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Traditional high performance electronic substrates are currently fabricated with molds and screens by stacking punched green ceramic tapes and selectively screen printing electrical interconnects with silver-particle pastes and inks. The structures are spatially registered and stacked, then subsequently fired with pressure to provide electrically-conductive traces in thermally-conductive high-performance dielectric substrates. However, Low Temperature Co-Fired Ceramics (LTCC) processes require tooling and are geometrically limited as opposed to the fully-digital 3D nature of additive manufacturing. Printing alumina substrates is now possible with high spatial resolution, superior surface finish and complex geometries (overhangs, density-varying lattices, internal microfluidics). This facilitates the production of distinctive circuitry that would otherwise be constrained by current manufacturing limitations, paving the way for novel sensing capabilities, secure electronics, heat exchangers, placement in extreme environments, and the integration of circuitry into otherwise inaccessible locations. This work is focused on thermal processing of dielectric ceramics and conductive inks, with a three-step furnace profile accounting for the disparate temperatures of the different materials: high temperature ceramics, mid temperature metal inks and finally adhesion of active electronic components. In the proof of concept demonstration, complex alumina substrates were fabricated which can accommodate miniaturized electronic components (including known good silicon die) and channels for the protection of deposited conductive inks to serve as interconnects. The electrical conductivity of commercially-available silver inks was explored for a range of thermal processing treatments (up to 1000°C) given the thermal stability of 3D printed alumina. An electrical conductivity of $3.13\times 10^{7}$ S/m which is within 53% of bulk copper plated in traditional printed circuit boards (PCB), the theoretical conductivity of bulk silver was achieved at about half the melting temperature.

The advent of conductive extrudable materials has broadened the range of additive manufacturing applications to include smart devices, circuits, actuators and sensors – all requiring electrical power. 3D printing of components dedicated to energy storage has also gained interest, with the goal of the monolithic printing of batteries directly integrated into subsuming smart components. This review focuses on the state of the art of extrusion-based 3D printed batteries, appearing as the most widespread, inexpensive and simple additive process. The paper is intended to introduce the processes and materials of 3D printing batteries, while highlighting the main manufacturing challenges and associated solutions proposed in literature. Particular attention is dedicated to describing the extrusion-based printers being employed and the required modifications, printing parameters and multi-material capabilities, with the aim of highlighting the most promising solutions required to print composite individual components and complete rechargeable batteries in a single non-assembly step.

Abstract Additive manufacturing, also called 3D printing, has the potential to enable the development of flexible, wearable and customizable batteries of any shape, maximizing energy storage while also reducing dead-weight and volume. In this work, for the first time, three-dimensional complex electrode structures of high-energy density LiNi1/3Mn1/3Co1/3O2 (NMC 111) material are developed by means of a vat photopolymerization (VPP) process combined with an innovative precursor approach. This innovative approach involves the solubilization of metal precursor salts into a UV-photopolymerizable resin, so that detrimental light scattering and increased viscosity are minimized, followed by the in-situ synthesis of NMC 111 during thermal post-processing of the printed item. The absence of solid particles within the initial resin allows the production of smaller printed features that are crucial for 3D battery design. The formulation of the UV-photopolymerizable composite resin and 3D printing of complex structures, followed by an optimization of the thermal post-processing yielding NMC 111 is thoroughly described in this study. Based on these results, this work addresses one of the key aspects for 3D printed batteries via a precursor approach: the need for a compromise between electrochemical and mechanical performance in order to obtain fully functional 3D printed electrodes. In addition, it discusses the gaps that limit the multi-material 3D printing of batteries via the VPP process.

High-resolution additive manufacturing offers access to the production of intricate architectures with small features that can revolutionize the fabrication of next-generation batteries. Relegated to two-dimensional sheets, commercial lithium-ion batteries consist of stacked leaflets, which are manufactured in restricted stacked or rolled geometries. By leveraging the most recent advancements of vat photopolymerization (VPP), the next-generation of shape-conformable three-dimensional batteries can be co-designed with known application requirements and provide enhanced safety and power performance based on reduced weight and dead volume. Herein, an overview of the state of the art with perspectives towards the development of electroactive photo-polymerizable resins for the direct fabrication of complete multi-material three-dimensional batteries is presented. Different approaches are described, including the formulation of composite resin through the introduction of solid electroactive particles, soluble components or metal precursors. Finally, the impact of the thermal post-processing steps on the resulting electrochemical properties of the VPP printed battery component or device is thoroughly discussed. This study paves the way towards the manufacturing of a complete high-resolution shape conformable 3D battery via VPP with enhanced power density.

In this work, the ability to print shape-conformable batteries with multi-process additive manufacturing is reported. Vat photopolymerization (VPP) 3D printing process is employed to manufacture gel polymer electrolytes (GPEs) for sodium-ion batteries (SIBs), while direct ink writing process is used to prepare positive electrodes. The sodium-ion chemistry has proven to be an adequate substitute to lithium-ion due to the availability of resources and their potential lower production cost and enhanced safety. Three-dimensional printing technologies have the potential to revolutionize the production of shape-conformable batteries with intricate geometries that have been demonstrated to increase the specific surface area of the electrode and ion diffusion, thus leading to improved power performances. This study shows the preparation of composite UV-photocurable resins with different polymer matrix-to-liquid electrolyte ratios, designed to act as GPEs once printed via VPP. The impact of the liquid electrolyte ratio within the GPEs is thoroughly examined through a variety of electrochemical techniques. The exposure time printing parameter is optimized to ensure adequate print accuracy of the GPE. Using the optimized resin composition as material feedstock, shape-conformable 3D printed GPE exhibiting an ionic conductivity of 3.3 × 10 ^−3 S·cm ^−1 at room temperature and a stability window up to 4.8 V vs. Na ^0 /Na ^+ is obtained. In parallel, a composite ink loaded with Na _0.44 MnO _2 and conductive additives is developed to 3D print via direct ink writing positive electrodes. After demonstrating the functionality of the independent 3D printed components in SIBs, the last part of this work is focused on combining the 3D printed Na _0.44 MnO _2 electrode and the 3D printed GPE into the same battery cell to pave the way towards the manufacturing of a complete 3D printed battery thanks to different additive manufacturing processes.

This article focuses on the development of polylactic acid– (PLA-) based thermoplastic composite filament for its use, once 3D printed via thermoplastic material extrusion (TME), as current collector at the negative electrode side of a lithium-ion battery or sodium-ion battery. High electronic conductivity is achieved through the introduction of Ag-coated Cu charges, while appropriate mechanical performance to allow printability was maintained through the incorporation of poly(ethylene glycol) dimethyl ether average Mn ∼ 500 (PEGDME500) as a plasticizer into the PLA polymer matrix. Herein, thermal, electrical, morphological, electrochemical, and printability characteristics are discussed thoroughly. While Ag-Li alloy formation is reported at 0.1V upon cycling, its use with active materials such as Li4Ti5O12 (LTO) or Li2-terephthalate (Li2TP) operating at a plateau at higher potential is demonstrated. Furthermore, its ability to be used with negative electrode active material of sodium-ion battery technology in a wide potential window is demonstrated.