3D‐Printing Electrolytes for Solid‐State Batteries

Solid-state batteries have many enticing advantages in terms of safety and stability, but the solid electrolytes upon which these batteries are based typically lead to high cell resistance. Both components of the resistance (interfacial, due to poor contact with electrolytes, and bulk, due to a thick electrolyte) are a result of the rudimentary manufacturing capabilities that exist for solid-state electrolytes. In general, solid electrolytes are studied as flat pellets with planar interfaces, which minimizes interfacial contact area. Here, multiple ink formulations are developed that enable 3D printing of unique solid electrolyte microstructures with varying properties. These inks are used to 3D-print a variety of patterns, which are then sintered to reveal thin, nonplanar, intricate architectures composed only of Li7 La3 Zr2 O12 solid electrolyte. Using these 3D-printing ink formulations to further study and optimize electrolyte structure could lead to solid-state batteries with dramatically lower full cell resistance and higher energy and power density. In addition, the reported ink compositions could be used as a model recipe for other solid electrolyte or ceramic inks, perhaps enabling 3D printing in related fields.

[1]  Qingsong Wang,et al.  Thermal runaway caused fire and explosion of lithium ion battery , 2012 .

[2]  Yan Yu,et al.  A Review on Lithium-Ion Batteries Safety Issues: Existing Problems and Possible Solutions , 2012 .

[3]  Venkataraman Thangadurai,et al.  Lithium Lanthanum Titanates: A Review , 2003 .

[4]  Chee Kai Chua,et al.  Layer-by-layer printing of laminated graphene-based interdigitated microelectrodes for flexible planar micro-supercapacitors , 2015 .

[5]  J. Ryu,et al.  Electrochemical properties of Li7La3Zr2O12-based solid state battery , 2014 .

[6]  T. Yoshida,et al.  Compatibility of Li7La3Zr2O12 Solid Electrolyte to All-Solid-State Battery Using Li Metal Anode , 2010 .

[7]  Philippe Knauth,et al.  Inorganic solid Li ion conductors: An overview , 2009 .

[8]  Yutao Li,et al.  Optimizing Li+ conductivity in a garnet framework , 2012 .

[9]  T. P. Kumar,et al.  Safety mechanisms in lithium-ion batteries , 2006 .

[10]  Tetsuro Kobayashi,et al.  High lithium ionic conductivity in the garnet-type oxide Li7−X La3(Zr2−X, NbX)O12 (X = 0–2) , 2011 .

[11]  Lei Cheng,et al.  Interrelationships among Grain Size, Surface Composition, Air Stability, and Interfacial Resistance of Al-Substituted Li7La3Zr2O12 Solid Electrolytes. , 2015, ACS applied materials & interfaces.

[12]  Kang Xu,et al.  Electrolytes and interphases in Li-ion batteries and beyond. , 2014, Chemical reviews.

[13]  Shengbo Zhang A review on the separators of liquid electrolyte Li-ion batteries , 2007 .

[14]  L. Dhivya,et al.  Lithium ion transport properties of high conductive tellurium substituted Li7La3Zr2O12 cubic lithium garnets , 2013 .

[15]  J. Lewis,et al.  3D Printing of Interdigitated Li‐Ion Microbattery Architectures , 2013, Advanced materials.

[16]  Kun Fu,et al.  Negating interfacial impedance in garnet-based solid-state Li metal batteries. , 2017, Nature materials.

[17]  Stephen Beirne,et al.  Three dimensional (3D) printed electrodes for interdigitated supercapacitors , 2014 .

[18]  James W. Evans,et al.  Direct write dispenser printing of a zinc microbattery with an ionic liquid gel electrolyte , 2010 .

[19]  J. Rupp,et al.  Interface‐Engineered All‐Solid‐State Li‐Ion Batteries Based on Garnet‐Type Fast Li+ Conductors , 2016 .

[20]  Shogo Komagata,et al.  All-solid-state lithium ion battery using garnet-type oxide and Li3BO3 solid electrolytes fabricated by screen-printing , 2013 .

[21]  Ki‐Hyun Kim,et al.  High lithium ion conductive Li7La3Zr2O12 by inclusion of both Al and Si , 2011 .

[22]  Y. Iriyama,et al.  In-situ Li7La3Zr2O12/LiCoO2 interface modification for advanced all-solid-state battery , 2014 .

[23]  John R. Owen,et al.  Rechargeable lithium batteries , 1997 .

[24]  Asma Sharafi,et al.  Characterizing the Li–Li7La3Zr2O12 interface stability and kinetics as a function of temperature and current density , 2016 .

[25]  Steven D. Lacey,et al.  Transition from Superlithiophobicity to Superlithiophilicity of Garnet Solid-State Electrolyte. , 2016, Journal of the American Chemical Society.

[26]  Wolfgang G. Zeier,et al.  Direct Observation of the Interfacial Instability of the Fast Ionic Conductor Li10GeP2S12 at the Lithium Metal Anode , 2016 .

[27]  Tetsuro Kobayashi,et al.  Electrochemical performance of an all-solid-state lithium ion battery with garnet-type oxide electrolyte , 2012 .

[28]  M. Armand,et al.  Issues and challenges facing rechargeable lithium batteries , 2001, Nature.

[29]  Brett L. Lucht,et al.  Thermal Decomposition of LiPF6-Based Electrolytes for Lithium-Ion Batteries , 2005 .

[30]  E. Wachsman,et al.  Three-Dimensional Reconstruction of Porous LSCF Cathodes , 2007 .

[31]  Yayuan Liu,et al.  Solid-State Lithium-Sulfur Batteries Operated at 37 °C with Composites of Nanostructured Li7La3Zr2O12/Carbon Foam and Polymer. , 2017, Nano letters.

[32]  E. Wachsman,et al.  Evaluation of the relationship between cathode microstructure and electrochemical behavior for SOFCs , 2009 .