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Sputter Deposited Thin Film Cathodes from Powder Target for Micro Battery ApplicationsRao, K Yellareswara January 2015 (has links) (PDF)
All solid state Li-ion batteries (thin film micro batteries) have become inevitable for miniaturized devices and sensors as power sources. Fabrication of electrode materials for batteries in thin film form has been carried out with the existing technologies used in semiconductor industry. In the present thesis, radio frequency (RF) sputtering has been chosen for deposition of cathode material (ceramic oxides) thin films because of several advantages such as precise thickness control and deposition of compound thin films with equivalent composition. Conventional sputtering involves fabrication of thin film using custom made pellet according to the specification of sputter gun. However several issues such as target breaking are inevitable with the pellet sputtering. To forfend the issues, powder sputtering has been implemented for the deposition of various thin film cathodes in an economically feasible approach. Optimization of various process parameters during film deposition of cathode materials LiCoO2, Li2MnO3, LiNixMnyO4, mixed oxide cathodes of LiMn2O4, LiCoO2 and TiO2 etc., have been executed successfully by the present approach to achieve optimum electrochemical performance. Thereafter the optimized process parameters would be useful for selection of cathode layers for micro battery fabrication.
Chapter 1 gives a brief introduction to the Li ion and thin film solid state batteries. It also highlights the advantages of powder sputtering compared to conventional pellet sputtering.
In Chapter 2, the materials used and methods employed for the fabrication of thin film electrodes and analytical characterizations have been discussed.
In chapter 3, implementation of powder sputtering for the deposition of LiCoO2 thin films has been discussed. X-Ray diffraction (XRD), X-Ray photoelectron spectroscopy (XPS) and electrochemical investigations have been carried out and promising results have been achieved. Charge discharge studies delivered a discharge capacity of 64 µAh µm-1 cm-2 in the first cycle in the potential range
3.0-4.2 V vs. Li/Li+. The possible causes for the moderate cycle life performance have been discussed.
Systematic investigations for RF power optimization for the deposition of Li2-xMnO3-y thin films have been carried out. Galvanostatic charge discharge studies delivered a highest discharge capacity of 139 µAh µm-1cm-2 in the potential window 2.0-3.5 V. Thereafter, effect of LMO film thickness on electrochemical performance has been studied in the thickness range 70 nm to 300 nm. Films of lower thickness delivered higher discharge capacity with good cycle life than the thicker films. These details are discussed in chapter 4.
In Chapter 5, fabrication and electrochemical performance of LiNixMnyO4 thin films are presented. LMO thin films have been deposited on nickel coated stainless steel substrates. The as deposited films were annealed at 500 °C in ambient conditions. Nickel diffuses in to LMO film and results in LiNixMnyO4 (LMNO) film. These films were further characterized. Electrochemical studies were conducted up to higher potential 4.4 V resulted in discharge capacities of the order of 55 µAh µm-1cm-2.
In chapter 6, electrochemical investigations of mixed oxide thin films of LiCoO2 and LiMn2O4 have been carried out. Electrochemical investigations have been carried out in the potential window 2.0–4.3 V and a discharge capacity of 24 µAh µm-1cm-2 has been achieved. In continuation, TiO2 powder was added to the former composition and the deposited films were characterized for electrochemical performance. The potential window as well as the discharge capacity enhanced after TiO2 doping. Electrochemical characterization has been carried out in the potential window 1.4–4.5 V, and a discharge capacity of 135 µAh µm-1cm-2 has been achieved.
Finally chapter 7 gives overall conclusions and future directions to the continuation of the work.
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