that the following disproportionation reaction occurs above the weight loss onset
LiNi05Mn1 504 5

0.2

0.4

0.5

sample. Indeed, x-ray diffraction on this sample does show

the presence of the rock-salt LiNi1_0 phase. The amount
of Ni deficiency is easily estimated from the length of the
4.1 V plateau (Fig. 3f) for sample 8. We estimate a Ni con-

centration of x = 0.43, not x = 0.5, in this sample. The

advantage of the sol-gel method is that it allows the production of materials at lower synthesis temperatures than
the solid-state method, for example, entirely below 650C,
where oxygen loss occurs.
At this point, it is worth discussing the results present-

ed in Ref. 13, Amine et al. claim that NiO, not LiNi10,

coexists with LiNi05Mn15O4 when sol-gel samples are
recalcined at 650C. (See their Fig. 2.) Since they did not
carefully measure the lattice constant of their impurity
phase, it is likely that they really have LiNi1_,0, with z
near 0.2, just like us. Figure 4 in Ref. 13, shows the variation of the spinel lattice constant with x in LiNi.Mn204.
The data show substantial upward curvature near x 0.5,
unlike our data in Fig. 2. This suggests that Amine et al's

101

qLiNi10
+ rLiNj55 ,,,Mn1 5+,o04 + s

0.3

x in LiNiMn2.04

x in LiNiMn2,O4

100

02 [1]

This reaction can be balanced by equating the Ni, Mn, Li,

and 0 amounts on the right and left sides of the equation,
s is obtained from the weight loss vs. temperature. This
qualitatively explains the observed data. Figure 5 shows
that as the temperature increases above 650C, s increases,
necessitating the formation of a phase with a larger cation
to anion ratio than the 3:4 found in spinel. Since LiNi10
has a cation to anion ratio of 1:1, q and w increase, and r
decreases while s increases. Further work is needed to ver-

ify Eq. 1 quantitatively, and this will be the subject of

future investigations.
Now that we have learned that the oxygen loss in samples heated above 650C reduces the amount of Ni in the
spinel phase, the 4.1 V plateau in sample 8 (Fig. 3f) is due
to Ni deficiency probably caused by excessively fast cooling and insufficient oxygen uptake during cooling of the

I,
rM

0
.z

. 98
97
96
95
100

300

500

700

900

Temperature C
Fig. 5. TGA measurement on sample 10 (x = 0.5 in LiNiMn1OJ
in air.

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210

1 Electrochem. Soc., Vol. 144, No. 1, January 1997 The Electrochemical Society, Inc.

Fig. 6. X-ray diffraction pro-

files of (a) sample 28, (b) sample

29, (c) sample 30, quenched

from 650, 750, and 850C,

respectively. All samples had
x = 0.5 in LiNi,,Mn1.O4. The
insets show the region near the

p6000

4000
02000

spinel (400) peak. The (peak)

from a U,Ni1.Z0 phase appears

to the left of the spinel (400)

peak in the samples quenched
from higher temperature.

40

60

50

70

80

90

SCM iuzRING ANGLE (deg.)

samples with large x are Ni deficient. This suggestion is

further supported by an examination of the potential profiles in Ref. 13, shown in Fig. 10a of that reference. A substantial 4.1 V plateau is still observed for Amine's x = 0.5
sample, unlike our sol-gel sample shown in Fig. 3a. This
further proves that Amine's x = 0.5 samples have less
incorporated Ni than ours.
Now we examine the effect of heating temperature on

desired nickel. Thus slow cooling and an oxygen atmosphere help eliminate the LiNi1.0 impurity.

Figure 13 shows the differential capacity, dy/dy of

Li/LiiyNirMns..x04 cells plotted vs. potential. The sol-gel

samples are samples 19-23, respectively, and the solidstate samples are samples 3, 5, 6, and 8. Figure 13 shows
the shift of the capacity to higher potential as x increases,

sol-gel LiNi55Mn1504 samples. Figure 8 shows the diffraction patterns of samples 10, 13, and 15 (x = 0.5, sol-gel)
heated at 300, 600, and 800C. Only in the sample heated
to 800C is evidence of LiNi1O observed. Figure 9 shows

and the complete elimination of the 4.1 V plateau for sample 23. The dy/dy data for the sol-gel sample suffers due
to the simultaneous electrolyte decomposition reactions.
The data for the solid-state samples are particularly beautiful. The solid-state sample with x = 0.5 (Fig. 13f) shows

samples 9-15 (x = 0.5, sol-gel) plotted vs. heating temperature. The lattice constant is minimum, and the Mn oxida-

up in potential from 4.1 to 4.7 V. This helps to demonstrate

the lattice constant and average Mn oxidation state of

tion state is maximum, near 600C heating temperature.

The increase of lattice constant and decrease of Mn oxidation state above 600C is explained by the disproportiona-

tion reaction 1. The reasons for the variations below 600C

are now explored.
In the sol-gel method, the reactants used do not contain
enough oxygen for the final product, once that needed for
the gaseous decomposition products is accounted for. The
extra oxygen needed must come from the atmosphere. In

samples heated at low temperatures, this oxygen uptake

may be slow and hence incomplete for samples heated for
short times in air. Then the samples will contain excess

Mn3, and their lattice constants should be larger (as

observed) since Mn3 is larger than Mn4t Figure 10 shows
the manganese oxidation state and the lattice constant for
samples heated at 250C in air (sample 9) and in pure oxygen (sample 16) compared to the optimum sol-gel sample

made at 600C (sample 13). Heating in pure oxygen

improves the sample, as its lattice constant decreases and

Mn oxidation state increases..
It is possible to make LiNi55Mn5 504 at 80 0C which is
approximately single phase. This is done with a combination of slow cooling and an oxygen atmosphere. Figure 11
shows the lattice constant of sol-gel samples 15, 17, and
18. These were made in air, in oxygen, and in oxygen with
slow cooling, respectively. They are compared to the sample (sample 13) made at 600C. Figure 12 shows the potential profiles for samples 15, 17, and 18, measured with a
current of 14.8 mA/g. The 4.1 V plateau is almost absent in
samples 17 and 18, proving that they contain almost all the

a double-peaked feature centered at 4.7 V, which looks

almost identical to that of Li/LiMn2O4 cells19 but shifted
that the double-peaked feature is not due to some structure in the electronic density of states, because it is unlikely that the Mn e5 and Ni e9 levels would show the same
structure. Instead, this feature is most likely due to the
ordering of lithium on 8a sites at 50% filling as we have

8.22C

'C
C

(0
(I)

8.210

8.200 .

C-)

t
a)

Ca
-J

8.190

8.180
8.1 C
Slow
Cool

800
700
600
Quench Temperature (C)

500

900

Fig. 7. The lattice constant of the quenched samples (28, 29, 30)
planed vs. quenching temperature. Each of the samples had x =
0.5 in liNi,,Mn1.,04 before quenching.

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211

J. Electrochem. Soc., Vol. 144, No. 1, January 1997 The Electrochemicat Society, Inc.

1800
1200

600

0
C/) 1200

800
4oo0

c)8ocLxNAj.
4243444546

800
600

-I

Fig. 8. Selected diffraction

600C

patterns of the sd-gel samples

with x = 0.5 in LiNiMn1O4 as
a function of heating tempera-

. 1.LL1
,.

.
a)

400
200

42 43 44 45 46

ture as indicated. The inset

shows the region of the spine1
(400) peak. The samples are (a)

sample 10, (b) sample 13, Cc)

300C

sample 15.

42 43 44 45 46

Il

0
20

10

30

40

50

60

70

80

90

SCM rRJNG ANGLE (deg.)

discussed thoroughly elsewhere.2 Since the lattice of 8a

sites is not changed by the addition of nickel, this is reasonable. The details of dy/dV for samples with intermediate x are more difficult to explain, and further work is
needed to do so.

present when x = 0 shifts to 4.7 V when x = 0.5. At intermediate compositions, the 4.1 V plateau has a length given

As a final result, Fig. 14 shows the discharge capacity vs.

cycle number for sample 13 (501-gel, x = 0.5, 600C) for a
cell cycled at 14.8 mA/g. The cell was cycled between 4.9
and 3.0 V. The recharge capacity is always about 10 mAh

a
to-

C
0?

longer than the discharge capacity due to electrolyte

a
0?
a

decomposition, but the cell maintains its discharge capacity quite well, suggesting that the material itself is quite
stable to cycling.

0?

55
00
to.

0?

Conclusions
The structure and electrochemistry of LiNirMni_O4
have been studied for 30 samples prepared by two routes
under a variety of synthesis conditions. The 4.1 V plateau
24 hrs, air
24 hrs, air
250C
/24hrs, 02, 250C

Fig. 10. Variation of both the lattice constant and the average

8.190

a
to,

24 hrs, air
600C

valence of Mn with synthesis conditions for L1Ni05Mn15O5 samples

9, 16, and 13. Synthesis conditions are given in the figure.

8.186

8.182
8.178

4?

. 8.174
8.170

(a)
200

200

300

300

400

500

600

700

800

400

500

600

700

800

Heating temperature (C)

Fig. 9. Comparison of the lattice constant of the unit cell and the
average valence of Mn for sal-gel LiNi0 5Mn 504 samples 9-15 heat-

ed at different temperatures: (a) lattice constant vs. synthesis temperature, (b) oxidation state of Mn vs. synthesis temperature.

800C

air

800C 800C, 02
slow cool
02

6000

air

Fig. 11. Lattice constant for sal-gel samples 15, 17, and 18 compared to sample 13. The preparation conditions are given in the
figure.

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212

J. Elect rochem. Soc., Vol. 144, No. 1, January 1997 The Electrochemical Society, Inc.

plateau potential is caused by the 0.6 eV higher binding

energy of the Ni e5 electrons compared to the Mn eg electrons.

5.3

LiNi.Mn1O4 loses oxygen and disproportionates to a

spinel with a smaller Ni content and LiNi1_,O when it is
heated over about 650C. The reaction is reversible if slow

5.1

cooling rates are used, but samples which are rapidly

cooled end up with less nickel in the spinel phase than

4.9

4.7

desired. The importance of a careful understanding of the

solid-state chemistry of these complex spinels is critical to

4.5

the successful interpretation of their electrochemical

.14

behavior.

4.1

LiMMn1_O4 materials are warranted, even though there

have been numerous works on such materials before. This
is because most of the early workers did not pay attention
to the oxygen loss from spinels at high temperatures and
hence may have had impure samples, and also because
much of the electrochemistry was limited to potentials

It is our opinion that similar careful studies of other

3.9
3.7

3.5

below 4.3 V
0

10

12

14

16

Time
Fig. 12. Potential profiles of samples 15, 17, and 18, measured
at C/1O (14.7 mA/g). The preparation conditions are given in the
legend to the figure.

by 1 to 2x Li per formula unit, and the 4.7 V plateau has a

length given by 2x Li per formula unit. The shift of the

Acknowledgment

One

of the authors (M.Z.) would like to thank the

Natural Sciences and Engineering Research Council of

Canada (NSERC) for the award of an NSERC Postdoctoral

Fellowships. The useful comments of Ulrich von Sacken
and Jan Reimers are gratefully acknowledged.

Manuscript submitted May 24, 1996; revised manuscript

received Sept. 2, 1996.

Fig. 13. Differential capacity

of Li/LiNiMn1.O4 cells vs.

potential. The samples studied
have the same nomenclature as
in Fig. 3. Notice that the vertical
axes on the left and right panels
for each sample are different.

I>

>1

.9

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J. Electrochem. Soc., Vol. 144, No. 1, January 1997 The Electrochemical Society, Inc.

213

This Journal, 142, 2149 (1995).

4. T. Ohzuku, M. Kitogawa, and T. Hirai, ibid., 137, 769
(1990).

5. J. M. Tarascon, E. Wang, E K. Shokoohi, W. R.

Mckinnon, and S. Colson, ibid., 138, 2859 (1991).
6. T. Nagaura and K. Tozawa, Frog. Batteries Sal. Cells,
9, 20 (1990).

7. T. Nishi, H. Azuma, and A. Omaru, U.S. Pat. 4,959,281

(1990).

8. J. M. Tarascon, U.S. Pat. 5,424,205 (1995).

9. R. J. Gummow, A. de Kock, and M. M. Thackeray,

Solid State lonics, 69, 59 (1994).
10. R. Bittihn, R. Herr, and D. Hoge, J. Power Sources, 4344, 223 (1993).

11. G. Li, H. Ikuta, T. Uchida, and M. Wakihara, This

Journal, 143, 178 (1996).
12. C. Sigala, D. Guyomard, A. Verbaere, Y. Piffard, and
M. Tournoux, Solid State lonics, 81, 167 (1995).
13. K. Amine, H. Tukamoto, H. Yasuda, and Y. Fujita,

Abstract 70, p. 114, The Electrochemical Society

Meeting Abstracts, Vol. 95-2, Chicago, IL, Oct. 8-13,
1995.

20

Cycle number
Fig. 14. Capacity vs. cycle number for an Li/LiNi05Mn15O4 cell
using sample 13 as the cathode. The cell was cycled at 14.7 mA/g.

Daihousie University assisted in meeting the publication

costs of this article.

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