SILMARA NEVES, ELIRIA M.J.A.

PALLONE and CARLA POLO FONSECA NEVES,

Laboratrio de Caracterizao e Aplicao de Materiais - LCAM Universidade So Francisco - Campus Itatiba/SP, 13251-900 - BRAZIL silmara.neves@saofrancisco.edu.br, http://www.saofrancisco.edu.br/laboratorios/lcam

Combustion synthesis is a novel powder processing technique that produces a multicomponent oxide material using an exothermic reaction between dissolved metal nitrates and fuel as reducing reactant. In this study, combustion synthesis was used in order to improve the electrode properties of LiMn2O4. The films were prepared using polyaniline (PAni) as an electronic conductor and the electrochemical behavior in lithium cells at room temperature was assessed1.
[1] C.P. Fonseca, E.M.J.A. Pallone, S.Neves, Solid State Science, in press.
Aqueous solution - lithium nitrate and manganese nitrate and urea (1:1:9 mol).
LiMn2O4 + 15%wt. PAni + 5% PVDF in DMA

First heat : 300rC

Muffle furnace at 600rC, where ignition took place

 SEM
Oxide consisted of nanosized crystallites, about 8080500 nm across, that fused into small agglomerates of 1-3 1Qm during the combustion reaction. The addition of PAni addition resulted in porous agglomerates with irregular particles formed by small oxide crystallites stuck together with 20 Qm polymer plates. plates.

 X-Ray Diffraction
500
(111) j
jLiMn 2O 4

 Cyclic Voltammetry
Two pairs of redox peaks at 2.75/2.30 V and 3.50/3.30 V were related to the cubic and tetragonal phases of manganese oxide and to the deintercalation/intercalation of Li respectively.
100
LiMn2 O4/PAni in PC/EC/1.0 mol L LiClO4 at 0.1 mV s .
-1 -1

600 400 200

Intensity (CPS)

400 300

17 18 19 20 21

200 100 10 20

(311) j

(400) (511) j
j

(440)

30

40

50

60

70

80

j (QA cm )

-2

75 50 25 0 -25 2.0

All diffraction peaks for this sample were attributed to the diffraction indices of the spinel phase of LiMn2O4. The crystalline grain size determined was 77 s 2.0 nm, which agreed with the SEM results.

2U

2.4

2.8

3.2

3.6

4.0

E vs. Li (V)

 Electrochemical Impedance Spectroscopy

20
10 Hz
-2

 Charge/Discharge Tests
E vs. Li (V)
4 2 0 4 2
1 charge cycle 25 charge cycle
th st

15

-Z" / k; cm

Rct (k ; cm )

Rp (; cm )

10
3
10 Hz
5

3.0 V 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 3.9 4.0 4.1 4.2

 Fittings used the equivalent circuit Re(RpCPE1)(RctCPE2) where Rct is the charge-transfer resistance, Rp is the resistance associated with particle-to-particle contact among the mixed oxide/conducting polymer particles, and Re is the electrolyte resistance. CPE1 and CPE2 CPE3 are the constant phase elements.
3 00
2 2

80 60 40 20 0

2 50

1 discharge cycle th 25 discharge cycle

-2

st

5
10 Hz
-2

2 1 0

2 00

j = +/- 0.1 mA.cm

1 50 3 .0 3 .2 3.4 3 .6 3 .8 4.0 4.2

0
3.0 3.2 3.4 3.6 3.8 4.0 4.2

10
2

15

20

50

100

150
-1

Z' / k; cm

E vs. Li (V)

E vs. Li (V)

pecific capacity (mAh g )

The variation in impedance as a function of the lithium intercalation/deintercalation process reflected the interaction between the oxide and/or polyaniline particles at a high frequency range, and a diffusion tendency was observed at medium and low frequency ranges.

The capacity values of the composite electrodes relative to the LiMn2O4 mass were 178.6/177.5 mAh g-1 and 145/140 mAh g-1 for the first and 25th charge/discharge cycles, respectively.

Business Card:

Comparison of specific capacity of LiMn2O4 with values

reported in the literature confirmed the potential usefulness of the combustion reaction for synthesizing lithiated manganese oxide for use in Li rechargeable batteries.