Digital light processing of porous LLZTO scaffolds for Li-garnet solid-state batteries

Chen, Bor-Rong; Monson, Asa G.; Barnes, Pete L.; Efaw, Corey M.; Chuirazzi, William C.; Woods, Michael E.; Rollins, Harry W.; Rufner, Jorgen F.; Preston, Arin S.; Guillen, Donna P.; Dufek, Eric J.

doi:10.1016/j.xcrp.2025.102918

Digital light processing of porous LLZTO scaffolds for Li-garnet solid-state batteries

Journal Article · Tue Oct 28 00:00:00 EDT 2025 · Cell Reports Physical Science

DOI:https://doi.org/10.1016/j.xcrp.2025.102918· OSTI ID:3000100

^[1]; Monson, Asa G. ^[1]; ^[1]; Efaw, Corey M. ^[1]; ^[1]; ^[1]; ^[1]; ^[1]; Preston, Arin S. ^[1]; ^[1]; ^[1]

Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Li₇La₃Zr₂O₁₂ (LLZO)-based solid-state electrolytes (SEs) are promising materials for next-generation solid-state batteries. In this work, digital light processing (DLP), an emerging additive manufacturing technology, is employed to produce porous Ta-doped LLZO (LLZTO) scaffolds. The self-standing scaffolds are 100 μm thick and have 40% porosity. The scaffolds demonstrate symmetric cell cycling stability exceeding 1,500 h at 0.1 mA/cm2 current density, with a capacity of 0.1 mAh/cm² (1 h for each half cycle). At higher current densities, reversible soft shorts frequently happen, while immediate hard shorts are prevented due to Li dendrite growth being hindered by the tortuous pore network. In addition to the cycling stability, the phase stability of LLZTO is investigated during the post-printing thermal process for printing resin removal. We discovered that the LLZTO partially decomposes into Li₂Zr₂O₇ and other impurity phases from 400°C to 800°C, but the pure LLZTO phase is restored upon the completion of resin removal beyond 800°C.

View Accepted Manuscript (DOE)

Research Organization:: Idaho National Laboratory (INL), Idaho Falls, ID (United States)

Sponsoring Organization:: USDOE Office of Nuclear Energy (NE)

Grant/Contract Number:: AC07-05ID14517

OSTI ID:: 3000100

Report Number(s):: INL/JOU--25-83911

Journal Information:: Cell Reports Physical Science, Journal Name: Cell Reports Physical Science; ISSN 2666-3864

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

References (51)

3D-Printing Electrolytes for Solid-State Batteries McOwen, Dennis W.; Xu, Shaomao; Gong, Yunhui Advanced Materials, Vol. 30, Issue 18 https://doi.org/10.1002/adma.201707132	journal	March 2018
Reversible Short‐Circuit Behaviors in Garnet‐Based Solid‐State Batteries Ping, Weiwei; Wang, Chengwei; Lin, Zhiwei Advanced Energy Materials, Vol. 10, Issue 25 https://doi.org/10.1002/aenm.202000702	journal	May 2020
Intermediate‐Stage Sintered LLZO Scaffolds for Li‐Garnet Solid‐State Batteries Okur, Faruk; Zhang, Huanyu; Karabay, Dogan Tarik Advanced Energy Materials, Vol. 13, Issue 15 https://doi.org/10.1002/aenm.202203509	journal	March 2023
High-Performance 3-D Fiber Network Composite Electrolyte Enabled with Li-Ion Conducting Nanofibers and Amorphous PEO-Based Cross-Linked Polymer for Ambient All-Solid-State Lithium-Metal Batteries Yan, Chaoyi; Zhu, Pei; Jia, Hao Advanced Fiber Materials, Vol. 1, Issue 1 https://doi.org/10.1007/s42765-019-00006-x	journal	July 2019
Study on defect-free debinding green body of ceramic formed by DLP technology Wang, Kai; Qiu, Mingbo; Jiao, Chen Ceramics International, Vol. 46, Issue 2 https://doi.org/10.1016/j.ceramint.2019.09.237	journal	February 2020
Processing and manufacturing of next generation lithium-based all solid-state batteries Zaman, Wahid; Hatzell, Kelsey B. Current Opinion in Solid State and Materials Science, Vol. 26, Issue 4 https://doi.org/10.1016/j.cossms.2022.101003	journal	August 2022
Text mining for processing conditions of solid-state battery electrolytes Mahbub, Rubayyat; Huang, Kevin; Jensen, Zach Electrochemistry Communications, Vol. 121 https://doi.org/10.1016/j.elecom.2020.106860	journal	December 2020
Intergranular Li metal propagation through polycrystalline Li6.25Al0.25La3Zr2O12 ceramic electrolyte Cheng, Eric Jianfeng; Sharafi, Asma; Sakamoto, Jeff Electrochimica Acta, Vol. 223 https://doi.org/10.1016/j.electacta.2016.12.018	journal	January 2017
Poly (ethylene oxide) based solid polymer electrolyte improved by multifunctional additives of poly (acrylamide) and LiI Li, Xurui; Liu, Shuai; Shi, Jing Electrochimica Acta, Vol. 445 https://doi.org/10.1016/j.electacta.2023.142062	journal	March 2023
Manipulating Li2O atmosphere for sintering dense Li7La3Zr2O12 solid electrolyte Huang, Xiao; Lu, Yang; Song, Zhen Energy Storage Materials, Vol. 22 https://doi.org/10.1016/j.ensm.2019.01.018	journal	November 2019
Interfaces in all solid state Li-metal batteries: A review on instabilities, stabilization strategies, and scalability Paul, Partha P.; Chen, Bor-Rong; Langevin, Spencer A. Energy Storage Materials, Vol. 45 https://doi.org/10.1016/j.ensm.2021.12.021	journal	March 2022
Fabrication of Li7La3Zr2O12 films with controlled porosity and fast Li+ transport Parascos, Kade; Watts, Joshua L.; Alarco, Jose A. Journal of Energy Storage, Vol. 92 https://doi.org/10.1016/j.est.2024.111996	journal	July 2024
Li7La3Zr2O12 solid electrolyte sintered by the ultrafast high-temperature method Ihrig, Martin; Mishra, Tarini Prasad; Scheld, Walter Sebastian Journal of the European Ceramic Society, Vol. 41, Issue 12 https://doi.org/10.1016/j.jeurceramsoc.2021.05.041	journal	September 2021
Are solid-state batteries safer than lithium-ion batteries? Bates, Alex M.; Preger, Yuliya; Torres-Castro, Loraine Joule, Vol. 6, Issue 4 https://doi.org/10.1016/j.joule.2022.02.007	journal	April 2022
The phantom menace of dynamic soft-shorts in solid-state battery research Counihan, Michael J.; Chavan, Kanchan S.; Barai, Pallab Joule, Vol. 8, Issue 1 https://doi.org/10.1016/j.joule.2023.11.007	journal	January 2024
Lithium Dendrite in All-Solid-State Batteries: Growth Mechanisms, Suppression Strategies, and Characterizations Cao, Daxian; Sun, Xiao; Li, Qiang Matter, Vol. 3, Issue 1 https://doi.org/10.1016/j.matt.2020.03.015	journal	July 2020
High-rate lithium cycling in a scalable trilayer Li-garnet-electrolyte architecture Hitz, Gregory T.; McOwen, Dennis W.; Zhang, Lei Materials Today, Vol. 22 https://doi.org/10.1016/j.mattod.2018.04.004	journal	January 2019
A porous garnet Li7La3Zr2O12 scaffold with interfacial modification for enhancing ionic conductivity in PEO-based composite electrolyte Xie, Yuexin; Huang, Liwu; Chen, Yungui Journal of Membrane Science, Vol. 683 https://doi.org/10.1016/j.memsci.2023.121784	journal	October 2023
Atomic Layer Deposition of the Solid Electrolyte Garnet Li ₇ La ₃ Zr ₂ O ₁₂ Kazyak, Eric; Chen, Kuan-Hung; Wood, Kevin N. Chemistry of Materials, Vol. 29, Issue 8 https://doi.org/10.1021/acs.chemmater.7b00944	journal	April 2017
Surface Chemistry Mechanism of Ultra-Low Interfacial Resistance in the Solid-State Electrolyte Li ₇ La ₃ Zr ₂ O ₁₂ Sharafi, Asma; Kazyak, Eric; Davis, Andrew L. Chemistry of Materials, Vol. 29, Issue 18 https://doi.org/10.1021/acs.chemmater.7b03002	journal	September 2017
Inorganic Solid-State Electrolytes for Lithium Batteries: Mechanisms and Properties Governing Ion Conduction Bachman, John Christopher; Muy, Sokseiha; Grimaud, Alexis Chemical Reviews, Vol. 116, Issue 1 https://doi.org/10.1021/acs.chemrev.5b00563	journal	December 2015
Garnet-Type Solid-State Electrolytes: Materials, Interfaces, and Batteries Wang, Chengwei; Fu, Kun; Kammampata, Sanoop Palakkathodi Chemical Reviews, Vol. 120, Issue 10 https://doi.org/10.1021/acs.chemrev.9b00427	journal	April 2020
Optimization of Tape Casting for Fabrication of Li _6.25 Al _0.25 La ₃ Zr ₂ O ₁₂ Sheets Jonson, Robert A.; Yi, Eongyu; Shen, Fengyu Energy & Fuels, Vol. 35, Issue 10 https://doi.org/10.1021/acs.energyfuels.1c00566	journal	May 2021
Amorphous-Carbon-Coated 3D Solid Electrolyte for an Electro-Chemomechanically Stable Lithium Metal Anode in Solid-State Batteries Xie, Hua; Yang, Chunpeng; Ren, Yaoyu Nano Letters, Vol. 21, Issue 14 https://doi.org/10.1021/acs.nanolett.1c01748	journal	July 2021
All-Solid-State Batteries Using Rationally Designed Garnet Electrolyte Frameworks Yi, Eongyu; Shen, Hao; Heywood, Stephen ACS Applied Energy Materials, Vol. 3, Issue 1 https://doi.org/10.1021/acsaem.9b02101	journal	December 2019
Understanding the Influence of Li₇La₃Zr₂O₁₂ Nanofibers on Critical Current Density and Coulombic Efficiency in Composite Polymer Electrolytes Counihan, Michael J.; Powers, Devon J.; Barai, Pallab ACS Applied Materials & Interfaces, Vol. 15, Issue 21 https://doi.org/10.1021/acsami.3c04262	journal	May 2023
Effect of Li_6.4La₃Zr_1.4Ta_0.6O₁₂ Fillers on the Interfacial Properties between Composite PEO-LiTFSI Electrolytes with Li Metal during Cycling Zhang, Lun; Feng, Junrun; Zhu, Guanghan ACS Applied Materials & Interfaces, Vol. 16, Issue 11 https://doi.org/10.1021/acsami.3c19519	journal	March 2024
Are Three-Dimensional Batteries Beneficial? Analyzing Historical Data to Elucidate Performance Advantages Hung, Chih-Hsuan; Huynh, Phong; Teo, Katrina ACS Energy Letters, Vol. 8, Issue 1 https://doi.org/10.1021/acsenergylett.2c02208	journal	November 2022
A low ride on processing temperature for fast lithium conduction in garnet solid-state battery films Pfenninger, Reto; Struzik, Michal; Garbayo, Iñigo Nature Energy, Vol. 4, Issue 6 https://doi.org/10.1038/s41560-019-0384-4	journal	May 2019
Processing thin but robust electrolytes for solid-state batteries Balaish, Moran; Gonzalez-Rosillo, Juan Carlos; Kim, Kun Joong Nature Energy, Vol. 6, Issue 3 https://doi.org/10.1038/s41560-020-00759-5	journal	February 2021
On the feasibility of all-solid-state batteries with LLZO as a single electrolyte Kravchyk, Kostiantyn V.; Karabay, Dogan Tarik; Kovalenko, Maksym V. Scientific Reports, Vol. 12, Issue 1 https://doi.org/10.1038/s41598-022-05141-x	journal	January 2022
Flame made nanoparticles permit processing of dense, flexible, Li ⁺ conducting ceramic electrolyte thin films of cubic-Li ₇ La ₃ Zr ₂ O ₁₂ (c-LLZO) Yi, Eongyu; Wang, Weimin; Kieffer, John Journal of Materials Chemistry A, Vol. 4, Issue 33 https://doi.org/10.1039/C6TA04492A	journal	January 2016
Three-dimensional bilayer garnet solid electrolyte based high energy density lithium metal–sulfur batteries Fu, Kun (Kelvin); Gong, Yunhui; Hitz, Gregory T. Energy & Environmental Science, Vol. 10, Issue 7 https://doi.org/10.1039/C7EE01004D	journal	January 2017
Impact of air exposure and surface chemistry on Li–Li ₇ La ₃ Zr ₂ O ₁₂ interfacial resistance Sharafi, Asma; Yu, Seungho; Naguib, Michael Journal of Materials Chemistry A, Vol. 5, Issue 26 https://doi.org/10.1039/C7TA03162A	journal	January 2017
Prospects of production technologies and manufacturing costs of oxide-based all-solid-state lithium batteries Schnell, Joscha; Tietz, Frank; Singer, Célestine Energy & Environmental Science, Vol. 12, Issue 6 https://doi.org/10.1039/C8EE02692K	journal	January 2019
A bird's-eye view of Li-stuffed garnet-type Li ₇ La ₃ Zr ₂ O ₁₂ ceramic electrolytes for advanced all-solid-state Li batteries Samson, Alfred Junio; Hofstetter, Kyle; Bag, Sourav Energy & Environmental Science, Vol. 12, Issue 10 https://doi.org/10.1039/C9EE01548E	journal	January 2019
Oriented porous LLZO 3D structures obtained by freeze casting for battery applications Shen, Hao; Yi, Eongyu; Amores, Marco Journal of Materials Chemistry A, Vol. 7, Issue 36 https://doi.org/10.1039/C9TA06520B	journal	January 2019
Reducing the thickness of solid-state electrolyte membranes for high-energy lithium batteries Wu, Jingyi; Yuan, Lixia; Zhang, Wuxing Energy & Environmental Science, Vol. 14, Issue 1 https://doi.org/10.1039/D0EE02241A	journal	January 2021
Controlling the lithium proton exchange of LLZO to enable reproducible processing and performance optimization Rosen, Melanie; Ye, Ruijie; Mann, Markus Journal of Materials Chemistry A, Vol. 9, Issue 8 https://doi.org/10.1039/D0TA11096E	journal	January 2021
Pore and grain chemistry during sintering of garnet-type Li_6.4La₃Zr_1.4Ta_0.6O₁₂ solid-state electrolytes Hammons, Joshua A.; Espitia, J. Ali; Ramos, Erika Journal of Materials Chemistry A, Vol. 10, Issue 16 https://doi.org/10.1039/D1TA10338E	journal	January 2022
Insights into soft short circuit-based degradation of lithium metal batteries Menkin, Svetlana; Fritzke, Jana B.; Larner, Rebecca Faraday Discussions, Vol. 248 https://doi.org/10.1039/D3FD00101F	journal	January 2024
Impact of thermal treatment on the Li-ion transport, interfacial properties, and composite preparation of LLZO garnets for solid-state electrolytes Ghorbanzade, Pedram; Pesce, Arianna; Gómez, Kerman Journal of Materials Chemistry A, Vol. 11, Issue 22 https://doi.org/10.1039/D3TA01145C	journal	January 2023
3D printing of self-supported solid electrolytes made of glass-derived Li_1.5Al_0.5Ge_1.5P₃O₁₂ for all-solid-state lithium-metal batteries Sabato, A. G.; Nuñez Eroles, M.; Anelli, S. Journal of Materials Chemistry A, Vol. 11, Issue 25 https://doi.org/10.1039/D3TA01435E	journal	January 2023
Vat photopolymerization of tantalum-doped Li₇La₃Zr₂O₁₂ electrolytes: a new Frontier in solid-state battery design Karuppiah, Diwakar; Komissarenko, Dmitrii; Thakur, Tamanna Journal of Materials Chemistry A, Vol. 13, Issue 1 https://doi.org/10.1039/D4TA06160H	journal	January 2025
Growing three-dimensional objects with light Lipkowitz, Gabriel; Saccone, Max A.; Panzer, Matthew A. Proceedings of the National Academy of Sciences, Vol. 121, Issue 28 https://doi.org/10.1073/pnas.2303648121	journal	July 2024
Perspective on design and technical challenges of Li-garnet solid-state batteries Kravchyk, Kostiantyn V.; Kovalenko, Maksym V. Science and Technology of Advanced Materials, Vol. 23, Issue 1 https://doi.org/10.1080/14686996.2021.2018919	journal	January 2022
Toward High Resolution 3D Printing of Shape-Conformable Batteries via Vat Photopolymerization: Review and Perspective Maurel, Alexis; Martinez, Ana C.; Grugeon, Sylvie IEEE Access, Vol. 9 https://doi.org/10.1109/ACCESS.2021.3119533	journal	January 2021
A general method to synthesize and sinter bulk ceramics in seconds Wang, Chengwei; Ping, Weiwei; Bai, Qiang Science, Vol. 368, Issue 6490 https://doi.org/10.1126/science.aaz7681	journal	April 2020
Practical cone-beam algorithm Feldkamp, L. A.; Davis, L. C.; Kress, J. W. Journal of the Optical Society of America A, Vol. 1, Issue 6 https://doi.org/10.1364/JOSAA.1.000612	journal	January 1984
impedance.py: A Python package for electrochemical impedance analysis Murbach, Matthew; Gerwe, Brian; Dawson-Elli, Neal Journal of Open Source Software, Vol. 5, Issue 52 https://doi.org/10.21105/joss.02349	journal	August 2020
PEO Infiltration of Porous Garnet-Type Lithium-Conducting Solid Electrolyte Thin Films Waidha, Aamir Iqbal; Vanita, Vanita; Clemens, Oliver Ceramics, Vol. 4, Issue 3 https://doi.org/10.3390/ceramics4030031	journal	July 2021

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