IP Library Granted Patent US 12,347,830
Granted Patent B2
US 12,347,830 · App. 16/784,543 · Granted Jul 1, 2025

Interface design for high current density cycling of solid state battery

Inventors: Yisi Zhu (Naperville, IL); Sanja Tepavcevic (Chicago, IL); Justin Grant Connell (Chicago, IL); Peter Zapol (Hinsdale, IL); Nenad Markovic (Hinsdale, IL)
Assignee: UCHICAGO ARGONNE, LLC
H01M10/0585H01M4/382H01M4/405H01M4/505H01M4/525H01M4/5825H01M10/052H01M10/0562H01M2300/0071
View Patent ↗
Loading inventors, assignments & file history…
Monitor This Case
Get email alerts when status or documents change.
Order Certified Copies
Most orders are placed with the USPTO same day — all within 24 business hours.
Order via The Patent Place →
Pre-filled with this patent's details
Quick Facts
Patent No.
US 12,347,830
App. No.
16/784,543
Granted
Jul 1, 2025
Kind
B2
Abstract

Solid-state batteries offer improved safety and the high-energy-density capabilities required for next generation demands of electric vehicles. Disclosed is a method for fabricating high-current-density solid-state batteries, and the associated device structures and systems. The method of fabrication includes purifying surfaces of a solid electrolyte, depositing materials to form deposition layers on the surfaces of the solid electrolyte in a vacuum, and forming oxygen-deficient interfaces at the interface of the deposition layers and the solid electrolyte. The methods and associated devices form high-current-density solid-state batteries with stable electrochemical performance over hundreds of electric cycles.

Claims (32)

1. A solid-state battery cell, comprising:

a first electrode comprising lithium metal or a lithium metal alloy, the first electrode having a first electrode first surface and an oppositely disposed first electrode second surface;

a second electrode having a second electrode first surface and an oppositely disposed second electrode second surface;

a solid electrolyte comprising a cubic lithium ion conducting metal oxide, the solid electrolyte extending between the first and second electrodes and the solid electrolyte having oppositely disposed first and second electrolyte surfaces, wherein the first electrolyte surface is in facing relation to the first electrode second surface and the second electrolyte surface is in facing relation to the second electrode first surface; and

a first oxygen-deficient interface layer formed by reduction of the first electrolyte surface of the solid electrolyte, the first oxygen-deficient interface layer formed in the solid electrolyte at an interface between the first electrolyte surface and the first electrode second surface, and the first oxygen-deficient interface layer extending only partially through the solid electrolyte, wherein the solid electrolyte has an ionic conductivity in the range of 0.1×10 −3 to 10×10 −2 S/cm at temperatures of 66° F. to 74° F., wherein the oxygen-deficient layer has a thickness of less than 10 nm.

2. The solid-state battery cell of claim 1 , wherein the second electrode comprises one or more of lithium nickel manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt aluminum oxide, or lithium iron phosphate.

3. The solid-state battery cell of claim 1 , wherein the electrolyte comprises lithium lanthanum zirconium oxide (LLZO).

4. The solid-state battery cell of claim 1 , wherein the electrolyte is doped with one or more of aluminum, tantalum, and niobium.

5. The solid-state battery cell of claim 1 , further comprising a second oxygen-deficient interface layer disposed between the second electrolyte surface and the second electrode first surface.

6. The solid-state battery cell of claim 1 , further comprising a first deposition layer disposed between the first electrode and the electrolyte such that the first oxygen-deficient interface layer is disposed between the first deposition layer and the first electrolyte surface.

7. The solid-state battery cell of claim 6 , wherein the first deposition layer is deposited in a vacuum.

8. The solid-state battery cell of claim 6 , further comprising:

a first lithium layer physically coupled to the first deposition layer, wherein the first lithium layer is in electrical communication with the first deposition layer.

9. The solid-state battery cell of claim 1 , wherein the solid-electrolyte comprises a material having a crystalline structure.

10. The solid-state battery cell of claim 1 , wherein the solid electrolyte comprises at least one of doped lithium lanthanum zirconium oxide (LLZO), undoped LLZO, doped lithium lanthanum titanium oxide (LLTO), and undoped LLTO.

11. The solid-state battery cell of claim 10 , wherein the solid electrolyte comprises doped LLZO.

12. The solid-state battery cell of claim 10 , wherein the solid electrolyte comprises undoped LLZO.

13. The solid-state battery cell of claim 10 , wherein the solid electrolyte comprises doped LLTO.

14. The solid-state battery cell of claim 10 , wherein the solid electrolyte comprises undoped LLTO.

15. A solid-state battery cell, comprising:

a first electrode comprising lithium;

a second electrode comprising one or more of lithium nickel manganese cobalt oxide, lithium nickel cobalt aluminum oxide, or lithium nickel manganese oxide;

a solid electrolyte extending between the first and second electrodes, the solid electrolyte comprising cubic lithium lanthanum zirconium oxide (LLZO);

a first lithium deposition layer on a first surface of the solid electrolyte, wherein the first deposition layer extends between the first electrode and the first surface of the solid electrolyte; and

an oxygen-deficient interface at an interface of the first lithium deposition layer and the first surface of the solid electrolyte and formed by reduction of the first surface of the solid electrolyte, the oxygen deficient interface extending only partially through the solid electrolyte, wherein the solid electrolyte has a conductivity in the range of 0.1×10 −3 to 10×10 −2 S/cm at temperatures of 66° F. to 74° F., wherein the oxygen-deficient layer has a thickness of less than 10 nm.

16. A solid-state battery cell, comprising:

a first electrode comprising lithium metal or a lithium metal alloy, the first electrode having a first electrode first surface and an oppositely disposed first electrode second surface;

a second electrode having a second electrode first surface and an oppositely disposed second electrode second surface;

a solid electrolyte comprising a cubic lithium ion conducting metal oxide, the solid electrolyte extending between the first and second electrodes and the solid electrolyte having oppositely disposed first and second electrolyte surfaces, wherein the first electrolyte surface is in facing relation to the first electrode second surface and the second electrolyte surface is in facing relation to the second electrode first surface;

a first oxygen-deficient interface layer formed by reduction of the first electrolyte surface of the solid electrolyte, the first oxygen-deficient interface layer formed in the solid electrolyte at an interface between the first electrolyte surface and the first electrode second surface, and the first oxygen-deficient interface layer extending only partially through the solid electrolyte, wherein the solid electrolyte has an ionic conductivity in the range of 0.1×10 −3 to 10×10 −2 S/cm at temperatures of 66° F. to 74° F.; and

a first deposition layer disposed between the first electrode and the electrolyte such that the first oxygen-deficient interface layer is disposed between the first deposition layer and the first electrolyte surface,

wherein the first deposition layer is deposited in a vacuum.

Assignments (2)
CONFIRMATORY LICENSE Recorded Jan 22, 2021
From: UCHICAGO ARGONNE, LLC
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 054998/0724 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 26, 2020
From: ZHU, YISI; TEPAVCEVIC, SANJA; CONNELL, JUSTIN G.; ZAPOL, PETER; MARKOVIC, NENAD
To: UCHICAGO ARGONNE, LLC
Reel/Frame 051940/0222 →
Continuity (1)
Related Publication 20210249693A1 · Aug 12, 2021
References Cited (37)
US 5448080A · Han et al. · 1995 [cited by applicant]
US 20100291431A1 · Shih · 2010 [cited by examiner]
US 20140087092A1 · Nieh · 2014 [cited by examiner]
US 20160248117A1 · Liang · 2016 [cited by examiner]
US 20160301063A1 · Yukinobu · 2016 [cited by examiner]
US 20170179472A1 · Allie · 2017 [cited by examiner]
US 20180301752A1 · Sakamoto et al. · 2018 [cited by applicant]
US 20200052326A1 · Hu · 2020 [cited by examiner]
US 20200358086A1 · Hu · 2020 [cited by examiner]
US 20210194045A1 · Beck · 2021 [cited by examiner]
US 20240113279A1 · Hu · 2024 [cited by examiner]
CN 102749726A · 2012 [cited by applicant]
CN 108365152A · 2018 [cited by examiner]
CN 208315666U · 2019 [cited by examiner]
CN 108365152B · 2020 [cited by examiner]
WO WO2016196688A1 · 2016 [cited by examiner]
WO WO2019193324A1 · 2019 [cited by examiner]
Author: Lei Fan, Shuya Wei, Siyuan Li, Qi Li, Yingying Lu, Title: “Recent progress of the Solid-State Electrolytes for High-Energy Metal-Based Batteries”, Advanced Energy Materials vol. 8, 1702657, Date: Jan. 26, 2018 (… [cited by examiner]
Author: Jianneng Liang, Jing Luo, Qian Sun, Xiaofei Yang, Ruying Li, Xueliang Sun, Title: “Recent progress on solid-state hybrid electrolytes for solid-state lithium batteries”, Energy Storage Materials vol. 21, 308, Da… [cited by examiner]
CN108365152B, machine English translation of document, Inventor: Zhang Qiang; Zhao Chenzi; Cheng Xinbing, Title: “Composite separator for lithium battery”, Date: Feb. 28, 2022 retrieved from https://worldwide.espacenet.… [cited by examiner]
Yonemoto, Fumihiro, et al. “Temperature effects on cycling stability of Li plating/stripping on Ta-doped Li7La3Zr2O12.” Journal of Power Sources 343 (2017): 207-215. (Year: 2017). [cited by examiner]
CN108365152A, Zhang Qiang; Zhao Chenzi; Cheng Xinbing, “Composite separator for lithium battery”, retrieved from https://worldwide.espacenet.com/ Oct. 13, 2022 (Year: 2018). [cited by examiner]
Senevirathne, Keerthi, et al. “A new crystalline LiPON electrolyte: Synthesis, properties, and electronic structure.” Solid State Ionics 233 (2013): 95-101 (Year: 2013). [cited by examiner]
Xiong, Yuli, et al. “Effects of annealing temperature on structure and opt-electric properties of ion-conducting LLTO thin films prepared by RF magnetron sputtering.” Journal of Alloys and Compounds 509.5 (2011): 1910-1… [cited by examiner]
Nong, Jian, et al. “Properties and preparation of Li—La—Ti—Zr—O thin film electrolyte.” Materials Letters 154 (2015): 167-169 (Year: 2015). [cited by examiner]
Jena, Anirudha, et al. “Ameliorating interfacial ionic transportation in all-solid-state Li-ion batteries with interlayer modifications.” ACS Energy Letters 3.11 (2018): 2775-2795 (Year: 2018). [cited by examiner]
Duvel, Andre, et al. “Mechanosynthesis of solid electrolytes: preparation, characterization, and Li ion transport properties of garnet-type Al-doped Li7La3Zr2O12 crystallizing with cubic symmetry.” The Journal of Physic… [cited by examiner]
Wenzel, Sebastian, et al. “Interphase formation on lithium solid electrolytes—An in situ approach to study interfacial reactions by photoelectron spectroscopy.” Solid State Ionics 278 (2015): 98-105. (Year: 2015). [cited by examiner]
Lu, Yang, et al. “An in situ element permeation constructed high endurance Li-LLZO interface at high current densities.” Journal of Materials Chemistry A 6.39 (2018): 18853-18858. (Year: 2018). [cited by examiner]
CN208315666U, Wang, et al. “Lithium anode prefabricated component, lithium anode and lithium metal secondary cell”, machine English translation retrieved from https://worldwide.espacenet.com Date: Jan. 27, 2025 (Year: 2… [cited by examiner]
Sastre et al., Aluminum-Assisted Densification of Cosputtered Lithium Garnet Electrolyte Films for Solid-State Batteries, ACS Applied Energy Materials 2019 2 (12), 8511-8524. [cited by applicant]
Balaish et al., “Processing thin but robust electrolytes for solid-state batteries,” Nature Energy, vol. 6, pp. 227-239, Mar. 2021. [cited by applicant]
Connell et al., Crystal Orientation—Dependent Reactivity of Oxide Surfaces in Contact with Lithium Metal, ACS Applied Materials & Interfaces 2018 10(20):17471-9. [cited by applicant]
Peloton et al., Carrier Cooling in Colloidal Quantum Wells, Nano Lett. 2012, 12, 12, 6158-6163. [cited by applicant]
Tepavcevic et al. Advanced Solid-State Interfaces in Li-ion Batteries, presented at Lithium Metal Anode Deep Dive Meeting, Aug. 28-29, 2018, Pittsburgh, Pennsylvania. [cited by applicant]
Thompson et al., Electrochemical Window of the Li-Ion Solid Electrolyte Li [cited by applicant]
Zhu et al., Dopant-Dependent Stability of Garnet Solid Electrolyte Interfaces with Lithium Metal, Adv. Energy Mater. 2019, 9, 1803440. [cited by applicant]