Inks Development for 3D Printing Cathode of Li-Ion Microbatteries

Abstract

Due to the demand for wearable and implantable microelectronic devices (MED), there is growing interest in the development of thin-film lithium-ion microbatteries (LiBs) with high-energy density. The high cost of production is an issue restraining thin-film LiBs’ wide application. Inkjet printing is a method of applying materials to the substrate surface: ink droplets formed on piezoelectric nozzles fall on the substrate, whereafter evaporation of the solvent thin layer of film is formed. The proposed technology can simplify the production of LiBs for MED and reduce their cost. The present work reports the results of inkjet printing 3D cathode development for LiBs. The 3D printed cathodes were produced using synthesized Li-rich cathode material (Li1.2+xMn0.54Ni0.13Co0.13O2, 0 < x < 0.05) which has a larger capacity (>250 mAh/g) in comparison with the materials used in modern lithium-ion cells. For LiB electrode printing, the non-aqueous solvent-based inks were used. The prepared cathode material was dispersed in N-methyl-2-pyrrolidone. The effect of various additives such as ethylene glycol, diethylene glycol, propylene glycol on the viscosity and stability of the ink was studied. Inkjet printing was performed with the use of a Dimatix Material Printer 2831. Substrate temperature, number of layers and other parameters were varied to determine the optimal printing conditions.

Fabrication of modern lithium ion batteries by 3D inkjet printing: opportunities and challenges

“… Active material Solvent Additives Printer Printed layer thickness Electrochemical performance of printed structure Ref. Cathode LiCoO 2 DI-water CMC, commercial surfactant solution Canon BJC-1000sp 1.2 μm (30 layers) 120 mAh/g at 180 μA/cm 2 , 95% capacity retention after 100 cycles [30] LiFePO 4 buffer solution (HCl + NaOH) CMC, TritonX-100, glycerin Dimatix-2800 20 μm 129.9 mAh/g at 0.1 C (Al foil), 151.3 mAh/g at 0.1 C (CNT) [164] LiFePO 4 DI-water PAMA piezoelectric ink-jet printer 4 μm (40 layers) 80 mAh/g at 9 C, 70 mAh/g at 90 C [143] LMNCO NMP PVDF, surfactant Dimatix-2831 11.5 μm (25 layers) 240 mAh/g at 0.01 C [166] 1.20 NCM/1.25 NCM NMP PVDF, ethylene glycol, diethylene glycol, propylene glycol Dimatix-2831 – – [145] V 2 O 5 /MXene – – Dimatix-2800 – 321 mAh/g at 1 C, 91.8% capacity retention after 680 cycles [169] Anode SnO 2 DI-water/absolute ethanol/diethylene glycol/triethanolamine/isopropylalcohol CMC, CH10B, CH12B Canon BJC-1000sp 2.3 μm (10 layers) 812.7 mAh/g at 33 μA/cm 2 [16] Li 4 Ti 5 O 12 aqueous solution (LDS+Li-PAA) PVP Flat-bed Breva thermal inkjet 3.3 μm (20 layers) 128 mAh/g at 0.5 C …”

“…Printer manufacturers set their values which usually fall within a narrow range. For instance, Fujifilm recommends a viscosity of 10–12 mPa.s, and surface tension of 28–33 mN/m for Dimatix 2800 [144] and 8–10 mPa.s, 28–32 mN/m for Dimatix 2831 [145] . Lawes et al [112] , [146] used HP Deskjet 2540 inkjet printer to fabricate Si and TiO 2 composite electrodes.…”

“…Maximov et al [145] fabricated NMC cathode using the IJP. Ink was dispersed by an ultrasonic bath, and large agglomerates were eliminated by centrifugation.…”

3D Printed Micro‐Electrochemical Energy Storage Devices: From Design to Integration

“…Typical anode materials in 3D printing include carbon‐based materials, [ 119 ] silicon, [ 120 ] lithium, [ 117 ] titanium compounds (e.g., Li 4 Ti 5 O 12 ), [ 121 ] metal (e.g., Ag), [ 122 ] and metal oxides (e.g., SnO 2 ). [ 123 ] Meanwhile, 3D printed cathodes include lithium transition metal layered oxides (marked as LMO) (e.g., LiCoO 2 , LiMn 2 O 4 ), [ 124 ] doped LMO‐like materials, [ 125 ] olivine, and polyanion compounds (LiFePO 4 , LiMn 1‐ x Fe x PO 4 ). [ 1a,126 ] Those can be utilized as printed raw material independently or prepared by combining noble metals [ 127 ] or various carbon‐based conductive materials, such as carbon shell, [ 126a ] CNFs, [ 128 ] CNTs, [ 129 ] GO, [ 130 ] and graphene.…”

A single layer of Fe3O4@TiO2 submicron spheres as a high-performance electrode for lithium-ion microbatteries

“…The separation of the large agglomerates from the cathode by centrifugation has led to active material with a size of less than 140 nm which was considered well meeting the requirements for ink-inkjet of cathode suitable for microbattery application. 28 An olivine-structured LiFePO 4 cathode has slightly lower voltage than LiCoO 2 and comparable capacity; however, it is characterized by a very long cycle life and rate capability. 29 In addition, this material may be very suitable for thin-layer configurations since its morphology may be finely controlled at the micro-and nanometric levels both in the laboratory 30 and in large-scale production plants.…”