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This article reports the studies on Li-ion full-cell fabrication using Li4Ti5O12 (LTO) as anode and LiCoO2 (LCO) as cathode materials with emphasis on scaling from coin cell (2032 type) to rectangular pouch-type cells (45 × 58 mm). The electrode materials were synthesized in-house and characterized for their phase purity and morphology using XRD and FE-SEM techniques. Their electrochemical performance is evaluated against Li/Li+ using cyclic voltametry, electrochemical impedence spectrosopy and galvanostatic charge–discharge. The optimized materials were further used for fabrication of full cells in 2032 type initially and later in pouch cell geometry with different negative (N) to positive (P) electrode ratio (N/P ratio) and tested its effect on the cell performance. It is found that cells employing an N/P ≥ 1.0 can give steady and good performance in terms of discharge capacity. In case of 2032 type full cell, for N/P ≥ 1.0, the maximum achieved specific capacity is 118 mAh g−1 while 110 mAh g−1 for pouch cell in the same N/P ratio. The impedance spectroscopy has been employed to support the performance of the cells. This finding can be used as a guideline for preparing full cells for other electrode combinations as well as higher capacity cells. This will also help in designing efficient battery management system. [ABSTRACT FROM AUTHOR]