The status and challenging perspectives of 3D-printed micro-batteries

Abstract

In the era of the Internet of Things and wearable electronics, 3D-printed micro-batteries with miniaturization, aesthetic diversity and high aspect ratio, have emerged as a recent innovation that solves the problems of limited design diversity, poor flexibility and low mass loading of materials associated with traditional power sources restricted by the slurry-casting method. Thus, a comprehensive understanding of the rational design of 3D-printed materials, inks, methods, configurations and systems is critical to optimize the electrochemical performance of customizable 3D-printed micro-batteries. In this review, we offer a key overview and systematic discussion on 3D-printed micro-batteries, emphasizing the close relationship between printable materials and printing technology, as well as the reasonable design of inks. Initially, we compare the distinct characteristics of various printing technologies, and subsequently emphatically expound the printable components of micro-batteries and general approaches to prepare printable inks. After that, we focus on the outstanding role played by 3D printing design in the device architecture, battery configuration, performance improvement, and system integration. Finally, the future challenges and perspectives concerning high-performance 3D-printed micro-batteries are adequately highlighted and discussed. This comprehensive discussion aims at providing a blueprint for the design and construction of next-generation 3D-printed micro-batteries.

Fig. 1. Overview of 3D-printed MBs including printing techniques, electrode designs, printable devices and their applications.

Fig. 2. Schematic of printing and characteristics of four representative 3D printing techniques (DIW, FDM, IJP and SLA) to fabricate MBs.

Fig. 3. Current representative 3D-printed cathodes, anodes, electrolytes via various printing methods. LiFePO₄ (LFP), LiCoO₂ (LCO), LiMn₂O₄ (LMO), LiMn_1−xFe_xPO₄ (LMFP), LiNi_0.8Co_0.15Al_0.05O₂ (NCA), LiNi₀₆Co_0.2Mn_0.2O₂ (NCM), Na₃V₂(PO₄)₃ (NVP), NaMnO₂ (NMO), sulfur and carbon (S/C), poly(ethylene glycol) (PEG), Li₇La₃Zr₂O₁₂ (LLZO), Li₄Ti₅O₁₂ (LTO), and polyaniline (PANI)-coated carbon fiber (PANI/CF).

Fig. 4. 3D-printed cathodes for LIBs and NIBs. (a) Schematic of 3D-printed LFP cathodes by DIW technique (3DP electrode: 3D-printed electrode). Reproduced from ref. . Copyright 2022, Wiley-VCH. (b) Galvanostatic charge–discharging profiles, (c) rate capability and (d) Li-ion transport in 3D-printed LMFP@C cathodes. Reproduced from ref. . Copyright 2016, Wiley-VCH. (e) G′ and G′′ of NVP inks. (f) SEM image of 3D-printed NVP cathodes. (g) Cycling performance of 3D-printed NVP cathodes tested at 1 C. Reproduced from ref. . Copyright 2017, The American Chemical Society.

Fig. 5. 3D-printed cathodes for Li–S batteries and Li–O₂ batteries. (a) Schematic of growth mechanism of thin electrodes by ice template. Reproduced from ref. . Copyright 2020, Elsevier. (b) 3D-printed GO electrodes with hierarchical porous structures for Li–O₂ batteries. Reproduced from ref. . Copyright 2018, Wiley-VCH. (c) Schematic of 3D-printed hierarchically porous carbon networks accelerating the deposition and conversion of Li₂O₂ for Li–O₂ batteries. Reproduced from ref. . Copyright 2019, Wiley-VCH.

Fig. 6. 3D-printed anodes for LIBs. (a) Schematic of 3D-printed LTO inks composed of Ag nanowires, GO nanosheets and LTO nanoparticles as anodes enhancing the ion/electron transport in LIBs and (b) corresponding cycling performance at 0.2 C. Reproduced from ref. . Copyright 2020, Elsevier. (c) Galvanostatic charge–discharge (GCD) profiles and photograph of 3D-printed graphite anodes via FDM method. Reproduced from ref. . Copyright 2018, The American Chemical Society. (d) SEM image of 3D-printed serpentine graphite anodes via DIW printing. Reproduced from ref. . Copyright 2022, Elsevier. (e) Schematic illustration of the enhanced electrochemical performance mechanism of 3D-printed anodes with PEDOT:PSS additive. Reproduced from ref. . Copyright 2017, Elsevier.

Fig. 7. 3D-printed conductive frameworks for stable metal anodes (Li, Na, Zn). (a–c) Schematic of 3D-printed MXene lattices suppressing dendrite growth and volume changes in Li metal. Reproduced from ref. . Copyright 2023, Elsevier. (d–h) SEM images of 3D-printed GO frameworks showing hierarchical structure on multiple scales. Reproduced from ref. . Copyright 2019, The American Chemical Society. (i) Schematic illustration of 3D-printed gradient-structure Ag lattices for protecting Zn anodes. Reproduced from ref. . Copyright 2023, Wiley-VCH.

Fig. 8. 3D-printed hybrid-based solid-state electrolytes. (a) Schematic illustration of the composition and preparation process of 3D-printed Pyr₁₃TFSI-based electrolyte inks. Reproduced from ref. Copyright 2018, Wiley-VCH. (b) Schematic of 3D-printed and structure-free electrolytes via SLP method (SPE: solid polymer electrolyte). Reproduced from ref. . Copyright 2020, The American Chemical Society.

Fig. 9. 3D-printed ceramic-based solid-state electrolytes. (a) Schematic illustration of the preparation process of 3D-printed LAGP electrolytes. Reproduced from ref. . Copyright 2018, The Royal Society of Chemistry. (b) SEM images of 3D-printed LLZO electrolytes at different magnifications. Reproduced from ref. . Copyright 2018, Wiley-VCH.

Fig. 10. 3D-printed current collectors and substrates. (a) Schematic of 3D-printed double-spiral current collectors and electrodes. Reproduced from ref. . Copyright 2018, The Royal Society of Chemistry. (b) Schematic of 3D-printed polymer-derived ceramics substrates. Reproduced from ref. . Copyright 2022, The Royal Society of Chemistry. (c) 3D-printed polymer lattice for substrate. Reproduced from ref. . Copyright 2021, Wiley-VCH. (d and e) Schematic and (f) photograph of 3D-printed different patterns and sizes of substrates by FDM printing. Reproduced from ref. . Copyright 2021, Wiley-VCH.

Fig. 11. 3D-printed separators. (a) Schematic of the 3D-printed BN separators. Reproduced from ref. . Copyright 2018, Elsevier. (b) Photograph (i) and SEM images (ii and iii) of 3D-printed PVDF-HFP separators. Reproduced from ref. . Copyright 2020, Elsevier. (c–e) Photographs of 3D-printed bendable and stretchable NFC/Al₂O₃ separators. Reproduced from ref. . Copyright 2022, Elsevier.

Fig. 12. 3D-printed packages. (a) Schematic of the components of 3D-printed LIBs. Reproduced from ref. . Copyright 2018, Wiley-VCH. Photographs of 3D-printed different-shape packages (b) and Zn-PANI batteries (c). (d) Photographs of LED powered by 3D-printed packaged Zn-PANI battery. Reproduced from ref. . Copyright 2018, The American Chemical Society. (e and f) Schematic of the fabrication process of 3D-printed planar LIBs. Reproduced from ref. . Copyright 2019, Wiley-VCH. (g) Photographs of 3D printed coin cell. Reproduced from ref. . Copyright 2018, The American Chemical Society.

Fig. 13. Timeline of the development of 3D-printed various MBs. Inset images: “3D-printed Zn–Ag micro-battery by IJP”. Reproduced from ref. . Copyright 2009, IOP Publishing. “3D-printed interdigital LIBs by DIW”. Reproduced from ref. . Copyright 2013, Wiley-VCH. “3D-printed GO-based electrode inks for LIBs by DIW”. Reproduced from ref. . Copyright 2016, Wiley-VCH. “3D-printed all-fiber LIBs by DIW”. Reproduced from ref. . Copyright 2017, Wiley-VCH. “3D-printed Li–O₂ battery by DIW”. Reproduced from ref. . Copyright 2018, Wiley-VCH. “3D-printed Zn–air battery by DIW”. Reproduced from ref. . Copyright 2018, The American Chemical Society. “3D-printed ZIMBs by DIW”. Reproduced from ref. . Copyright 2018, The American Chemical Society. “3D-printed Li–S battery by DIW”. Reproduced from ref. . Copyright 2018, Wiley-VCH. “3D-printed interdigital LMBs by DIW”. Reproduced from ref. . Copyright 2019, Wiley-VCH. “3D-printed Na–O₂ battery by DIW”. Reproduced from ref. . Copyright 2020, The American Chemical Society. “3D-printed twisted yarn-type LIBs by DIW”. Reproduced from ref. . Copyright 2021, Elsevier. “3D-printed planar NIMBs by DIW”. Reproduced from ref. . Copyright 2022, Wiley-VCH. “3D-printed K–Se battery by DIW”. Reproduced from ref. . Copyright 2022, The American Chemical Society. “3D-printed ZIMBs for wearable electronics by DIW”. Reproduced from ref. . Copyright 2023, The Royal Society of Chemistry.

Fig. 14. 3D-printed planar LIMBs. (a) Schematic illustration of 3D-printed interdigital LIMBs on Au current collectors. (b) SEM image of 3D-printed interdigital microelectrodes. (c) Photograph of the packaged LIMBs by PMMA. Reproduced from ref. . Copyright 2013, Wiley-VCH. (d) Photograph of 3D-printed GO-based microelectrodes. (e and f) Cycling performance and corresponding GCD profiles of 3D-printed LIMBs, respectively. Reproduced from ref. . Copyright 2016, Wiley-VCH. (g) Schematic illustration of the fabrication process of 3D-printed stretchable electrodes. Reproduced from ref. . Copyright 2020, Elsevier.

Fig. 15. 3D-printed fiber-based LIMBs. (a) Schematic of the fabrication process of 3D-printed fiber-based LIMBs. Photographs of 3D-printed fiber-based LIMBs lighting up a LED in the bent state (b) and integrated into textile fabrics (c). Reproduced from ref. . Copyright 2017, Wiley-VCH. (d) Schematic of interface reinforcement for 3D-printed fiber electrodes. (e) GCD profiles of PDA@LFP cathodes at different current densities. (f) GCD profiles in various bending states. Reproduced from ref. . Copyright 2023, Elsevier. (g and h) SEM images of twisted electrode yarns. (i) GCD profiles of fabricated NCM811‖graphite full cell at various cycling numbers. (j) Rate capability of fabricated NCM811‖graphite full cell. Reproduced from ref. . Copyright 2021, Elsevier.

Fig. 16. 3D-printed NIMBs. (a) Schematic of the fabrication process of 3D-printed interdigital NIMBs including cathodes, anodes and electrolytes. (b) Schematic illustration of the conductive networks in thick microelectrodes. (c and d) Photographs of customizable shapes of 3D-printed electrodes. (e) Rate capability of 3D-printed NIMBs with different electrode thickness. (f) Photograph of the letters “DICP” powered by three serial NIMBs. Reproduced from ref. . Copyright 2022, Wiley-VCH. (g) Schematic of the fabrication process of 3D-printed fiber NIMBs. Rate capability (h) and cycling performance tested at 200 mA g⁻¹ (i) of fiber batteries. Reproduced from ref. . Copyright 2022, Elsevier.

Fig. 17. 3D-printed Zn-based MBs. (a) Schematic of the 3D-printed planar Zn–MnO₂ MBs (left) and photographs of Zn–MnO₂ MBs under different bending states (right). Reproduced from ref. . Copyright 2022, Elsevier. (b) Schematic of 3D-printed Zn symmetric cells. (c) Voltage profiles of 3D-printed Cu-modified Zn symmetric cells at 1 mA cm⁻² and 1 mA h cm⁻². (d) Galvanostatic discharge profiles of 3D-printed ZIMBs with different layers. Reproduced from ref. . Copyright 2022, Elsevier. (e) Photographs of the 3D-printed ZIMBs integrated into a self-powered smart watch. Charging profiles under (f) sunlight and (g) room light of the ZIMBs powering the smart watch. Reproduced from ref. . Copyright 2023, The Royal Society of Chemistry.

Jiaxin Ma

Shuanghao Zheng

Yinghua Fu

Xiao Wang

Jieqiong Qin

Zhong-Shuai Wu