Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Solvent-Mediated, Reversible Ternary Graphite Intercalation Compounds for Extreme-Condition Li-Ion Batteries

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.4c04594· OSTI ID:2382649
 [1];  [1];  [2];  [3];  [3];  [4];  [5];  [2];  [1];  [1];  [1];  [6];  [6];  [7];  [5];  [5];  [2];  [3];  [1]
  1. Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)
  2. Washington Univ., St. Louis, MO (United States)
  3. Pennsylvania State Univ., University Park, PA (United States)
  4. Brookhaven National Laboratory (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
  5. Argonne National Laboratory (ANL), Argonne, IL (United States)
  6. Purdue Univ., West Lafayette, IN (United States)
  7. Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
+ Show Author Affiliations

Traditional Li-ion intercalation chemistry into graphite anode exclusively utilizes the co-intercalation-free or co-intercalation mechanism. The latter mechanism is based on ternary graphite intercalation compounds (t-GICs), where glyme solvents were explored and proved to deliver unsatisfied cyclability in LIBs. Herein, we report a novel intercalation mechanism, that is, in-situ synthesis of t-THF-GICs in the tetrahydrofuran (THF) electrolyte via a spontaneous, controllable reaction between binary-GICs and free THF molecules during initial graphite lithiation. The spontaneous transformation from b-GIC to t-GIC, which is different from conventional co-intercalation chemistry, is characterized and quantified via operando synchrotron X-ray and electrochemical analyses. The resulting t-GIC chemistry obviates the necessity for complete Li-ion desolvation, facilitating rapid kinetics and synchronous charge/discharge of graphite particles even under high current densities. Consequently, the graphite anode demonstrates unprecedented fast charging (1 min), dendrite-free low-temperature performance, and ultralong lifetimes exceeding 10,000 cycles. Full cells coupled with layered cathode, display remarkable cycling stability upon a 15-min charging and excellent rate capability even at -40 °C. Furthermore, our chemical strategies are shown to extend beyond Li-ion batteries to encompass Na-ion and K-ion batteries, underscoring their broad applicability. Our work contributes to the advancement of graphite intercalation chemistry and presents a low-cost, adaptable approach to achieving fast-charging and low-temperature batteries.

Research Organization:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF); USDA AFRI
Grant/Contract Number:
SC0012704
OSTI ID:
2382649
Alternate ID(s):
OSTI ID: 2440987
Report Number(s):
BNL--225765-2024-JAAM
Journal Information:
Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 24 Vol. 146; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

References (36)

Sodium Storage Behavior in Natural Graphite using Ether-based Electrolyte Systems journal November 2014
An Ultrahigh‐Power Mesocarbon Microbeads|Na + ‐Diglyme|Na 3 V 2 (PO 4 ) 3 Sodium‐Ion Battery journal December 2021
Recent Progress in Graphite Intercalation Compounds for Rechargeable Metal (Li, Na, K, Al)-Ion Batteries journal June 2017
Conditions for Reversible Na Intercalation in Graphite: Theoretical Studies on the Interplay Among Guest Ions, Solvent, and Graphite Host journal September 2016
Exploiting Lithium-Ether Co-Intercalation in Graphite for High-Power Lithium-Ion Batteries journal June 2017
Non‐Flammable Electrolyte Enables High‐Voltage and Wide‐Temperature Lithium‐Ion Batteries with Fast Charging journal January 2023
Use of Graphite as a Highly Reversible Electrode with Superior Cycle Life for Sodium-Ion Batteries by Making Use of Co-Intercalation Phenomena journal July 2014
Understanding High‐Rate K + ‐Solvent Co‐Intercalation in Natural Graphite for Potassium‐Ion Batteries journal May 2020
A TiSe2‐Graphite Dual Ion Battery: Fast Na‐Ion Insertion and Excellent Stability journal July 2021
Ether‐Based Electrolyte Chemistry Towards High‐Voltage and Long‐Life Na‐Ion Full Batteries journal November 2021
Rechargeable LiNi0.65Co0.15Mn0.2O2||Graphite Batteries Operating at −60 °C journal September 2022
Overview on the Chemistry of Intercalation into Graphite of Binary Metallic Alloys book January 1993
Synthesis and properties of lithium-graphite intercalation compounds journal June 1979
The reversible intercalation of tetrahydrofuran in some graphite-alkali metal lamellar compounds journal October 1979
Lithium ion secondary batteries; past 10 years and the future journal November 2001
The state of understanding of the lithium-ion-battery graphite solid electrolyte interphase (SEI) and its relationship to formation cycling journal August 2016
Reconstructed Orthorhombic V2O5 Polyhedra for Fast Ion Diffusion in K-Ion Batteries journal January 2019
High-Energy-Density Flexible Potassium-Ion Battery Based on Patterned Electrodes journal April 2018
Highly stable and ultrafast electrode reaction of graphite for sodium ion batteries journal October 2015
A sodium-ion battery exploiting layered oxide cathode, graphite anode and glyme-based electrolyte journal April 2016
New Concepts in Electrolytes journal February 2020
Design Criteria of Dilute Ether Electrolytes toward Reversible and Fast Intercalation Chemistry of Graphite Anode in Li-Ion Batteries journal February 2023
General Observation of Lithium Intercalation into Graphite in Ethylene-Carbonate-Free Superconcentrated Electrolytes journal March 2014
Electrolytes and Interphases in Li-Ion Batteries and Beyond journal October 2014
Correlating Li-Ion Solvation Structures and Electrode Potential Temperature Coefficients journal January 2021
Weakly Solvating Solution Enables Chemical Prelithiation of Graphite–SiO x Anodes for High-Energy Li-Ion Batteries journal June 2021
Tailoring sodium intercalation in graphite for high energy and power sodium ion batteries journal June 2019
Defect-free potassium manganese hexacyanoferrate cathode material for high-performance potassium-ion batteries journal April 2021
Li-ion battery electrolytes journal July 2021
Electrolyte design for Li-ion batteries under extreme operating conditions journal February 2023
Intercalation chemistry of graphite: alkali metal ions and beyond journal January 2019
Self-terminating, heterogeneous solid–electrolyte interphase enables reversible Li–ether cointercalation in graphite anodes journal January 2024
Intercalation compounds of graphite journal January 2002
Electrochemical Intercalation of  PF 6 into Graphite journal January 2000
Electrochemical Intercalation of Lithium into Graphite journal January 1993
Studies of Lithium Intercalation into Carbons Using Nonaqueous Electrochemical Cells journal January 1990

Similar Records

Asymmetric K/Li-Ion Battery Based on Intercalation Selectivity
Journal Article · Sun Nov 26 23:00:00 EST 2017 · ACS Energy Letters · OSTI ID:1461414

Related Subjects

25 ENERGY STORAGE
Li-ion batteries
co-intercalation
fast charging
low temperature
ternary graphite intercalation compounds