IP Library › Granted Patent US 12,368,190
Granted Patent B2
US 12,368,190 · App. 16/973,671 · Granted Jul 22, 2025

Systems and methods of detecting Li dendrites

Inventors: James M. Tour (Bellaire, TX); Tuo Wang (Houston, TX); Rodrigo Villegas Salvatierra (Houston, TX)
Assignee: William Marsh Rice University
H01M10/48G01R31/367G01R31/3842G01R31/392H01M4/382H01M10/0525H01M10/425H01M50/431H01M50/443H01M50/449G01R31/389H01M10/052H01M10/4235H01M2010/4271Y02E60/10
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 12,368,190
App. No.
16/973,671
Granted
Jul 22, 2025
Kind
B2
Abstract

Systems and methods that utilize a separator coated by particles for Li dendrite detection in an ordinary two-electrode battery system. The particles can be red phosphorus (RP) particles and/or other particles that are poor electronic conductors, are able to react with Li, and will form an insoluble product with Li, such as silicon, germanium, arsenic, metal oxides, metal halides, metal chalcogenides, chalcogenides, and LiM x E y O z (M=metal, E=nonmetal, O=oxygen, x≥0, y≥0, z≥0). These other particles can be used by themselves or in combination with one another. No additional electrode is needed, and the presence of Li dendrites can be detected simply based on the voltage profile during the charging step.

Claims (23)

1. An energy-storage device with dendrite detection, the energy-storage device comprising:

(a) an anode;

(b) a cathode;

(c) an electrolyte containing cations of a metal, wherein the electrolyte is disposed between the anode and the cathode; and

(d) an electrodeless dendrite-detection interlayer in the electrolyte between the anode and the cathode, the dendrite-detection interlayer to generate a voltage change detectable between the anode and the cathode responsive to dendrites of the metal extending from the anode to the dendrite-detection interlayer, wherein

(i) the electrodeless dendrite-detection interlayer consists essentially of red phosphorus.

2. The energy-storage device of claim 1 , wherein the metal comprises lithium.

3. The energy-storage device of claim 1 , wherein the dendrite-detection layer comprises at least one material selected from a group consisting of silicon, germanium, arsenic, metal oxides, metal fluorides, and LiMxEyOz with M=metal, E=nonmetal, O=oxygen, and x≥0, y≥0, and z≥0.

4. The energy-storage device of claim 1 further comprising a separator extending through the electrolyte between the dendrite-detection interlayer and the anode.

5. The energy-storage device of claim 4 , wherein the dendrite-detection interlayer is disposed on the separator.

6. The energy-storage device of claim 1 , wherein the dendrite-detection interlayer is an electrical insulator.

7. The energy-storage device of claim 6 , wherein the dendrite-detection interlayer has a conductivity of less than 10 −5 S/cm.

8. The energy-storage device of claim 1 , wherein the electrolyte is a liquid.

9. The energy-storage device of claim 1 , wherein the electrodeless dendrite-detection interlayer comprises multiple separator layers.

10. An energy-storage device with dendrite detection, the energy-storage device comprising:

(a) an anode;

(b) a cathode;

(c) an electrolyte containing cations of a metal, wherein

(i) the electrolyte is disposed between the anode and the cathode, and

(ii) the metal comprises lithium; and

(d) an electrodeless dendrite-detection interlayer in the electrolyte between the anode and the cathode, the dendrite-detection interlayer to generate a detectable electrical response between the anode and the cathode responsive to dendrites of the metal extending from the anode to the dendrite-detection interlayer, wherein

(i) the dendrite-detection layer comprises phosphorous that reacts with the lithium to generate the detectable electrical response between the anode and the cathode.

11. The energy-storage device of claim 10 , wherein the dendrite-detection layer comprises red phosphorous.

Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 11, 2020
From: TOUR, JAMES M.; WANG, TUO; SALVATIERRA, RODRIGO VILLEGAS
To: WILLIAM MARSH RICE UNIVERSITY
Reel/Frame 054618/0547 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Dec 11, 2020
From: TOUR, JAMES M.; WANG, TUO; SALVATIERRA, RODRIGO VILLEGAS
To: WILLIAM MARSH RICE UNIVERSITY
Reel/Frame 054618/0661 →
Continuity (3)
Provisional Application 62683158 · Jun 11, 2018
Provisional Application 62720033 · Aug 20, 2018
Related Publication 20210257679A1 · Aug 19, 2021
References Cited (38)
US 20140329120A1 · Cui · 2014 [cited by examiner]
EP 3151328A1 · 2017 [cited by applicant]
WO 2018045226A1 · 2018 [cited by applicant]
WO 2019241291A1 · 2019 [cited by applicant]
Armand, M. et al. “Building Better Batteries”, Nature 2008, 451 (7179), 652-657 (“Armand 2008”), 6 pages. [cited by applicant]
Bruce, P. et al. “Li—O2 and Li—S Batteries with High Energy Storage”, Nat. Mater. 2011, 11 (2), 172-172 (“Bruce 2011”). 12 pages. [cited by applicant]
Burns, J., et al. “In-Situ Detection of Lithium Plating Using High Precision Coulometry”, Journal of the Electrochemical Society, 162 (6) A959-A964 (2015); 6 pages. [cited by applicant]
Cano, Z., et al. “Batteries and fuel cells for emerging electric vehicle markets” Nat. Energy. 2018, 3, 279-289 (“Cano 2018”). 11 pages. [cited by applicant]
Cheng, X., et al., “Toward Safe Lithium Metal Anode in Rechargeable Batteries: A Review”, Chem. Rev. 2017, 117, 10403-10473 (“Cheng 2018”). 71 pages. [cited by applicant]
Ding, F. et al. “Dendrite-Free Lithium Deposition via Self-Healing Electrostatic Shield Mechanism”, J. Am. Chem. Soc. 2013, 135 (11), 4450-4456 (“Ding 2013”), 7 pages. [cited by applicant]
Dunn, B. et al. “Electrical Energy Storage for the Grid: A Battery of Choices”. Science (80). 2011, 334 (6058), 928-935 (“Dunn 2011”), 9 pages. [cited by applicant]
Girishkumar, G. et al. “Lithium-Air Battery: Promise and Challenges”. J. Phys. Chem. Lett. 2010, 1 (14), 2193-2203 (“Girishkumar 2010”); 11 pages. [cited by applicant]
Goodenough, J. et al., “The Li-Ion Rechargeable Battery: A Perspective”. J. Am. Chem. Soc. 2013, 135 (4), 1167-1176 (“Goodenough 2013”) 10 pages. [cited by applicant]
Harry, K., et al. “Influence of Electrolyte Modulus on the Local Current Density at a Dendrite Tip on a Lithium Metal Electrode”. J. Electrochem. Soc. 2016, 163, A2216-A2224 (“Harry 2016”). 10 pages. [cited by applicant]
Li, L., et al. “Self-heating-induced healing of lithium dendrites”. Science 2018, 359, 1513-1516 (“Li 2018”). 5 pages. [cited by applicant]
Li, W., et al. “Amorphous Red Phosphorus Embedded in Highly Ordered Mesoporous Carbon with Superior Lithium and Sodium Storage Capacity”. Nano Lett. 2016, 16, 1546-1553 (“Li 2016”). 8 pages. [cited by applicant]
Lin, D. et al. “Layered Reduced Graphene Oxide with Nanoscale Interlayer Gaps as a Stable Host for Lithium Metal Anodes”, Nat. Nanotechnol. 2016, 11, 626-632 (“Lin 2016”); 8 pages. [cited by applicant]
Lin, D., et al. “All-Integrated Bifunctional Separator for Li Dendrite Detection via Novel Solution Synthesis of a Thermostable Polyimide Separator”. J. Am. Chem. Soc. 2016, 138, 11044-11050 (“Lin 2016”). 7 pages. [cited by applicant]
Liu, B., et al. “Advancing Lithium Metal Batteries”. Joule 2018, 2, 833-845 (“Liu 2018”). 13 pages. [cited by applicant]
Liu, K., et al. “Extending the Life of Lithium-Based Rechargeable Batteries by Reaction of Lithium Dendrites with a Novel Silica Nanoparticle Sandwhiched Separator”, Adv. Mater. 2017, 29, 1603987; 6 pages. [cited by applicant]
Liu, S.-Q. et al. “Kinetic study on Li2.8(Vo.9Geo.1)2(P04)3 by EIS measurement”. J Alloys Compd 2008, 450, 499-504 (“Liu 2008”). 6 pages. [cited by applicant]
Manthiram, A. et al. “Lithium-Sulfur Batteries: Progress and Prospects”. Adv. Mater. 2015, 27 (12), 1980-2006 (“Manthiram 2015”), 27 pages. [cited by applicant]
Mayo, M., et al. “Ab Initio Study of Phosphorus Anodes for Lithium- and Sodium-Ion Batteries”. Chem. Mater. 2016, 28, 2011-2021 (“May 2016”). 11 pages. [cited by applicant]
Noorden, R. “The Rechargeable Revolution: A Better Battery”. Nature 2014, 507, 26-28 (“Noorden 2014”), 3 pages. [cited by applicant]
Orsini, F., et al. “In situ SEM study of the interfaces in plastic lithium cells”. J Power Sources. 1999, 81-82, 918-921 (“Orsini 1999”). 4 pages. [cited by applicant]
Qian, J. et al. “High Rate and Stable Cycling of Lithium Metal Anode”. Nat. Commun. 2015, 6, 6362 (“Qian 2015”), 9 pages. [cited by applicant]
Raji, A., et al. “Lithium Batteries with Nearly Maximum Metal Storage”. ACS Nano 2017, 11, 6362-6369 (“Raji 2017”). 8 pages. [cited by applicant]
Shen, X., et al. “Beyond lithium ion batteries: Higher energy density battery systems based on lithium metal anodes”. Energy Storage Mater. 2018, 12, 161-175 (“Shen 2018”). 16 pages. [cited by applicant]
Wang, T. “Detecting Li Dendtrites in a Two-Electrode Battery System”, Department of Chemistry, Rice University; 34 pages. [cited by applicant]
Wang, T. et al. “Detecting Li Dendtrites in a Two-Electrode Battery System”, Department of Chemistry, Smalley-Curl Institute and the NanoCarbon Center, Department of Materials Science and NanoEngineering, Rice Universit… [cited by applicant]
Wang, T. et al. “Detecting Li Dendtrites in a Two-Electrode Battery System-Supplementary Information”, Department of Chemistry, Smalley-Curl Institute and the NanoCarbon Center, Department of Materials Science and NanoE… [cited by applicant]
Wang, T., et al. “Ultrafast Charging High Capacity Asphalt-Lithium Metal Batteries”. ACS Nano 2017, 11, 10761-10767 (“Wang 2017”). 7 pages. [cited by applicant]
Wood, K., et al. “Dendrites and Pits: Untangling the Complex Behavior of Lithium Metal Anodes through Operando Video Microscopy”. ACS Cent. Sci. 2016, 2, 790-801 (“Wood 2016”). 12 pages. [cited by applicant]
Wu, H., et al. “Improving Battery Safety by Early Detection of Internal Shorting With a Bifunctional Separator”. Nat. Commun. 2014, 5, 5193-5198 (“Wu 2016”). 6 pages. [cited by applicant]
Xu, W. et al. “Lithium Metal Anodes for Rechargeable Batteries”, Energy Environ. Sci. 2014, 7 (2), 513-537 (“Xu 2014”); 25 pages. [cited by applicant]
Zhang, J. et al. “Lithium Metal Anodes and Rechargeable Lithium Metal Batteries”, 1st ed.; Hull, R. et al., Eds.; Springer International Publishing, 2017 (“J. Zhang 2017”); 206 pages. [cited by applicant]
Zhang, S., et al. “Electrochemical impedance study on the low temperature of Li-ion batteries”. Electrochimi. Acta 2004, 49, 1057-1061 (“Zhang 2004”). 5 pages. [cited by applicant]
International Searching Authority, International Search Report and Written Opinion; PCT/US2019/036609; date of mailing Nov. 15, 2019; 23 pages. [cited by applicant]