(Battery Division Postdoctoral Associate Research Award Sponsored by MTI Corporation and the Jiang Family Foundation) 3D Printing of Batteries: Fiction or Reality?
Authors: Maurel Alexis , Martinez Ana Cristina , Grugeon Sylvie , Panier Stephane , Dupont Loic , Armand Michel , Russo Roberto , Boudeville Victor , Cortes Pedro , Yelamanchi Bharat , Chavari Sina Bakhtar , Aranzola Ana , Sreenivasan Sreeprasad T , Sherrard Cameroun , MacDonald Eric 
Published: November 2022

Motivated by the request to build shape-conformable flexible, wearable and customizable batteries while maximizing the energy storage and electrochemical performances, additive manufacturing (AM) appears as a revolutionary discipline. Battery components such as electrodes, separator, electrolyte, current collectors and casing can be tailored with any shape, allowing the direct incorporation of batteries and all electronics within the final three-dimensional object. AM also paves the way toward the implementation of complex 3D electrode architectures that could enhance significantly the power battery performances. Transitioning from conventional 2D to complex 3D lithium-ion battery (LIB) architectures will increase the electrochemically active surface area, enhance the Li+ diffusion paths, thus leading to improved specific capacity and power performance [1]. Our recent modeling studies [2] involving the simulation of a classical Ragone plot illustrated that a gyroid 3D battery architecture has +158% performance at a high current density of 6C, in comparison to planar geometry.

In this presentation, an overview of current trends in energy storage 3D printing will be discussed [3-11]. A summary of our recent works on lithium-ion battery 3D printing via Thermoplastic Material Extrusion / Fused Deposition Modeling will be presented [12-16]. The development of printable composite filaments (Graphite-, LiFePO4-, Li2TP-, PEO/LiTFSI-, SiO2-, Ag/Cu-based) corresponding to each part of a LIB (electrodes, electrolyte, separator, current collectors), and the importance of introducing a plasticizer (polyethylene glycol dimethyl ether average Mn 500 for polylactic acid) as an additive to enhance the printability will be addressed. Printing of the complete LIB in a single step using multi-material printing options, and the implementation of a solvent-free protocol [14] will also be discussed. Second part of this presentation will be dedicated to AM of batteries by means of Vat Photopolymerization (VPP) processes, including stereolithography, digital light processing and two-photon polymerization (offering a greater resolution down to 0.1μm), to print high resolution battery components [10]. Composite resins formulation approaches based on the introduction of solid battery particles or precursor salts will be introduced [17, 18]. Finally, an overview of our ongoing project dedicated

to AM of sodium-ion batteries from resources available on the Moon and Mars will be presented. Due to its relative abundance in the Lunar regolith, the development of a composite photocurable resin loaded with TiO2 negative electrode material and conductive additives, to feed a VPP printer, will be discussed [18].

[1] Long et al., Three-dimensional battery architectures, Chemical Reviews 104(10) (2004) 4463-4492.

[2] Maurel et al., Considering lithium-ion battery 3D-printing via thermoplastic material extrusion and polymer powder bed fusion, Additive Manufacturing (2020) 101651.

[3] Maurel et al., Overview on Lithium-Ion Battery 3D-Printing By Means of Material Extrusion, ECS Transactions 98(13) (2020) 3-21.

[4] Ragones et al., Towards smart free form-factor 3D printable batteries, Sustainable Energy & Fuels 2(7) (2018) 1542-1549.

[5] Reyes et al., Three-Dimensional Printing of a Complete Lithium Ion Battery with Fused Filament Fabrication, ACS Applied Energy Materials 1(10) (2018) 5268-5279.

[6] Yee et al., Hydrogel-Based Additive Manufacturing of Lithium Cobalt Oxide, Advanced Materials Technologies 6(2) (2021).

[7] Saccone et al., Understanding and mitigating mechanical degradation in lithium–sulfur batteries: additive manufacturing of Li2S composites and nanomechanical particle compressions, Journal of Materials Research (2021).

[8] Tagliaferri et al., Direct ink writing of energy materials, Materials Advances 2(2) (2021) 25.

[9] Sun et al., 3D Printing of Interdigitated Li-Ion Microbattery Architectures, Advanced Materials 25(33) (2013) 4539-4543.

[10] Maurel et al., Toward High Resolution 3D Printing of Shape-Conformable Batteries via Vat Photopolymerization: Review and Perspective, IEEE Access 9 (2021) 140654-140666.

[11] Seol et al., All-Printed In-Plane Supercapacitors by Sequential Additive Manufacturing Process, Acs Applied Energy Materials 3(5) (2020) 4965-4973.

[12] Maurel et al., Highly Loaded Graphite-Polylactic Acid Composite-Based Filaments for Lithium-Ion Battery Three-Dimensional Printing, Chemistry of Materials 30(21) (2018) 7484-7493.

[13] Maurel et al., Three-Dimensional Printing of a LiFePO4/Graphite Battery Cell via Fused Deposition Modeling, Scientific Reports 9(1) (2019) 18031.

[14] Maurel et al., Environmentally Friendly Lithium-Terephthalate/Polylactic Acid Composite Filament Formulation for Lithium-Ion Battery 3D-Printing via Fused Deposition Modeling, ECS Journal of Solid State Science and Technology 10(3) (2021) 037004.

[15] Maurel et al., Poly(Ethylene Oxide)-LiTFSI Solid Polymer Electrolyte Filaments for Fused Deposition Modeling Three-Dimensional Printing, Journal of the Electrochemical Society 167(7) (2020).

[16] Maurel et al., Ag-Coated Cu/Polylactic Acid Composite Filament for Lithium and Sodium-Ion Battery Current Collector Three-Dimensional Printing via Thermoplastic Material Extrusion, Frontiers in Energy Research 9(70) (2021).

[17] Martinez et al., Additive Manufacturing of LiNi1/3Mn1/3Co1/3O2 battery electrode material via vat photopolymerization precursor approach, (submitted).

[18] Maurel et al., Vat Photopolymerization Additive Manufacturing of Sodium-Ion Battery TiO2 Negative Electrodes from Lunar In-Situ Resources, (submitted).