Transitioning advanced ceramic electrolytes into manufacturable solid-state EV batteries J. Sakamoto (PI), University of Michigan

Co-PI(s), Prof. N. Dasgupta (UM), Prof. D. J. Siegel (UM) Prof. K. Thornton (UM), and Dr. N. J. Dudney (ORNL)

Project Vision Develop manufacturing solutions to enable large-scale production of Li metal-ceramic membrane batteries.

Total project cost: $3.5M Length 34 mo. 2X energy density vs Li-ion (1,200 Wh/L) & non-flammable

Li-ion Conducting Ceramic

20 µm cycled

• Developed ceramic membrane4 tech to physically stabilize Li metal anodes • Supplanting graphite with Li metal doubles energy density • Replacing combustible liquid with solid electrolyte improves safety • Developed a manufacturing vision that leverages the Li-ion industry • Demonstrated thin Li anode integration The Team

PI: Prof. Jeff Sakamoto: Mechanical Engineering & Materials Science

amorphous crystalline Precision ALD Interfaces Co-PI: Prof. Neil Dasgupta: Mechanical Engineering

Co-PI: Prof. Don Siegel: Mechanical Engineering Interface Computation

Co-PI: Prof. Katsuyo Thornton: Materials Science Interface Mechanics Finite Element Analysis Interface Co-PI: Dr. Nancy Dudney: Materials Science & Tech Engineering: Physical Vapor Deposition

2 Project Objectives: Develop a Scalable Manufacturing Approach Materials Thin film processing Interfaces Cell Architecture Goal 20 Post Plating EIS 18

16 Li-ion Conducting Ceramic

) 14

2

m

c

* 12

m h 10

O

(

)

Z 20 µm cycled ( 8 R R m R LLZO CT I UC

- 6

4 4" • > 1000 Wh/L 2 Cell Developed ceramic Cathode 0 • 90 mAh 0 5 10 15 20 architecture formulations that LLZO Re(Z)*Area (Ohm*cm2) • 5 cm bend M addresses are stable against Engineered surfaces • 400 cycles brittle nature 2 Li.1-7 2 • > 3mAh/cm enable < 15 W.cm ASR of ceramic 50 µm • 1 C rate produced with a scale- 8 Processing of high membranes. able process.6 density ceramic battery components. Engineer to minimize peripheral mass/volume.1,3,4

July 26, 2019 3 Maintaining Mechanical Integrity Challenging When Li & Ceramic ≈ 10 – 20 µm

Reinforce Ceramic with Li Distortion  Fracture Robust Cathode Load Bearing Cathode

~1mm Electrolyte Cathode Cathode

Pellet Rigid Assembly Rigid Li-ion Conducting Ceramic Li

10 µm 10 µm • Strong & stiff as Al alloy Li metal9 • E-chem performance maintained.10

July 26, 2019 4 Thin Film Ceramic Tile Array & Li Anode Integration

Cerami Li c 50 µm

5 cm bend radius.8 Maintain < 15 W.cm2 ASR after rolling.

July 26, 2019 5 Challenges and Potential Technical Partnerships

‣ Relevant Ceramic Processing Expertise in US is not Common – Fortunate to have Identified A Potential Ceramic Partner

‣ Currently Pursuing Li-ion Battery Manufacturers Interested in SSB Pilot- Line Manufacturing

‣ Interest in Engaging End Users Requiring High Energy Density & High Stability Batteries T2M Ceramic membrane & Integrate new composite cathode processes into pilot line Micro • Material suppliers Li-ion manufacturer electronics • Ceramic processing Mobility

Start-up option to license in place Next steps: 18 Patents • Launch UM spin-off (Zakuro LLC) with Arpa-E Plus-Up 2 issued • Translate to full-scale manufacturing with partner Exit Strategy • Acquisition by partner • Maintain research arm to advance SSB technology

July 26, 2019 7 Referenced Patents (of 18) and *Peer-Reviewed Manuscripts (of 44)

1. US 9093717 B2 (Issued): Methods of making and using oxide ceramic solids and products and devices related thereto. 2. US 20160293988 A1 (Issued): Template-based methods of making and using ceramic solids and products and devices related thereto. 3. US Application: 62/268,545, filed 12/17/2015 OTT 6746, Slurry Formulation for the Formation of Layers for Solid State Batteries. 4. US Application: 62/360,770, filed 7/11/2016 OTT 7102: Ceramic Based Ionically Conducting Material. 5. *Thompson, T., Yu, S., Williams, L., Schmidt, R.D., Garcia-Mendez, R., Wolfenstine, J., Allen, J.L., Kioupakis, E., Siegel, D.J. and Sakamoto, J., 2017. Electrochemical window of the Li-ion solid electrolyte Li7La3Zr2O12. ACS Energy Letters, 2(2), pp.462-468. 6. *Sharafi, A., Kazyak, E., Davis, A.L., Yu, S., Thompson, T., Siegel, D.J., Dasgupta, N.P. and Sakamoto, J., 2017. Surface chemistry mechanism of ultra- low interfacial resistance in the solid-state electrolyte Li7La3Zr2O12. Chemistry of Materials, 29(18), pp.7961-7968. 7. *Ma, C., Cheng, Y., Yin, K., Luo, J., Sharafi, A., Sakamoto, J., Li, J., More, K.L., Dudney, N.J. and Chi, M., 2016. Interfacial stability of Li metal–solid electrolyte elucidated via in situ electron microscopy. Nano letters, 16(11), pp.7030-7036. 8. US Application: 62/289,559, filed 2/1/2017 OTT 6744, Segmented Cell Architecture for Solid State Batteries. 9. *Masias, A., Felten, N., Garcia-Mendez, R., Wolfenstine, J. and Sakamoto, J., 2019. Elastic, plastic, and creep mechanical properties of lithium metal. Journal of Materials Science, 54(3), pp.2585-2600. 10. US Provisional Patent Application filed May 24, 2019.

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