Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

This content will become publicly available on Wed Sep 11 00:00:00 EDT 2024

Title: Scalable Metal Phosphides as a Dual-Function Catalyst and Lithium–Metal Stabilizer for Lithium–Sulfur Batteries

Abstract

Although lithium-sulfur batteries are a promising approach for achieving high energy density, their commercial viability is limited by poor sulfur redox kinetics, polysulfide shuttling, and lithium metal instability. To resolve these issues concurrently, we utilize titanium phosphides (TiPx) as dual-function materials to catalyze the sulfur redox kinetics at the cathode and stabilize the lithium metal at the anode. Importantly, these phosphides are synthesized via a facile, highly scalable one-step mechanochemical ball-milling process that does not generate toxic phosphine gas as a byproduct, making it more viable compared to traditional synthesis routes. At the cathode, we find that higher phosphorus contents in the phosphide as in TiP2 leads to superior redox kinetics and reduced polysulfide shuttling due to improved polysulfide adsorption ability. Meanwhile, at the anode, TiP2 acts as a lithiophilic seed in a 3-dimensional carbonaceous host that can be lithiated to form a Li-TiP2/C composite. This composite alleviates the volume changes of lithium metal while utilizing TiP2 to form a more favorable solid-electrolyte interface (SEI). Full coin cells employing TiP2 in the cathode and anode were assembled with a sulfur loading of 4 mg cm-2 and a negative to positive capacity (N/P) ratio of 6. After 50 cycles, the TiP2more » full cells retain a higher capacity of 643 mA h g-1 compared to 422 mA h g-1 for the conventional cell, despite the higher N/P ratio of 12 for the conventional cell. Altogether, we showcase the viability of employing metal phosphides as catalysts in practical lithium-sulfur batteries.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. University of Texas at Austin, TX (United States)
Publication Date:
Research Org.:
University of Texas at Austin, TX (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Office of Sustainable Transportation. Vehicle Technologies Office (VTO)
OSTI Identifier:
2217469
Grant/Contract Number:  
EE0007762
Resource Type:
Accepted Manuscript
Journal Name:
ACS Applied Energy Materials
Additional Journal Information:
Journal Volume: 6; Journal Issue: 18; Journal ID: ISSN 2574-0962
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Lithium-sulfur batteries; catalysts; dual-function materials; phosphide catalysts; lithium−metal stabilizer; mechanochemical synthesis; electrochemical cells; electrodes; inorganic compounds; lithium; sulfur

Citation Formats

Liao, Kameron, Bhargav, Amruth, and Manthiram, Arumugam. Scalable Metal Phosphides as a Dual-Function Catalyst and Lithium–Metal Stabilizer for Lithium–Sulfur Batteries. United States: N. p., 2023. Web. doi:10.1021/acsaem.3c01606.
Copy to clipboard
Liao, Kameron, Bhargav, Amruth, & Manthiram, Arumugam. Scalable Metal Phosphides as a Dual-Function Catalyst and Lithium–Metal Stabilizer for Lithium–Sulfur Batteries. United States. https://doi.org/10.1021/acsaem.3c01606
Copy to clipboard
Liao, Kameron, Bhargav, Amruth, and Manthiram, Arumugam. Mon . "Scalable Metal Phosphides as a Dual-Function Catalyst and Lithium–Metal Stabilizer for Lithium–Sulfur Batteries". United States. https://doi.org/10.1021/acsaem.3c01606.
Copy to clipboard
@article{osti_2217469,
title = {Scalable Metal Phosphides as a Dual-Function Catalyst and Lithium–Metal Stabilizer for Lithium–Sulfur Batteries},
author = {Liao, Kameron and Bhargav, Amruth and Manthiram, Arumugam},
abstractNote = {Although lithium-sulfur batteries are a promising approach for achieving high energy density, their commercial viability is limited by poor sulfur redox kinetics, polysulfide shuttling, and lithium metal instability. To resolve these issues concurrently, we utilize titanium phosphides (TiPx) as dual-function materials to catalyze the sulfur redox kinetics at the cathode and stabilize the lithium metal at the anode. Importantly, these phosphides are synthesized via a facile, highly scalable one-step mechanochemical ball-milling process that does not generate toxic phosphine gas as a byproduct, making it more viable compared to traditional synthesis routes. At the cathode, we find that higher phosphorus contents in the phosphide as in TiP2 leads to superior redox kinetics and reduced polysulfide shuttling due to improved polysulfide adsorption ability. Meanwhile, at the anode, TiP2 acts as a lithiophilic seed in a 3-dimensional carbonaceous host that can be lithiated to form a Li-TiP2/C composite. This composite alleviates the volume changes of lithium metal while utilizing TiP2 to form a more favorable solid-electrolyte interface (SEI). Full coin cells employing TiP2 in the cathode and anode were assembled with a sulfur loading of 4 mg cm-2 and a negative to positive capacity (N/P) ratio of 6. After 50 cycles, the TiP2 full cells retain a higher capacity of 643 mA h g-1 compared to 422 mA h g-1 for the conventional cell, despite the higher N/P ratio of 12 for the conventional cell. Altogether, we showcase the viability of employing metal phosphides as catalysts in practical lithium-sulfur batteries.},
doi = {10.1021/acsaem.3c01606},
journal = {ACS Applied Energy Materials},
number = 18,
volume = 6,
place = {United States},
year = {Mon Sep 11 00:00:00 EDT 2023},
month = {Mon Sep 11 00:00:00 EDT 2023}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
This content will become publicly available on September 11, 2024
Publisher's Version of Record
https://doi.org/10.1021/acsaem.3c01606
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

A Review of Composite Lithium Metal Anode for Practical Applications
journal, November 2019

  • Shi, Peng; Zhang, Xue‐Qiang; Shen, Xin
  • Advanced Materials Technologies, Vol. 5, Issue 1
  • DOI: 10.1002/admt.201900806

Tubular CoFeP@CN as a Mott–Schottky Catalyst with Multiple Adsorption Sites for Robust Lithium−Sulfur Batteries
journal, May 2021

  • Zhang, Chaoqi; Du, Ruifeng; Biendicho, Jordi Jacas
  • Advanced Energy Materials, Vol. 11, Issue 24
  • DOI: 10.1002/aenm.202100432

Role of LiNO3 in rechargeable lithium/sulfur battery
journal, May 2012

Three-dimensional stable lithium metal anode with nanoscale lithium islands embedded in ionically conductive solid matrix
journal, April 2017

  • Lin, Dingchang; Zhao, Jie; Sun, Jie
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 18
  • DOI: 10.1073/pnas.1619489114

Core–Shell ZIF-8@ZIF-67-Derived CoP Nanoparticle-Embedded N-Doped Carbon Nanotube Hollow Polyhedron for Efficient Overall Water Splitting
journal, January 2018

  • Pan, Yuan; Sun, Kaian; Liu, Shoujie
  • Journal of the American Chemical Society, Vol. 140, Issue 7
  • DOI: 10.1021/jacs.7b12420

Phosphorous Pentasulfide as a Novel Additive for High-Performance Lithium-Sulfur Batteries
journal, June 2012

  • Lin, Zhan; Liu, Zengcai; Fu, Wujun
  • Advanced Functional Materials, Vol. 23, Issue 8
  • DOI: 10.1002/adfm.201200696

Electrolyte Additives for Lithium Metal Anodes and Rechargeable Lithium Metal Batteries: Progress and Perspectives
journal, October 2018

  • Zhang, Heng; Eshetu, Gebrekidan Gebresilassie; Judez, Xabier
  • Angewandte Chemie International Edition, Vol. 57, Issue 46
  • DOI: 10.1002/anie.201712702

3D CoSe@C Aerogel as a Host for Dendrite‐Free Lithium‐Metal Anode and Efficient Sulfur Cathode in Li–S Full Cells
journal, September 2020

Low‐strain TiP2O7 with three‐dimensional ion channels as long‐life and high‐rate anode material for Mg‐ion batteries
journal, January 2022

  • Xiong, Fangyu; Jiang, Yalong; Cheng, Li
  • Interdisciplinary Materials, Vol. 1, Issue 1
  • DOI: 10.1002/idm2.12004

Emerging Catalysts to Promote Kinetics of Lithium–Sulfur Batteries
journal, January 2021

Deciphering the Modulation Essence of p Bands in Co-Based Compounds on Li-S Chemistry
journal, December 2018

Earth-Rich Transition Metal Phosphide for Energy Conversion and Storage
journal, May 2016

Rechargeable Lithium–Sulfur Batteries
journal, July 2014

  • Manthiram, Arumugam; Fu, Yongzhu; Chung, Sheng-Heng
  • Chemical Reviews, Vol. 114, Issue 23
  • DOI: 10.1021/cr500062v

Methods to Improve Lithium Metal Anode for Li-S Batteries
journal, December 2019

Designing high-energy lithium–sulfur batteries
journal, January 2016

  • Seh, Zhi Wei; Sun, Yongming; Zhang, Qianfan
  • Chemical Society Reviews, Vol. 45, Issue 20
  • DOI: 10.1039/C5CS00410A

Delineating the Lithium–Electrolyte Interfacial Chemistry and the Dynamics of Lithium Deposition in Lithium–Sulfur Batteries
journal, January 2021

Advances in Polar Materials for Lithium-Sulfur Batteries
journal, May 2018

  • Wang, Hongqiang; Zhang, Wenchao; Xu, Jianzhong
  • Advanced Functional Materials, Vol. 28, Issue 38
  • DOI: 10.1002/adfm.201707520

Anode-free, Lean-Electrolyte Lithium-Sulfur Batteries Enabled by Tellurium-Stabilized Lithium Deposition
journal, May 2020

Solid-state lithium batteries: Safety and prospects
journal, March 2022

Electrospinning Engineering Enables High-Performance Sodium-Ion Batteries
journal, July 2021

In Situ Grown 1T′‐MoTe 2 Nanosheets on Carbon Nanotubes as an Efficient Electrocatalyst and Lithium Regulator for Stable Lithium–Sulfur Full Cells
journal, November 2021

  • He, Jiarui; Bhargav, Amruth; Manthiram, Arumugam
  • Advanced Energy Materials, Vol. 12, Issue 1
  • DOI: 10.1002/aenm.202103204

TiO Phase Stabilized into Freestanding Nanofibers as Strong Polysulfide Immobilizer in Li–S Batteries: Evidence for Lewis Acid–Base Interactions
journal, October 2018

  • Singh, Arvinder; Kalra, Vibha
  • ACS Applied Materials & Interfaces, Vol. 10, Issue 44
  • DOI: 10.1021/acsami.8b11029

High-performance Li–S battery cathode with catalyst-like carbon nanotube-MoP promoting polysulfide redox
journal, June 2017

Lithium phosphide/lithium chloride coating on lithium for advanced lithium metal anode
journal, January 2018

  • Lin, Liangdong; Liang, Feng; Zhang, Kaiyuan
  • Journal of Materials Chemistry A, Vol. 6, Issue 32
  • DOI: 10.1039/C8TA05102J

Synthesis of Cd2+-functionalized titanium phosphate nanoparticles and application as labels for electrochemical immunoassays
journal, January 2012

  • Feng, Li-Na; Peng, Juan; Zhu, Ying-Di
  • Chemical Communications, Vol. 48, Issue 37
  • DOI: 10.1039/c2cc31552a

Composite lithium metal anode by melt infusion of lithium into a 3D conducting scaffold with lithiophilic coating
journal, February 2016

  • Liang, Zheng; Lin, Dingchang; Zhao, Jie
  • Proceedings of the National Academy of Sciences, Vol. 113, Issue 11
  • DOI: 10.1073/pnas.1518188113

Lithium-Sulfur Batteries: Attaining the Critical Metrics
journal, February 2020

Catalytic Effects in Lithium-Sulfur Batteries: Promoted Sulfur Transformation and Reduced Shuttle Effect
journal, September 2017

Surface Chemistry in Cobalt Phosphide-Stabilized Lithium–Sulfur Batteries
journal, January 2018

  • Zhong, Yiren; Yin, Lichang; He, Peng
  • Journal of the American Chemical Society, Vol. 140, Issue 4
  • DOI: 10.1021/jacs.7b11434

Exploiting XPS for the identification of sulfides and polysulfides
journal, January 2015

  • Fantauzzi, Marzia; Elsener, Bernhard; Atzei, Davide
  • RSC Advances, Vol. 5, Issue 93
  • DOI: 10.1039/C5RA14915K

Tunability of p- and n-channel TiOx thin film transistors
journal, June 2018

Mechanistic understanding of lithium-anode protection by organosulfide-based solid-electrolyte interphases and its implications
journal, January 2023

  • Bhargav, Amruth; Asl, Hooman Yaghoobnejad; Manthiram, Arumugam
  • Journal of Materials Chemistry A, Vol. 11, Issue 18
  • DOI: 10.1039/D3TA00417A

A Perspective toward Practical Lithium–Sulfur Batteries
journal, June 2020

Nanostructured Co 2 P Electrocatalyst for the Hydrogen Evolution Reaction and Direct Comparison with Morphologically Equivalent CoP
journal, May 2015

Protecting lithium metal anodes in lithium–sulfur batteries: A review
journal, January 2023

Catalysts for Hydrogen Evolution from the [NiFe] Hydrogenase to the Ni 2 P(001) Surface:  The Importance of Ensemble Effect
journal, October 2005

  • Liu, Ping; Rodriguez, José A.
  • Journal of the American Chemical Society, Vol. 127, Issue 42
  • DOI: 10.1021/ja0540019

Catalytic oxidation of Li 2 S on the surface of metal sulfides for Li−S batteries
journal, January 2017

  • Zhou, Guangmin; Tian, Hongzhen; Jin, Yang
  • Proceedings of the National Academy of Sciences, Vol. 114, Issue 5
  • DOI: 10.1073/pnas.1615837114

A review on the status and challenges of electrocatalysts in lithium-sulfur batteries
journal, July 2019

Sealing effect of surface porosity of Ti–P composite films on tinplates
journal, January 2019

  • Wang, Ziyu; Kong, Delong; Wang, Minghao
  • RSC Advances, Vol. 9, Issue 23
  • DOI: 10.1039/C8RA10523E

Cobalt Nanoparticles/Black Phosphorus Nanosheets: An Efficient Catalyst for Electrochemical Oxygen Evolution
journal, June 2018

Multifunctional Metal Phosphides as Superior Host Materials for Advanced Lithium‐Sulfur Batteries
journal, August 2021

  • Wang, Zhuosen; Xu, Xijun; Liu, Zhengbo
  • Chemistry – A European Journal, Vol. 27, Issue 54
  • DOI: 10.1002/chem.202101873

3D Heterogeneous Co3 O4 @Co3 S4 Nanoarrays Grown on Ni Foam as a Binder-Free Electrode for Lithium-Ion Batteries
journal, December 2017

Lithium Metal Anode Materials Design: Interphase and Host
journal, October 2019

    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: