Synthesis of Lithium Manganese Oxide (LiMn2O4) for Lithium Ion Battery Cathodes with Solution Method has been conducted. This experiment was carried out using the solution method. In this study, the synthesis was carried out by varying the calcination temperature. The raw materials used were Lithium Acetate (C2H3O2Li), Manganese Acetate (C4H6MnO4.4H2O), Hydrochloric Acid (HCl), and Ethanol (C2H5OH) as solvents which were dissolved to become LiMn2O4 precursors. Synthesis was carried out at calcination temperatures of 600oC, 700oC and 800oC, for 4 hours then pounded with a mortar until smooth. The characterization includes: The results of the STA test at 280oC-380oC showed a mass decrease of 11.9973% due to the release of mass of water vapor and decomposition of C4H6MnO4.4H2O raw material. XRD analysis shows that the increase in peak temperature of the LiMn2O4 phase intensity is getting sharper, the peak showing the impurity Li2O phase decreases. SEM analysis results show that the higher the calcination temperature, the larger the particle size is formed, because in the calcination process the densification process occurs

Priyono, Slamet

English

Talenta Publisher (E-Journals, Universitas Sumatera Utara)

Journal of Technomaterial Physics Vol. 2, No. 1, 2020 | 42 – 49  JoTP  Journal of Technomaterial Physics    *Corresponding author at: Kompleks Puspiptek Gedung 442 Serpong Tangerang Selatan Banten 15314, Indonesia  E-mail address: slamet.priyono@lipi.go.id  Copyright © 2020 Published by Talenta Publisher, ISSN: 2656-0747 e-ISSN: 2656-0755  Journal Homepage: https://talenta.usu.ac.id/index.php/JoTP Synthesis of Lithium Mangan Oxide (LiMn2O4) Using Solution Method for Lithium Ion Battery Catodes Materials Slamet Priyono1*, Kerista Sebayang2, Rike Yudianti3 and Siti Nur Aminah Sari Hasibuan4 1,3Pusat Penelitian Fisika-Lembaga Ilmu Pengetahuan Indonesia (LIPI) Kompleks Puspiptek Gedung 442 Serpong Tangerang Selatan Banten 15314, Indonesia 2,4Department of Physics, Faculty of Mathematics and Natural Science, Universitas Sumatera Utara 20155, Indonesia   Abstract. Synthesis of Lithium Manganese Oxide (LiMn2O4) for Lithium Ion Battery Cathodes with Solution Method has been conducted. This experiment was carried out using the solution method. In this study, the synthesis was carried out by varying the calcination temperature. The raw materials used were Lithium Acetate (C2H3O2Li), Manganese Acetate (C4H6MnO4.4H2O), Hydrochloric Acid (HCl), and Ethanol (C2H5OH) as solvents which were dissolved to become LiMn2O4 precursors. Synthesis was carried out at calcination temperatures of 600oC, 700oC and 800oC, for 4 hours then pounded with a mortar until smooth. The characterization includes: The results of the STA test at  280oC-380oC showed a mass decrease of 11.9973% due to the release of mass of water vapor and decomposition of C4H6MnO4.4H2O raw material. XRD analysis shows that the increase in peak temperature of the LiMn2O4 phase intensity is getting sharper, the peak showing the impurity Li2O phase decreases. SEM analysis results show that the higher the calcination temperature, the larger the particle size is formed, because in the calcination process the densification process occurs. Keyword: cathode material, solution method, Li-ion battery, lithium manganese oxide. Received 18 November 2019 | Revised [10 December 2019] | Accepted [14 February 2020] 1 Introduction Batteries are used in almost every aspect of modern life. Everyday household items such as flashlights, TV remotes, and electric drills require batteries. Even away from home, we rely on batteries to power our MP3 players, cell phones, and laptops. People with pacemakers or other portable medical devices trust batteries very much. With increasing concerns about dependence on fossil fuels and their environmental impact, alternative energy has become a major concern. However, alternative energy systems such as solar, wind, and water often require efficient batteries to store their energy. Hybrid or pure-electric vehicles require high-performance Journal of Technomaterial Physics Vol. 2, No. 1, 2020 | 42 – 49 43 batteries to compete with oil and gas engines. These devices drive the improvement of battery technology which is used in almost every aspect of modern life [1].  The battery is a device that converts chemical energy into electrical energy. Lithium batteries can be made as primary or secondary batteries. Both have different functions and characters. The primary battery has the ability to use only one time, one time discharge, while the secondary battery has the ability to charge / discharged repeatedly. In principle, this is due to the abundant availability of raw materials [2-3]. The electrochemical properties of LiMn2O4 are largely determined by crystal structure and oxide morphology [4-5]. LiMn2O4 has a spinel structure which has good structural stability during the charge-discharge process [6-7]. LiMn2O4 has a spinel structure with three dimensional intercalation capabilities. This causes the cathode material to be able to insert lithium ions in three directions. Lithium batteries are ion-based batteries with lithium ions as the spinel driving motor. LiMn2O4 shows a lack of resistance in the life cycle and an irreversible loss of capacity at high temperatures [8-9]. Insertion and extraction on LiMn2O4 spinel yields a mean voltage of 4 V. Spinel LiMn2O4 has advantages than Co and Ni material [10]. When a material is heated, the crystallization process will occur. Choosing the right temperature will determine the quality of the crystal structure formed and will affect the battery cell capacity. In this research, LiMn2O4 can be synthesized by solution method and calcination temperature variation will be studied. 2 Materials and Methods  Synthesis of LiMn2O4 powder using the solution method begins with weighing the raw materials, namely 2 g of LiMn2O4 powder, 0.7 g of C2H3O2Li, 6.1 g of C4H6MnO4.4H2O, 10 mL of ethanol to dissolve sample A and 30 mL of ethanol to dissolve sample B, and 0.25 mL of HCl in solution of sample A and 2 mL of HCl in solution of sample B to maintain the pH and to make the solution not to coagulate.  As much as 2 g sample were carried out in 2 different beakers. Each material is dissolved in a mixture of ethanol + HCl using a magnetic stirrer with a stirrer speed of 250 rpm, so that a solution of sample A (C2H3O2Li + HCl + ethanol) is formed and solution of sample B (C4H6MnO4.4H2O + HCl + ethanol), after the solution of sample B is finished then it remains stirred for 1 hour. After that solution of sample A is mixed with solution of sample B while continuing to stir until a sol is formed, then the solution is stirred for 5 hours, then the solution is poured into a petri dish and put in an oven for 16 hours, after it is dry then crushed and put into the plastic sample, before the calcination process is carried out. The refined LiMn2O4 is then weighed with a digital scale, this aims to find out how much LiMn2O4 was lost during the calcination process and to determine the accuracy of the characterization results. Then the sample in the plastic sample is put into a crucible and calcined at a temperature of 600°C, 700°C, 800° C for 4 hours then pounded with a mortar until smooth. The synthesis process of Journal of Technomaterial Physics Vol. 2, No. 1, 2020 | 42 – 49 44 making LiMn2O4 cathode material using the solution method between C2H3O2Li powder and 2C4H6MnO4.4H2O according to the reaction:                                                                    (1)  The samples were then characterized by STA, XRD and SEM. In the anode powder manufacturing process, the active ingedients of LTO are mixed with Al2O3 and Carbon Super P. The three ingedients are mixed in the milling chamber. The milling chamber is inserted into the Planetary Ball Miller tool. The milling time is set for 2 hours at a speed of 20.00 Hz. The material that is finished is milled and crushed using a spatula until smooth. Then the sample was sintered at a temperature of 850ºC for 4 hours. After sintering, crush the sample using a pastel until smooth and even. A small sample was taken for characterization using XRD to determine the phase and crystal structure of LTO, SEM to determine the morphology of the sample, and CV to determine the electrochemical performance of LTO powder. 3 Result and Discussion 3.1 STA Analysis LiMn2O4 powder was characterized thermally using a Simultaneous Thermal Analysis (STA) tool with the Linseis brand and the PT1600 type and the results of the data obtained were processed using Linseis Evaluation software to determine the sintering temperature of the LiMn2O4 powder.  Figure 1. DTA-TG LTO of LiMn2O4 The results of the STA analysis (Figure 1) shows that DTA (differential thermal analysis) temperature range of 20°C-280°C in the form of a downward curved graph with a peak, at temperatures around 280°C which is the release of organic elements such as CO2 and water vapor contained in the raw material and a phase occurs, in the temperature range 280°C-300°C which is an endothermic reaction (requiring heat) this peak is a decomposition process of C4H6MnO4.4H2O due to its melting point, at a temperature of 300°C there is a melting of Journal of Technomaterial Physics Vol. 2, No. 1, 2020 | 42 – 49 45 Lithium Acetate (C2H3O2Li), seen from material safety data that its melting point 80°C, in a temperature range of 400°C-800°C, there is a crystallization of LMO. In temperature of 570°C, it shows that the change in raw material has melted with a decrease in enthalpy of 34.43 J / g with the melting points of each raw material C2H3O2Li: 283°C-285°C and C4H6MnO4.4H2O: 80°C. In addition, adjusted to the TG (Thermogravimetry) graph that in the temperature range 280°C-380°C there was a mass decrease of 11.9973% due to the release of mass of water vapor and the decomposition of C4H6MnO4.4H2O raw material, in the next temperature range between 380°C-480°C there was a new phase formation, in the temperature range of 460°C-640°C, there was a mass decrease of 3.4191%, in the 640°C-1000°C temperature range there was a mass decrease of 6.5663%, and while the temperature range 480°C-900°C there was crystallization of LiMn2O4. 3.2 X-Ray Diffraction (XRD) Analysis   Figure 2. XRD Patterns of LiMn2O4 with calcination temperatures (a) 800°C, (b) 700°C, and (c) 600°C for 4 hours  Based on the results of the XRD analysis of LiMn2O4 powder, the resulting samples were sintered with calcination temperature variations of 600°C, 700°C and 800°C then XRD testing was carried out to identify the phase formed from each sample. The results of the XRD pattern of active material LiMn2O4 cathode in crystal field analysis can be seen in Figure 2. The crystal structure of the synthesized sample was characterized using Rigaku X-Ray Diffractometer with Cu Kα radiation operating at 40 kV and 30 mA. Diffraction data were collected every 4 s step with 0.010 with reference data with a measurement range at an angle of 10° - 90°. From the results of this test, it is obtained a curve that shows the intensity of the 2 angle, the XRD curve of the LiMn2O4 material with variations in calcination temperature can be seen in Figure 2. The test results with an angle of 2θ standard samples from ICDD data (International Center Journal of Technomaterial Physics Vol. 2, No. 1, 2020 | 42 – 49 46 Diffraction Database) on PDF (Powder Diffraction File) with number 01-070-3120 which can be seen in Figure 2.  The diffraction peaks that appear on XRD have the same thing as ICCD number 01-070-3120 for LiMn2O4 material. The full XRD analysis results can be seen in the attachment. Figure 2 shows the results of XRD processing with sinter temperature variations. The three samples were identified to have a LiMn2O4 crystal structure with the highest peak at an angle of 2θ = 18.710° with a plane distance of d = 4.7387 Å. The data matches or matches the ICDD data with PDF number 01-070-3120. Based on Figure 2, it can be seen that the active material of the LiMn2O4 cathode has a low level of crystallinity, this is indicated by the level of peak intensity obtained at each diffraction pattern is not so sharp. In Figure 2 (a) is the XRD pattern of the LiMn2O4 sample calcined at 800°C, after matching with the database (ICDD- 01-070-3120) [11-12]. At a calcination temperature of 600°C, it is almost the same as the pattern formed almost the same as the XRD pattern in the 800°C sample. From this curve, the peak intensity of LiMn2O4 is formed and the intensity of the impurities decreases even very small, the impurities contained in this pattern are the Li2O phase at the 2θ = 48.07°, this phase is a Li2O phase which is quite stable at high temperatures. At a calcination temperature of 700°C the pattern formed is almost the same as the XRD pattern in the 800°C sample, it's just that the intensity of the peak of the phase is different, the peak intensity of the LiMn2O4 phase looks lower while the peak intensity of the Li2O phase has increased. The Li2O impurity phase of these two samples is the metastable Li2O phase. In calcination temperature at 800°C indicates that the LiMn2O4 phase has been formed but there are impurities that were detected in the XRD spectrum. XRD measurements on LiMn2O4 material synthesized with LiOH.H2O showed that the LiMn2O4 phase had been formed but there were impurities detected in the XRD spectrum.  Meanwhile, with the synthesis of LiOH.H2O, the peak of the LiMn2O4 phase is at an angle of 2θ 18.710°; 23.070°; 32.87°; 35.970°; 37.720°; 43.920°; 48.070°; 49.450°; 55.170°; 58.080°; 63.800°; 65.840°; 67.200°; 75.630°; 76.600°; 80.670°; 83.680°. In this research, obtained LiMn2O4 material with a pure phase at a calcination temperature of 600°C with a long calcination time of 20 hours. So that Li2O impurities can be removed by increasing the temperature and the length of the calcination time [13]. From Figure 2, as a whole, it can be seen that the LiMn2O4 phase has been formed at a temperature range of 600°C - 800°C with a cubic crystal structure and Fd3m space group, but there is still impurity Li2O which does not completely react. But along with the increase in temperature, the peak intensity indicates that the LiMn2O4 phase is getting sharper, while the peak showing the Li2O phase the impurity decreases. The narrower and sharper peaks indicate that the crystal size formed from the LiMn2O4 phase is getting higher.  Journal of Technomaterial Physics Vol. 2, No. 1, 2020 | 42 – 49 47 3.3 Scanning Electron Microscope (SEM) Analysis           (a)          (b)   (c)  Figure 3. Morphology samples of LiMn2O4 with calcination temperatures (a) 600°C, (b) 700°C, and (c) 800°C  The results of the morphological characterization of the sample using SEM (Scanning Electron Microscope) with a magnification of 5 k SE can be seen in Figure 3. Morphologically, the surface of LiMn2O4 samples at 600°C has a rough texture, while the 700°C sample begins to form a smoother surface and in the 800°C sample. the texture formed is smoother than the other two samples. All samples consist of small and large particles that form agglomerations with various particle shapes such as round, rectangular, square and irregular shapes. But in the 800oC sample began to form gain boundaries on large particles, so that they appear to be in the form of smaller and finer particles. In calcination temperatures at 800°C sample there are also small particles that have a more uniform shape and gather to form one large material (bulk material). To determine the particle size of the LiMn2O4 powder material in data processing used Image-J software using images obtained from SEM test results with a magnification of 5k SE. Data taken 80 times with large, medium and small particle sizes, the processing results are displayed in a graph in the form of a histogram in Figure 4. Journal of Technomaterial Physics Vol. 2, No. 1, 2020 | 42 – 49 48     (a)      (b) /  (c)  Figure 4. Histogram Particle Distribution of LiMn2O4 with calcination temperature variations (a) 600°C, (b) 700°C, and (c) 800°C  Figure 4 shows that particles have a size with micro order (μ), particles with a size below 125 μm increase with increasing calcination temperatures. The smallest average particle size was owned by the sample with a calcination temperature of 600°C of 1.74 μm, while the largest average particle size was obtained in a sample with a calcination temperature of 800°C of 4.77 μm. So it can be compared that the higher the calcination temperature, the larger the particle size formed. This happens because in the calcination process the densification (compaction) of the particles occurs, but in this study the holding time is only 4 hours so that there is no gain growth, therefore when the temperature is higher the size of the particles that are formed the bigger. 4 Conclusion Synthesis of LiMn2O4 with calcination temperature variations of 400°C- 800°C is succesfully conducted by using solution method. DTA results that in temperature range 280°C-380°C decreased mass by 11.9973%, whereas in the temperature range between 380°C-480°C, there was a new phase formation, then in the temperature range 480°C-900°C occurred crystallization Journal of Technomaterial Physics Vol. 2, No. 1, 2020 | 42 – 49 49 of LiMn2O4. The XRD analysis results showed that the peak cathode intensity of the LiMn2O4 single phase was lower, while the peak intensity of the Li2O phase increased. LiMn2O4 phase change has been formed at a temperature range of 600°C-800°C with a cubic crystal structure and space goup Fd3m. The narrower and sharper peaks indicate that the crystal size formed from the LiMn2O4 phase is getting higher. The calcination temperature in LiMn2O4 material characteristics, the particles size had below 125 μm increased as the calcination temperature increased. REFERENCES    [1] L. Jonathan, “Improving Lithium-Ion Battery Power and Energy Densities using Novel Cathode Architectures and Materials,” M.S. thesis, University of Illinois, Urbana-Champaign, 2012. [2] C. Julien, A. Mauger, A. Vijh and K. Zaghib, Lithium Batteries: Science and Technology, Switzerland: Springer International Publishing, 2016. [3] C. A. Vincent, "Lithium Batteries: a 50-year Perspective, 1959–2009," Solid State Ionics, vol. 134, no. 1-2, pp. 159-167, 2000. [4] H. Wibowo, Konsep Dasar Kimia, Yogyakarta: Fakultas Teknik UNY, 2005. [5] M. O. Guler, A. Akbulut, T. Cetinkaya, M. Uysal and H. Akbulut, "Improvement of Electrochemical and Structural Properties of LiMn2O4 Spinel Based Electrode Materials for Li-Ion Batteries," International Journal of Hydrogen Energy, vol. 39, no. 36, pp. 21447-21460, 2014. [6]  H-W. Lee, P. Muralidharan, R. Ruffo, C.M. Mari, Y. Cui and D. K. Kim, "Ultrathin Spinel LiMn2O4 Nanowires as High Power Cathode Materials for Li-Ion Batteries," Nano Letters, vol. 10, no. 10, pp. 3852-3856, 2010. [7] D. Arumugam, G. P. Kalaignan and P. Manisankar, "Development of Structural Stability and the Electrochemical Performances of  „La‟ Substituted Spinel LiMn2O4 Cathode Materials for Rechargeable Lithium-Ion Batteries," Solid State Ionics, vol. 179, no. 15-16, pp. 580-586, 2008. [8]  S. Priyono, S. Hardiyani, N. Syarif, A. Subhan and A. Suhandi, "Electrochemical Performanceof LiMn2O4 with Varying Thickness of Cathode Sheet," Journal of Physics: Conference Series, vol. 1191, no. 1, IOP Publishing, 2019. [9] M. A. Kiani, M. F. Mousavi and M. S. Rahmanifar, "Synthesis of Nano- and Micro-Particles of LiMn2O4: Electrochemical Investigation and Assessment as a Cathode in Li Battery," Int. J. Electrochem. Sci., vol. 6, pp. 2581-2595, 2011. [10] K. A. Kasvayee, “Synthesis of Li-Ion Battery Cathode Materials Via Freeze Ganulation,” M.S. thesis, Chalmers University of Technology, Gothenburg, Sweden, 2011. [11] S. Priyono, N. R. Ginting, S. Humaidi, A. Subhan and B. Prihandoko, "Synthesis of Lithium Mangan Dioxide (LiMn2O4) for Lithium-ion Battery Cathode from Various Lithium Sources,” IOP Conf. Series: Journal of Physics, vol: 985, pp. 012054, 2018. [12] N. F. Yahya, N. Kamarulzaman, K. Elong, N. A. M. Mokhtar, A. F. M. Fadzil, N. H. Zainol and A. Azahidi, "Synthesis of LiMn1.9Ti0.1O4 via a Combustion Method," In AIP Conference Proceedings, vol. 1877, no.1, pp. 040008, 2017. [13] J. Zhang, Y. Li, L. Wang, C. Zhang and H. He, “Catalytic Oxidation of  Formaldehyde Over Manganese Oxides with Different Crystal Structures,” Catal. Sci. Technol., vol. 5, pp. 2305-2313, 2015.   

Synthesis of Lithium Mangan Oxide (LiMn2O4) Using Solution Method for Lithium Ion Battery Catodes Materials

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Synthesis of Lithium Mangan Oxide (LiMn2O4) Using Solution Method for Lithium Ion Battery Catodes Materials

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