Electrochemical and Solid-State Letters, 5 共6兲 A135-A137 共2002兲 A135

0013-4651/2002/5共6兲/A135/3/$7.00 © The Electrochemical Society, Inc.

LiMnPO4 as the Cathode for Lithium Batteries

Guohua Li,*,z Hideto Azuma, and Masayuki Tohda
Sony Corporation, Nishi Battery Laboratories, 4-16-1 Okata, Atsugi-shi, Kanagawa 243-0021, Japan

Olivine LiMnPO4 has been produced using a new synthetic method. Reversible extraction and insertion of lithium into olivine
LiMnPO4 at 4.1 V vs. lithium demonstrated that this material is a promising candidate for the cathode in lithium-ion batteries.
When charged to 4.5 V, ca. 0.94 Li per formula unit can be extracted during the first charge. When charged to 4.8 V, 152 mAh/g
was delivered in the first discharge. An overall reversible capacity of 140 mAh/g has been attained at room temperature. A flat
two-phase region with open-circuit voltage ⬇4.1 V was identified. The thermal stability of the charged cathode was evaluated by
thermogravimetric analysis and differential scanning calorimetry.
© 2002 The Electrochemical Society. 关DOI: 10.1149/1.1475195兴 All rights reserved.

Manuscript submitted December 17, 2001; revised manuscript received February 7, 2002. Available electronically April 11, 2002.

Since the pioneering study on LiFePO4 by Padhi et al.,1 signifi- was 0.28 mA/cm2 . For open-circuit voltage 共OCV兲 measurements,
cant efforts have been made to improve this material.2-10 In addition, the cell was first charged to 4.8 V, and then discharged in an inter-
a series of lithium transition metal phosphates with an ordered oli- mittent mode with alternating 30 min intervals of continuous dis-
vine structure LiMPO4 共M ⫽ Fe, Mn, Mny Fe1⫺y , Co, Ni兲 have charge at 0.28 mA/cm2 and 480 min rest intervals until the cell
recently been investigated as attractive cathode materials because of voltage dropped to 2.0 V.
their theoretical capacity of ca. 167-171 mAh/g based on the M3⫹/ The thermal stability of the 4.5 V charged cathode was evaluated
M2⫹ couple.11-15 Among these materials, LiMnPO4 is of particular using thermogravimetric analysis 共TGA兲 and differential scanning
interest as the cathode material for lithium-ion batteries because the calorimetry 共DSC兲, 共TG/DTA6300, DSC6200, Seiko Co.兲.
potential of Mn3⫹/Mn2⫹ is 4.1 V vs. Li/Li⫹, which is compatible
Results and Discussion
with the cathode used in present lithium-ion batteries. However,
Padhi et al.1 and Okada et al.15 were unable to take any lithium out The crystal phase of all of the samples was identified from the
of LiMnPO4 . Until now, the capacity at 4.1 V was achieved only in powder XRD experiments to be LiMnPO4 with an ordered olivine
LiMny Fe1⫺y PO4 solid solutions. structure indexed by orthorhombic Pnmb. No impurities were de-
We have developed a synthesis route for LiMny Fe1⫺y PO4 by tected with the XRD results. As an example, the XRD pattern for
adding carbon black to the synthetic precursor followed by sintering carbon-containing LiMnPO4 sintered at 500°C is shown in Fig. 1.
in a nitrogen atmosphere.16 A large reversible capacity of 164 The lattice constants were a ⫽ 6.106(1) Å, b ⫽ 10.452(1) Å, and
mAh/g was achieved over a wide Mn compositional range y, even at c ⫽ 4.746(1) Å. For samples sintered below 650°C, more than 95%
Mn contents as high as y ⫽ 0.75.17 of the particle volume is less than 10 ␮m using the particle size
We report the redox behavior of olivine LiMnPO4 synthesized by distributed measurements. This was also confirmed by the SEM ob-
this new method. The results demonstrate that this material is a servations.
promising candidate for the cathode in lithium-ion batteries. Although an olivine phase was obtained at various temperatures,
the cathode performance depended on the sintering temperature.
Samples synthesized around 500°C had the greatest capacity. Unless
Experimental indicated otherwise, the samples used for electrochemical testing
The carbon-containing LiMnPO4 compounds were prepared us- were sintered at 500°C. The charge-discharge profiles of a
ing a solid-state reaction by adding carbon black to the synthetic Li/Lix MnPO4 cell cycled between 4.5-2.0 V at room temperature are
precursors. Carbon black, Li2 CO3 , MnCO3 , and NH4 H2 PO4 , were
mixed in a stoichiometric ratio. The amount of carbon in the mixture
was 6 wt %. The carbon-containing precursor was then ground by
ballmilling. The carbon-containing olivine phase LiMnPO4 was syn-
thesized by sintering the carbon-containing precursor in a purified
N2 gas stream at temperatures ranging from 400 to 800°C. The
carbon content in the final LiMnPO4 -composite was calculated to be
9.8 wt %.
The X-ray powder diffraction 共XRD, RINT-2500V, Rigaku Co.兲
with Cu K␣ radiation was used to identify the phases. The particle
size distribution was measured by laser diffraction 共LA-920, Horiba
Co.兲. Scanning electron microscope 共SEM兲 images were observed
using the Hitachi S-800 microscope.
Electrochemical characterization of the LiMnPO4 cathode mate-
rials was accomplished using coin-type cells 共size 2016兲 with a
lithium metal anode. The cathodes were made by mixing the carbon-
containing LiMnPO4 powders with polyvinylidene fluoride 共PVDF兲
binder 共Aldrich兲 in a weight ratio of 97:3. The electrolyte was a
solution of 1 M LiPF6 in a 1:1 mixture of ethylene carbonate 共EC兲
and dimethyl carbonate 共DMC兲, 共Tomiyama Chemicals兲. The cells
were galvanostatically cycled at 23°C; the typical current density

* Electrochemical Society Active Member.

z
E-mail: Guohua.Li@jp.sony.com Figure 1. XRD pattern for carbon-containing LiMnPO4 sintered at 500°C.

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 A136 Electrochemical and Solid-State Letters, 5 共6兲 A135-A137 共2002兲

Figure 4. OCV curves for the Li/Lix MnPO4 cell.

Figure 2. Charge-discharge curves of the Li/Lix MnPO4 cell cycled between
4.5 and 2.0 V.

shown in Fig. 2. At the end of the charge process, the cell voltage
was kept at 4.5 V until the current density decreased to ⬍0.017 mA/
cm2 . When charging the cell to 4.5 V, the capacity of the first charge
was 162 mAh/g, which reveals that ca. 0.94 Li per formula unit can
be extracted. The capacity of the first discharge was 146 mAh/g. As
shown in Fig. 3, a reversible capacity of ca. 140 mAh/g was ob-
tained during the subsequent cycles with reasonably good cycling
performance when cycled between 4.5 and 2.0 V. When charged to
4.8 V, the capacity of the first charge approaches the theoretical
capacity of ⬃171 mAh/g for LiMnPO4 , 152 mAh/g was delivered
at the first discharge. However, as shown in Fig. 3, when cycled
between 4.8 and 2.0 V, a fast capacity fade was observed. This was
probably caused by the decomposition of the electrolyte.
Figure 4 shows the OCV curves for the Li/Lix MnPO4 cell. The
flat region with OCV ⬇ 4.1 V was identified over the entire lithium
compositional range. This showed that the charge-discharge reaction
proceeds in a two-phase manner between LiMnPO4 and Lix0 MnPO4
共x 0 is close to 0兲 phases.

Figure 5. Variations in lattice constants as a function of lithium composition

Figure 3. Cycling performance of the Li/Lix MnPO4 cell. x in Lix MnPO4 obtained from electrochemical cells.

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 Electrochemical and Solid-State Letters, 5 共6兲 A135-A137 共2002兲
Figure 6. TGA and DSC profiles for 4.5 V charged Lix MnPO4 at a heating
rate of 10°C /min.
The Lix MnPO4 samples were prepared by charging the cell to a
given lithium composition. Variations in the three lattice constants a,
b, and c of the orthorhombic Pmnb with lithium composition x are
shown in Fig. 5. When lithium is extracted from LiMnPO4 共phase
A兲, a new phase B Lix0 MnPO4 forms, in which the lithium content
x 0 is very close to zero. From phase A to phase B, both the a and b
lattice parameters contract, while the c lattice parameter expands
slightly. The lattice volume change during the extraction-insertion is
10.7% 共from 302.9 Å 3 of phase A to 270.4 Å 3 of phase B兲. As
pointed out by Padhi et al. using a LiFePO4 /FePO4 two-phase reac-
tion model, the cell performance becomes diffusion-limited at higher
currents, thus a larger surface area benefits the cathode
performance.1 Goodenough and Manivannan suggested that a large
amount of lithium could be extracted and reinserted reversibly in
samples with smaller grain size, which would result in better perfor-
mance for cathode materials with olivine structure.18 The addition of
carbon black to the synthetic precursors suppressed particle growth
during the crystallization process and created a large surface area.
This enabled the good cathode performance of LiMnPO4 powders.
Safety is the paramount concern for consumer batteries and good
thermal stability of the cathode material in a charged state is crucial
to improving reliability. TGA and DSC offer convenient means of
studying the thermal stability of charged cathodes under controlled
conditions. Figure 6 shows the TGA and DSC profiles for 4.5 V
charged Lix MnPO4 at a heating rate of 10°C/min. The total weight
loss was about 14% when the sample was heated to 500°C. Exother-
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A137
mic heat flow was detected over a wide temperature range of 130 to
380°C, the total heat evolution was about 290 J/g. In contrast, the
overall heat generation of the fully charged LiNiO2 and LiCoO2 was
ca. 1600 and 1000 J/g, respectively.19 The extremely stable nature of
the olivine structure1,20 will produce batteries with high tolerance to
extreme temperatures.
Conclusions
We have demonstrated that a reversible capacity of 140 mAh/g
can be achieved at room temperature for LiMnPO4 . The LiMnPO4
fine powder is prepared by adding carbon black to the synthetic
precursors followed by a single sintering process under optimized
conditions. The main effect of the carbon was to suppress the
growth of the LiMnPO4 particle size during the sintering process
and to enhance the electronic conductivity. Moreover, this material
has excellent thermal stability.
Acknowledgment
The authors thank Dr. K. Sekai for technical discussions.
Sony Corporation assisted in meeting the publication costs of this article.
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