Li7La3Zr2O12 Protonation as a Means to Generate Porous/Dense/Porous-Structured Electrolytes for All-Solid-State Lithium-Metal Batteries.

Ceramic Li7La3Zr2O12 (LLZO) represents a promising candidate electrolyte for next-generation all-solid-state lithium-metal batteries. However, lithium-metal batteries are prone to dendrite formation upon fast charging. Porous/dense and porous/dense/porous LLZO structures were proposed as a solution to avoid or at least delay the formation of lithium-metal dendrites by increasing the electrode/electrolyte contact area and thus lowering the local current density at the interface. In this work, we show the feasibility of producing porous/dense/porous LLZO by a new and scalable method. The method consists of LLZO chemical deep protonation in a protic or acidic solvent, followed by thermal deprotonation at high temperatures to create the porous structure by water and lithium oxide elimination. We demonstrate that the produced structure extends the lifetime of Li/LLZO/Li symmetric cells by a factor of 8 compared to a flat LLZO at a current density of 0.1 mA/cm2 and with a capacity of 1 mAh/cm2 per half-cycle. We also show clear improvement of the Li/LLZO/LiFePO4 full cell performance with a thermally deprotonated LLZO.

[1]  C. Battaglia,et al.  Low Na-β′′-alumina electrolyte/cathode interfacial resistance enabled by a hydroborate electrolyte opening up new cell architecture designs for all-solid-state sodium batteries , 2022, Materials Futures.

[2]  Kun Fu,et al.  Garnet Ceramic Fabric-Reinforced Flexible Composite Solid Electrolyte Derived from Silk Template for Safe and Long-term Stable All-Solid-State Lithium Metal Batteries , 2022, Energy Storage Materials.

[3]  D. Parkinson,et al.  Preparing Li‐garnet electrodes with engineered structures by phase inversion and high shear compaction processes , 2021, Journal of the American Ceramic Society.

[4]  C. Battaglia,et al.  Impact of Protonation on the Electrochemical Performance of Li7La3Zr2O12 Garnets. , 2021, ACS applied materials & interfaces.

[5]  Chen‐Zi Zhao,et al.  Critical Current Density in Solid‐State Lithium Metal Batteries: Mechanism, Influences, and Strategies , 2021, Advanced Functional Materials.

[6]  Michael J. Wang,et al.  Publisher Correction: Enabling “lithium-free” manufacturing of pure lithium metal solid-state batteries through in situ plating , 2020, Nature Communications.

[7]  Y. Ni,et al.  A three dimensional interconnected Li7La3Zr2O12 framework composite solid electrolyte utilizing lignosulfonate/ cellulose nanofiber bio-template for high performance lithium ion batteries , 2020, Journal of Power Sources.

[8]  Guoying Chen,et al.  All-Solid-State Batteries Using Rationally Designed Garnet Electrolyte Frameworks , 2020, ACS Applied Energy Materials.

[9]  N. Tamura,et al.  Scalable freeze tape casting fabrication and pore structure analysis of 3D LLZO solid-state electrolytes. , 2019, ACS applied materials & interfaces.

[10]  P. Bruce,et al.  The sodium/Na beta" alumina interface: Effect of pressure on voids. , 2019, ACS applied materials & interfaces.

[11]  Michael J. Wang,et al.  Characterizing the Li-Solid-Electrolyte Interface Dynamics as a Function of Stack Pressure and Current Density , 2019, Joule.

[12]  P. Bruce,et al.  Critical stripping current leads to dendrite formation on plating in lithium anode solid electrolyte cells , 2019, Nature Materials.

[13]  B. Kalkan,et al.  Structure and magnetic properties of (La1−Fe )FeO3 (x = 0, 0.25, 0.50) perovskite , 2019, Journal of Alloys and Compounds.

[14]  Jianyong Yu,et al.  Polymer Template Synthesis of Soft, Light, and Robust Oxide Ceramic Films , 2019, iScience.

[15]  Wolfgang G. Zeier,et al.  Toward a Fundamental Understanding of the Lithium Metal Anode in Solid-State Batteries-An Electrochemo-Mechanical Study on the Garnet-Type Solid Electrolyte Li6.25Al0.25La3Zr2O12. , 2019, ACS applied materials & interfaces.

[16]  Xiulin Fan,et al.  High electronic conductivity as the origin of lithium dendrite formation within solid electrolytes , 2019, Nature Energy.

[17]  Kun Fu,et al.  All-in-one lithium-sulfur battery enabled by a porous-dense-porous garnet architecture , 2018, Energy Storage Materials.

[18]  Kun Fu,et al.  3D lithium metal anodes hosted in asymmetric garnet frameworks toward high energy density batteries , 2018, Energy Storage Materials.

[19]  S. Miller,et al.  Dense freeze‐cast Li 7 La 3 Zr 2 O 12 solid electrolytes with oriented open porosity and contiguous ceramic scaffold , 2018, Journal of the American Ceramic Society.

[20]  Yunhui Gong,et al.  Three-Dimensional, Solid-State Mixed Electron-Ion Conductive Framework for Lithium Metal Anode. , 2018, Nano letters.

[21]  Liangbing Hu,et al.  3D‐Printing Electrolytes for Solid‐State Batteries , 2018, Advanced materials.

[22]  Xi Chen,et al.  Garnet Electrolyte with an Ultralow Interfacial Resistance for Li-Metal Batteries. , 2018, Journal of the American Chemical Society.

[23]  Yunhui Gong,et al.  Continuous plating/stripping behavior of solid-state lithium metal anode in a 3D ion-conductive framework , 2018, Proceedings of the National Academy of Sciences.

[24]  Donald J. Siegel,et al.  Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li7La3Zr2O12 , 2017 .

[25]  A. Roy,et al.  Structural properties and the fluorite–pyrochlore phase transition in La2Zr2O7: The role of oxygen to induce local disordered states , 2016 .

[26]  Candace K. Chan,et al.  Nanostructured Garnet-Type Solid Electrolytes for Lithium Batteries: Electrospinning Synthesis of Li7La3Zr2O12 Nanowires and Particle Size-Dependent Phase Transformation , 2015 .

[27]  J. Sakamoto,et al.  Resolving the Grain Boundary and Lattice Impedance of Hot-Pressed Li7La3Zr2O12 Garnet Electrolytes , 2014 .

[28]  Venkataraman Thangadurai,et al.  Fast Lithium Ion Conduction in Garnet‐Type Li7La3Zr2O12 , 2007 .

[29]  Michael T. Hutchings,et al.  Investigation of thermally induced Li+ ion disorder in Li2O using neutron diffraction , 1991 .

[30]  D. Sinclair,et al.  Electroceramics: Characterization by Impedance Spectroscopy , 1990 .

[31]  Yunhui Gong,et al.  High-rate lithium cycling in a scalable trilayer Li-garnet-electrolyte architecture , 2019, Materials Today.