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Materials Chemistry and Physics 109 (2008) 241248

Ammonium carboxylates assisted combustion process for the synthesis of nanocrystalline LiCoO2 powders
S. Vivekanandhan a , M. Venkateswarlu b , N. Satyanarayana a,
a

Department of Physics, Pondicherry University, Pondicherry 605014, India b HBL Power Systems Ltd., Hyderabad 500078, India

Received 26 July 2007; received in revised form 22 October 2007; accepted 10 November 2007

Abstract Nanocrystalline LiCoO2 powders were synthesized by combustion process using three different ammonium carboxylates named ammonium acetate (AA), ammonium citrate (AC) and ammonium tartarate (AT) as fuels and metal nitrates as the source of metal ions as well as oxidants. Effect of three different ammonium carboxylates on the synthesis of nanocrystalline LiCoO2 powders was investigated through FTIR, XRD, TG/DTA and SEM techniques. FTIR and XRD analysis conrmed that the LiCoO2 phase could obtain by calcining the polymeric intermediates at 450 C for 12 h. Among the three different fuels, ammonium citrate assisted combustion process exhibited the formation of organic free phase pure nanocrystalline LiCoO2 powders. The average crystallite size of the LiCoO2 powder prepared at 450 C for 12 h by ammonium citrate assisted process is found to be 24 nm. 2007 Elsevier B.V. All rights reserved.
Keywords: Nanostructures; Chemical synthesis; Fourier transform infrared spectroscopy (FTIR); Microstructure

1. Introduction Layered LiCoO2 powders have been widely investigated as a cathode material for rechargeable lithium batteries due to its advantages such as easy preparation, high voltage, better cyclicality and high theoretical specic capacity [15]. So, it has been used in commercial lithium cells [6]. The electrochemical properties of cathode materials like storage capacity, voltage and charging/discharging rates are considerably increase when their crystallite/particle size has reduced to nanosize [79]. In recent years, signicant effort has been made to synthesis the nanostructured cathode materials in order to enhance their electrochemical properties [1012]. Synthesis of nanocrystalline cathode powders by conventional solid-state reaction is often difcult due to higher operating temperature and the resulting powders exhibit poor homogeneity and wide distribution of crystallite size [13,14]. Hence, a variety of wet chemical methods such as solgel, co-precipitation, hydrothermal, combustion, etc., were developed and investigated for the synthesis

Corresponding author. Tel.: +91 413 2654404; fax: +91 413 2655265. E-mail address: nallanis2000@yahoo.com (N. Satyanarayana).

of nanocrystalline cathode powders with desired properties [1520]. Among the various wet chemical processes, combustion route is found to be simple and cost effective for the synthesis of wide range of nanocrystalline powders [2124]. Combustion process involves the exothermic decomposition of fuel and oxidant precursors, which results in the formation of oxide nanoparticles relatively at lower temperatures. Physicochemical properties of the oxide powders synthesized by combustion process are mainly depending on the nature and the amount of fuel that used [25,26]. In order to identify the suitable fuel for the synthesis of oxide ceramics in nanophase, wide range of research has been made using the various organic fuels such as urea, citric acid, glycine, etc. [2730]. Recently, we found that the formation of ammonium citrate with in the polymeric intermediates reduced the ignition temperature and also calcining duration, which resulted the formation of organic free phase pure nanocrystalline oxide powders [31]. The role of ammonium citrate is to ignite the combustion reaction relatively at lower temperatures and also caused the large gas evaluation, which lead to the formation of ultra ne particles. Hence, in the present work, combustion process using different ammonium carboxylates such as ammonium acetate (AA),

0254-0584/$ see front matter 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.matchemphys.2007.11.027

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Fig. 3. FTIR spectra of the polymeric intermediates prepared with three different ammonium carboxylates (AA, AC and AT).

2. Experimental procedure
Nanocrystalline LiCoO2 powders were synthesized using ammonium carboxylates assisted combustion process by following the procedure shown in Fig. 1. Stoichiometric amount of lithium nitrate (AR grade, s-d ne, India) and cobaltus(III) nitrate (AR grade, Merck, India) solutions were mixed with the solutions of different ammonium carboxylates named ammonium acetate, ammonium citrate and ammonium tartarate anhydrous (AR grade, Merck, India) under constant stirring. Total metal ion to ammonium carboxylate ratio (M:AA, M:AC and M:AT) was kept constant as 1:1. The obtained pink colour solutions were evaporated at 80 C for 6 to 8 h. Continuous evaporation leads to the formation of pink coloured polymeric resin. Obtained polymeric resign was further dried at 120 C for 12 h to remove the excess water, which lead to the formation of solid mass. Photograph of as obtained polymeric intermediates using ammonium acetate, ammonium citrate and ammonium tartarate is shown in Fig. 2. Further, these intermediates were ground and calcined at an optimum temperature to obtain nanocrystalline LiCoO2 powders.

Fig. 1. Schematic of ammonium carboxylates assisted combustion process for the synthesis of nanocrystalline LiCoO2 powders.

ammonium citrate (AC) and ammonium tartarate (AT) as fuels was investigated for the synthesis of nanocrystalline LiCoO2 powders. The effect of various ammonium carboxylates on the synthesis of LiCoO2 powders was identied through FTIR, XRD, TG/DTA and SEM techniques.

Fig. 2. Photograph of the polymeric intermediates prepared with three different ammonium carboxylates (AA, AC and AT).

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Fourier transform infrared (FTIR) spectra were recorded using FTIR-8000 spectrometer of Shimadzu, Japan, to identify structural coordination of as prepared as well as calcined polymeric intermediates. The measurement was carried out in the range of 4004000 cm1 with KBr diluter. X-ray diffraction (XRD) experiments were carried out using a Panalytical, X-ray powder diffractometer, Netherlands, with Cu K radiation. The average crystallite size was calculated from the Scherrers formula. NBS standard silicon was used for estimation of instrumental broadening [32]. Thermal behavior of the polymeric intermediates was investigated by simultaneous TG/DTA measurement using Labsys thermal analyzer, Setaram, France. Approximately, 3 mg of polymeric intermediate was heated at a rate of 10 C min1 between 30 and 600 C. All thermal studies were performed in owing oxygen. Microstructure of the polymeric intermediates was identied using scanning electron microscope, Hitachi, S-3400N, Japan.

3. Results and discussion 3.1. Characterization of polymeric intermediates Fig. 3 shows the FTIR spectra of polymeric intermediates prepared with three different ammonium carboxylates (ammonium acetate, ammonium citrate and ammonium tartarate). From Fig. 3, the IR absorption at 33983425 cm1 region is attributed to stretching of OH groups exist in the polymeric intermedi-

Fig. 4. XRD pattern of the polymeric intermediates prepared with three different ammonium carboxylates (AA, AC and AT).

Fig. 5. Scanning electron micrograph (two different magnications) of the polymeric intermediates prepared with three different ammonium carboxylates (AA, AC and AT).

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boxylates are shown in Fig. 4. The observed peaks in the XRD patterns indicate the formation of metal carboxylates (as precipitate) as well as metal carbonates, which may be due to the poor polymerization of ammonium carboxylates. Further, it is conrmed by SEM analysis. Fig. 5 shows the scanning electron micrographs of polymeric intermediates. SEM images of the polymeric intermediates synthesized using ammonium acetate and ammonium tartarate showed porous microstructure, where the voids are uniformly distributed through out the surface. Where as, the polymeric intermediates prepared with ammonium citrate, exhibits polymeric microstructure with big voids. The observed polymeric nature of the intermediate is well consistent with FTIR results. Ammonium tartarate assisted polymeric intermediate exhibits high porosity than other two intermediates, which are shown in higher magnication. 3.2. Thermal behavior of the polymeric intermediates TG/DTA thermograms of the polymeric intermediates prepared using three different ammonium carboxylates are shown in Fig. 6. From Fig. 6 the observed endothermic peak around 200 C for all the intermediates indicates the deformation of the polymeric structure. Endothermicity of the denaturing reaction is more for the ammonium citrate assisted intermediates, which indicates the strong bond between the citrate derivatives. Thermogram of all the polymeric intermediates showed two different exothermic peaks DTA curve and respective weight loss was observed in the TG curve. The exothermic peak observed at low-temperature region (240300 C) is might be due to the decomposition of ammonium carboxylate present in the dried intermediates. Weight loss is more for the polymeric intermediate prepared using ammonium tartarate (about 53%); where as the weight loss for ammonium acetate and ammonium citrate assisted intermediates are respectively found to be 28 and 30%. The second exothermic reaction, which may be due to the decomposition of metal carboxylate derivatives, starts at 281, 348 and 287 C, respectively for the intermediates prepared with AA, AC and AT. The exothermicity of above decomposition reaction defers with respect to the microstructures obtained from SEM. More exothermicity is observed for the AT assisted intermediate, which is due to the high-porous structure (Fig. 5c), also the observed lower exothermicity for the intermediate prepared with ammonium acetate is may be due to the lower porosity (Fig. 5a). Though the ammonium citrate assisted polymeric intermediates exhibits poor porosity in SEM analysis, it exhibits high exothermicity during the combustion, because of its combustion mechanism as shown in Fig. 7. Fig. 7 shows the photographs of the AC assisted polymeric intermediate at different temperatures. The intermediate begins to melt at 200 C (respective exothermic peak is observed in DTA curve) and the volume of the intermediate has increased, which results foam type product. Further heating, caused the decomposition at 250 C with large gas evaluation and it is observed in DTA curve as exothermic peak between 250280 C. And the complete decomposition has observed at 400 C and the respective exothermic peak was observed in DTA curve. Occurrence of

Fig. 6. TG/DTA thermograms of the polymeric intermediates prepared with three different ammonium carboxylates (AA, AC and AT).

ates [33]. The strong broad peak observed at 33253030 cm1 region for all the intermediates is attributed to NH4 + groups, which shows the presence of ammonium ions in polymeric intermediates [33]. IR peaks observed at 16081632 cm1 and 14001415 cm1 region for all the intermediates are, respectively due to the asymmetric and symmetric stretching vibration of COO groups, which conrms the chelation of metal ions by COO groups present in the ammonium carboxylates [34]. The weak band observed at 10871098 cm1 region for all the samples is assigned to CO3 2 functional groups, which may be due to the formation of metal carbonates [33]. The polymeric intermediate prepared with citric acid shows an additional IR peak at 1292 cm1 corresponds to the asymmetric vibration of COC group (ester) (where the respective symmetric vibration merged with the vibration of CO3 2 functional group), which caused the formation of branched polymeric network between citric acid derivatives, further it is conrmed by SEM analysis [33]. X-ray diffraction patterns of the polymeric intermediates prepared by combustion process, using different ammonium car-

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Fig. 7. Photographs of the combustion reaction of polymeric intermediate prepared with ammonium citrate (A) dried polymeric intermediate, (B) melt of polymeric intermediate (200 C), (C) combustion of polymeric foam intermediate (250 C) and (D) polymeric intermediate after the combustion (400 C).

the foam intermediate during the calcining process caused the better combustion and lead to the organic free nal products, which is not observed for the intermediates prepared using AA and AT. Further it is conrmed from FTIR results. From the TG/DTA analysis, all the combustion reactions are completed before 450 C and hence, it is optimized for the calcinations of polymeric intermediates in order to obtain the nal product. Typical FTIR spectra of the polymeric intermediate (prepared with citric acid) calcined at different temperatures are shown in Fig. 8. The FTIR peaks related to organic derivatives are begins to disappear at 300 C and completely disappeared when the intermediate is calcined at 450 C and above, which is consistence with TG/DTA results. The newly observed FTIR peaks at 510520 cm1 and 580610 cm1 regions are attributed to asymmetric stretching modes of [CoO6 ] octahedral in LiCoO2 structure [35,36]. Fig. 9 shows the typical XRD patterns of calcined polymeric intermediate prepared with ammonium citrate at different temperatures. From Fig. 9, it is clear that the layered LiCoO2 phase begins to form at 300 C and the complete phase was obtained at 450 C and above which is consistence with TG/DTA and FTIR results. Also, the observed intensication of the peaks as a function of calcining temperature indicates the increment in crystallinity. XRD pattern for the sample calcined at 450 C showed all the peaks, which indicates the completion of crystallization process. 3.3. Characterization of LiCoO2 powders Fig. 10 shows the FTIR spectra of synthesized LiCoO2 powders prepared by AA, AC and AT assisted combustion process at 450 C for 12 h. The observed FTIR peaks at 510520 cm1 and 580610 cm1 region are attributed to asymmetric stretch-

ing modes of [CoO6 ] octahedral, which conrmed the formation of LiCoO2 structure for all the samples. From Fig. 10, the FTIR spectra for the intermediates prepared with ammonium acetate and ammonium tartarate showed low intense peaks at 14551553 cm1 region, which is attributed to organic residuals that indicates the presence of undecomposed organic derivatives in the intermediates due to poor combustion. It is attributed to its microstructure as observed in scanning electron micrograph and thermal behavior as observed in TG/DTA. Organic free LiCoO2

Fig. 8. Typical FTIR Spectra of the polymeric intermediate calcined at different temperature prepared with ammonium citrate.

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Fig. 9. Typical XRD pattern of the polymeric intermediate calcined at different temperature prepared with ammonium citrate.

Fig. 11. XRD pattern of polymeric intermediate calcined at 450 C prepared with three different ammonium carboxylates (AA, AC and AT). Table 1 Comparison of lattice parameter values of synthesized LiCoO2 powders by AC assisted combustion process with literatures S. No. 1 2 3 4 5 a (A) 2.81 2.83 2.82 2.83 2.83 c (A) 13.99 13.85 14.06 14.00 13.87 c/a 4.97 4.90 4.99 4.95 4.9 References Present work [39] [40] [41] [42]

structure is observed only for the ammonium citrate assisted process, which conrms the better combustion and lead to the complete decomposition of organic derivatives. The XRD patterns of synthesized LiCoO2 powders at 450 C along with JCPDS standard are shown in Fig. 11. The observed three strong peaks at 19.00 (0 0 3), 37.38 (1 0 1) and 45.51 (1 0 4) regions for all the samples indicate the formation of crystalline LiCoO2 phase of -NaFeO2 type structure [37]. From Fig. 11, the observed small peak at 31.5 for LiCoO2 samples prepared by AA and AT assisted process indicates the presence of Co2 O3 impurity phase, which may be due to the poor combustion [38]. The XRD pattern for LiCoO2 sample prepared

by AC assisted process, exhibits not only pure phase but also the hexagonal doublets (0 0 6)/(0 1 2) and (1 0 8)/(1 1 0), which indicates the good hexagonal ordering and great layered characteristics and the obtained peaks are indexed to the hexagonal cell [39]. Cell parameters calculated for the LiCoO2 powders

Fig. 10. FTIR spectra of polymeric intermediates calcined at 450 C prepared with three different ammonium carboxylates (AA, AC and AT).

Fig. 12. Typical SEM image of the nanocrystalline LiCoO2 powder prepared with ammonium citrate.

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Fig. 13. SEMEDS spectrum and elemental mapping of nanocrystalline LiCoO2 powder prepared with ammonium citrate.

prepared by AC assisted process are a = 2.81 A, c = 13.99 A and c/a = 4.97, which are very much comparable with those reported in the literature. Table 1 gives the comparison of lattice parameters values of synthesized LiCoO2 powders with the reported values [4042]. The crystallite size of the synthesized LiCoO2 powders at 450 C by ammonium citrate assisted process was calculated using the broadening data of the 100% peak at 19.03 for the (0 0 3) plane (recorded at the scanning rate of 1/2 per min) obtained through Lorentz tting method and the Scherrers formula [32]. The calculated crystallite size of the LiCoO2 powders synthesized by ammonium citrate assisted process is found to be 24 nm. Fig. 12 shows the typical SEM micrographs of the LiCoO2 powders prepared by ammonium citrate process at 450 C for 12 h. SEM images of the LiCoO2 powders exhibit the loosely agglomerated ultra ne LiCoO2 particles. All the agglomerated LiCoO2 particles exhibit uniform size of 4070 nm. SEMEDS (energy dispersive spectroscopy) spectrum with elemental mapping of LiCoO2 powders synthesized using AC is shown in Fig. 13. EDS elemental mappings show the uniform distribution of Co and O, which indicates the formation of LiCoO2 structures. No evidence was identied for the presence of carbon in LiCoO2 powders from SEMEDS analysis, which also conrmed the formation of organic free LiCoO2 structure. FTIR, XRD and SEMEDS analysis conrmed that the ammonium citrate assisted combustion process results the phase pure organic free nanocrystalline LiCoO2 powders and hence it is optimized for the synthesis of LiCoO2 powders.

4. Conclusion Nanocrystalline LiCoO2 powders were synthesized using combustion process with three different ammonium carboxylates named ammonium acetate, ammonium citrate and ammonium tartarate as the fuels at 450 C. TG/DTA, XRD and FTIR studies showed that the LiCoO2 phase begun to form at 300 C and the complete phase was obtained at 450 C. There were remarkable differences in the process in terms of microstructure of the intermediates, combustion mechanism, residual carbon and the phase nature of the nal products. It was identied that the microstructures of the intermediates were well depend on the precursor chemical and plays major role in their physicochemical properties of the nal products. From FTIR, XRD, TG/DTA and SEMEDS analysis, it is concluded that ammonium citrate assisted process is more favorable than others for the synthesis of phase pure organic free nanocrystalline LiCoO2 powders. The crystallite size of LiCoO2 powders prepared by ammonium citrate assisted process was found to be 24 nm. Acknowledgements Dr. N. Satyanarayana gratefully acknowledges DST, CSIR, DRDO, Government of India, for the nancial support through major research projects. SV acknowledges the CSIR, Government of India, for the award of Senior Research Fellowship (SRF).

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