3D printing of LFP and graphene-based electrodes via DIW and FDM for high-performance energy storage devices: opportunities and perspectives

Three-dimensional printing is an emerging manufacturing route for lithium-ion battery electrodes. It enables controlled material placement and architectural complexity that conventional slurry casting cannot replicate. The combination of lithium iron phosphate (LFP) as a safer, nickel and cobalt free cathode chemistry with graphene derived conductive networks offers a useful platform for sustainable, design-flexible energy storage devices. However, LFP’s low electronic conductivity (∼10^-9 S cm⁻1) and moderate Li⁺ diffusion kinetics, together with the printability- performance conflict in additive manufacturing, restrict full electrochemical utilization in thick printed electrodes. This review systematically examines direct ink writing (DIW) and fused deposition modeling (FDM) of LFP and graphene-based electrodes. It analyzes the coupled relationships between material chemistry, ink and filament formulation, printing parameters and electrode architecture, and their effects on ion/electron transport, areal capacity and cycling stability. A scientometric analysis of 307 articles (2011–2026) identifies dominant research clusters centered on hierarchical pore engineering, GO/rGO inks, conductive binders such as PEDOT:PSS and full-cell integration. Architecture-controlled DIW electrodes have achieved areal capacities of 11–14 mAh cm⁻2 and conductivities up to ∼ 10 S cm⁻1, while FDM has produced flexible TPU based LFP electrodes with 98.9% capacity retention over 400 cycles. Critical issues including ionic tortuosity, inactive material accumulation at interlayer boundaries and environmental considerations of solvents, additives and polymer feedstocks are also addressed. Key gaps in laboratory-to-industrial transferability, metric comparability, manufacturing efficiency and techno-economic assessment are identified. DIW and FDM therefore offer their strongest near-term value in applications such as micro-batteries, wearable electronics, structural energy storage, and thick high areal capacity electrodes.