Next‐Generation Additive Manufacturing: Tailorable Graphene/Polylactic(acid) Filaments Allow the Fabrication of 3D Printable Porous Anodes for Utilisation within Lithium‐Ion Batteries

Abstract

Herein, we report the fabrication and application of Li‐ion anodes for utilisation within Li‐ion batteries, which are fabricated via additive manufacturing/3D printing (fused deposition modelling) using a bespoke graphene/polylactic acid (PLA) filament, where the graphene content can be readily tailored and controlled over the range 1–40 wt. %. We demonstrate that a graphene content of 20 wt. % exhibits sufficient conductivity and critically, effective 3D printability for the rapid manufacturing of 3D printed freestanding anodes (3DAs); simplifying the components of the Li‐ion battery negating the need for a copper current collector. The 3DAs are physicochemically and electrochemically characterised and possess sufficient conductivity for electrochemical studies. Critically, it is found that if the 3DAs are used in Li‐ion batteries the specific capacity is very poor but can be significantly improved through the use of a chemical pre‐treatment. Such treatment induces an increased porosity, which results in a 200‐fold increase (after anode stabilisation) of the specific capacity (ca. 500 mAh g−1 at a current density of 40 mA g−1). This work significantly enhances the field of additive manufacturing/3D printed graphene based energy storage devices demonstrating that useful 3D printable batteries can be realised.

Evolution of 3D Printing Methods and Materials for Electrochemical Energy Storage

“…Foster et al recently fabricated FDM printable graphene/PLA filaments with higher graphene content, and the specific capacity was significant improved after chemical pretreatment (500 mAh g −1 at current density of 40 mA g −1 ), which induced surface porosity to increase the available surface graphite, with some improvement in performance of the half cell anode. [116] Comparatively speaking, 3D electrodes prepared by MJ printing methods shown better half cell performance compared to PLA, ABS, or plastic counterparts. This is directly a function of the nature of active material composite, where in MJ processes that active material and/or conductive additives can be printed directly, rather than as a composite with plastic support materials as is common in ME printing.…”

“…The initial reports using ME, MJ, and VAT-P, commonly referred to as FDM, IJP and stereolithographic apparatus (SLA), respectively, have been used to fabricate substrates, thin film electrodes and electrolytes in half-cell and full-cell Li-batteries. As shown in Figure 7, the majority of systems reported so far are half-cell Li-batteries using electrodes mainly involving graphene, [115][116][117] Li 4 Ti 5 O 12 , [118] SnO 2 , [119] MnO 2 , [120] Si [121] as anodes, as well as LiFePO 4 [118,122,123] and LiCoO 2 cathodes; [124,125] the handful of full-cell 3D printed Li-electrodes focused on lithium iron phosphate cathode and lithium titanate anode. [31,126,127] Compared to ME and MJ methods, we are aware of just one report (at the time of writing) using the VAT-P method to print Li-battery electrodes.…”

Flexible and Wearable Power Sources for Next‐Generation Wearable Electronics

“…[15] Several writing/printing-based technique have been developed to fabricate electrodes, electrolytes, and packing cases of power supplies, including laser writing, photolithography, three-dimensional (3D) printing, flexography, gravure printing, screen printing, inkjet printing, etc. [2,[33][34][35][36][37][38][39][40][41][42][43] For instance, a cobalt-based metalÀ organic framework cathode has been prepared by 3D printing for lithiumÀ oxygen battery with a high energy density of 798 Wh kg À 1 . [44] In addition, a gel electrolyte embedded sulfur cathode was fabricated via ultraviolet curing-assisted stepwise stencil printing processes for solid-state lithiumÀ sulfur battery.…”

“…In addition, it can also diversify the device designs and improve the device integration with desired precision and accuracy to overcome the low production efficiency, instable quality, and slow production speed of handcrafted approaches [15] . Several writing/printing‐based technique have been developed to fabricate electrodes, electrolytes, and packing cases of power supplies, including laser writing, photolithography, three‐dimensional (3D) printing, flexography, gravure printing, screen printing, inkjet printing, etc [2,33–43] . For instance, a cobalt‐based metal−organic framework cathode has been prepared by 3D printing for lithium−oxygen battery with a high energy density of 798 Wh kg −1 [44] .…”

Construção De Equipamento De Baixo Custo Para Enrolar Filamentos De Impressoras 3d

“…4,11,[14][15][16][17] Isto se deve em grande parte ao fato de que filamentos condutores de compósitos PLA/grafeno para impressão 3D são de ampla comercialização atualmente. As aplicações desse material variam desde a criação de estruturas para a geração e o armazenamento de energia (eletrodos para baterias de íon-lítio, 18 supercapacitores de estado sólido, 16,19 eletrodos poliméricos para evolução de H 2 e O 2 ) 20,21 até o desenvolvimento de dispositivos eletrônicos vestíveis 14,16,19,22 e de sensores, 23,24 cujas sensibilidades têm sido enormemente melhoradas em decorrência do desenvolvimento de metodologias para ativar eletroquimicamente a superfície dos eletrodos poliméricos. 4,11,17,[25][26][27] Com o surgimento de extrusoras portáteis e de custo acessível, a confecção de filamentos de outros tipos de polímeros vem se tornando popular e atrativa para uso em química.…”