DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Vertical Co9S8 hollow nanowall arrays grown on a Celgard separator as a multifunctional polysulfide barrier for high-performance Li–S batteries

Journal Article · · Energy & Environmental Science
DOI: https://doi.org/10.1039/C8EE00893K · OSTI ID:1598185
 [1]; ORCiD logo [2]; ORCiD logo [3]
  1. Univ. of Texas, Austin, TX (United States). Materials Science and Engineering Program & Texas Materials Inst.; Univ. of Electronic Science and Technology of China, Chengdu (China)
  2. Univ. of Electronic Science and Technology of China, Chengdu (China)
  3. Univ. of Texas, Austin, TX (United States). Materials Science and Engineering Program & Texas Materials Inst.

Lithium–sulfur (Li–S) batteries have been regarded as one of the most promising next-generation energy-storage devices, due to their low cost and high theoretical energy density (2600 W h kg-1). However, the severe dissolution of lithium polysulfides (LiPSs) and the fatal shuttle effect of the sulfur cathode seriously hinder the practical applications of Li–S batteries. To address such issues, we present here, for the first time, a novel metal organic framework (MOF)-derived Co9S8 nanowall array with vertical hollow nanoarchitecture and high electrical conductivity, which is grown in situ on a Celgard separator (Co9S8–Celgard) via a feasible and scalable liquid-reaction approach, as an efficient barrier for LiPSs in Li–S batteries. Benefiting from the direct in situ growth of vertical Co9S8 hollow nanowall arrays as a multifunctional polar barrier, the Co9S8–Celgard separator possesses large surface area, excellent mechanical stability, and particularly strong LiPS-trapping ability via chemical and physical interactions. With these advantages, even with a pure sulfur cathode with a high sulfur loading of 5.6 mg cm-2, the Li–S cells with the Co9S8–Celgard separator exhibit outstanding electrochemical performance: the initial specific capacity is as high as 1385 mA h g-1 with a retention of 1190 mA h g-1 after 200 cycles. The cells deliver a high capacity of 530 mA h g-1 at a 1C rate (1675 mA g-1) even after an impressive number of 1000 cycles with an average capacity fade of only 0.039% per cycle, which is promising for long-term cycling application at high charge/discharge current densities, and pouch-type Li–S cells with the Co9S8–Celgard separator display excellent cycling performance. When the optimized cathode with the sulfur loading in well-designed yolk–shelled carbon@Fe3O4 (YSC@Fe3O4) nanoboxes is employed, the cell with Co9S8–Celgard delivers a high initial capacity of 986 mA h g-1 at a 1C rate with a capacity retention as high as 83.2% even after a remarkable number of 1500 cycles. In conclusion, this work presents a strategy to grow on the separator a multifunctional polar interlayer with unique nanoarchitecture and high conductivity to chemically and physically trap the LiPSs, thus significantly enhancing the performance of Li–S batteries.

Research Organization:
Univ. of Texas, Austin, TX (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division; China Scholarship Council
Grant/Contract Number:
SC0005397; 201606070032
OSTI ID:
1598185
Alternate ID(s):
OSTI ID: 1457805
Journal Information:
Energy & Environmental Science, Vol. 11, Issue 9; ISSN 1754-5692
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 457 works
Citation information provided by
Web of Science

References (45)

Atomic layer deposited TiO 2 on a nitrogen-doped graphene/sulfur electrode for high performance lithium–sulfur batteries journal January 2016
Lithium–sulfur batteries—the solution is in the electrolyte, but is the electrolyte a solution? journal January 2014
Rational design of a metal–organic framework host for sulfur storage in fast, long-cycle Li–S batteries journal January 2014
A flexible nanostructured sulphur–carbon nanotube cathode with high rate performance for Li-S batteries journal January 2012
Three-Dimensional Hierarchical Reduced Graphene Oxide/Tellurium Nanowires: A High-Performance Freestanding Cathode for Li–Te Batteries journal August 2016
Progress in flexible lithium batteries and future prospects journal January 2014
Tellurium-Impregnated Porous Cobalt-Doped Carbon Polyhedra as Superior Cathodes for Lithium–Tellurium Batteries journal July 2017
Lithium Iodide as a Promising Electrolyte Additive for Lithium-Sulfur Batteries: Mechanisms of Performance Enhancement journal November 2014
Long-Life and High-Areal-Capacity Li–S Batteries Enabled by a Light-Weight Polar Host with Intrinsic Polysulfide Adsorption journal March 2016
A novel synergistic composite with multi-functional effects for high-performance Li–S batteries journal January 2016
Hierarchically micro/mesoporous activated graphene with a large surface area for high sulfur loading in Li–S batteries journal January 2015
MWCNT porous microspheres with an efficient 3D conductive network for high performance lithium–sulfur batteries journal January 2016
Smaller Sulfur Molecules Promise Better Lithium–Sulfur Batteries journal October 2012
Free-standing TiO2 nanowire-embedded graphene hybrid membrane for advanced Li/dissolved polysulfide batteries journal March 2015
Highly flexible, freestanding tandem sulfur cathodes for foldable Li–S batteries with a high areal capacity journal January 2017
Yolk-Shelled C@Fe 3 O 4 Nanoboxes as Efficient Sulfur Hosts for High-Performance Lithium-Sulfur Batteries journal July 2017
From Metal–Organic Framework to Li 2 S@C–Co–N Nanoporous Architecture: A High-Capacity Cathode for Lithium–Sulfur Batteries journal November 2016
Graphene Oxide as a Sulfur Immobilizer in High Performance Lithium/Sulfur Cells journal November 2011
Three-Dimensional CNT/Graphene–Li 2 S Aerogel as Freestanding Cathode for High-Performance Li–S Batteries journal September 2016
A strategic approach to recharging lithium-sulphur batteries for long cycle life journal December 2013
A New Type of Multifunctional Polar Binder: Toward Practical Application of High Energy Lithium Sulfur Batteries journal February 2017
Suppressing Self-Discharge and Shuttle Effect of Lithium-Sulfur Batteries with V 2 O 5 -Decorated Carbon Nanofiber Interlayer journal January 2017
A Lightweight TiO 2 /Graphene Interlayer, Applied as a Highly Effective Polysulfide Absorbent for Fast, Long-Life Lithium-Sulfur Batteries journal March 2015
Lithium–sulphur batteries with a microporous carbon paper as a bifunctional interlayer journal January 2012
Rechargeable Lithium–Sulfur Batteries journal July 2014
A Polyethylene Glycol-Supported Microporous Carbon Coating as a Polysulfide Trap for Utilizing Pure Sulfur Cathodes in Lithium-Sulfur Batteries journal September 2014
Carbonized Eggshell Membrane as a Natural Polysulfide Reservoir for Highly Reversible Li-S Batteries journal November 2013
Effective Stabilization of a High-Loading Sulfur Cathode and a Lithium-Metal Anode in Li-S Batteries Utilizing SWCNT-Modulated Separators journal November 2015
Enhanced Performance of Lithium Sulfur Battery with a Reduced Graphene Oxide Coating Separator journal January 2015
Porous carbon nanofiber paper as an effective interlayer for high-performance lithium-sulfur batteries journal June 2015
V 2 O 5 Polysulfide Anion Barrier for Long-Lived Li–S Batteries journal May 2014
Metal–organic framework-based separator for lithium–sulfur batteries journal June 2016
Twinborn TiO 2 –TiN heterostructures enabling smooth trapping–diffusion–conversion of polysulfides towards ultralong life lithium–sulfur batteries journal January 2017
MOFs nanosheets derived porous metal oxide-coated three-dimensional substrates for lithium-ion battery applications journal August 2016
Cobalt oxide and N-doped carbon nanosheets derived from a single two-dimensional metal–organic framework precursor and their application in flexible asymmetric supercapacitors journal January 2017
Multifunctional Co 3 S 4 @sulfur nanotubes for enhanced lithium-sulfur battery performance journal July 2017
Three-dimensional CNT/graphene–sulfur hybrid sponges with high sulfur loading as superior-capacity cathodes for lithium–sulfur batteries journal January 2015
Wrinkled sulfur@graphene microspheres with high sulfur loading as superior-capacity cathode for LiS batteries journal October 2016
Yolk–Shell Structure of Polyaniline-Coated Sulfur for Lithium–Sulfur Batteries journal October 2013
A graphene-like metallic cathode host for long-life and high-loading lithium–sulfur batteries journal January 2016
Powering Lithium–Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts journal December 2015
Different distribution of in-situ thin carbon layer in hollow cobalt sulfide nanocages and their application for supercapacitors journal February 2017
Cobalt Sulfide/Graphene Composite Hydrogel as Electrode for High-Performance Pseudocapacitors journal February 2016
Self-Templated Formation of Interlaced Carbon Nanotubes Threaded Hollow Co 3 S 4 Nanoboxes for High-Rate and Heat-Resistant Lithium–Sulfur Batteries journal September 2017
Metallic and polar Co 9 S 8 inlaid carbon hollow nanopolyhedra as efficient polysulfide mediator for lithium−sulfur batteries journal August 2017

Cited By (52)

Synergistic Regulation of Polysulfides Conversion and Deposition by MOF‐Derived Hierarchically Ordered Carbonaceous Composite for High‐Energy Lithium–Sulfur Batteries journal March 2019
A Game Changer: Functional Nano/Micromaterials for Smart Rechargeable Batteries journal August 2019
Efficient Ni 2 Co 4 P 3 Nanowires Catalysts Enhance Ultrahigh‐Loading Lithium–Sulfur Conversion in a Microreactor‐Like Battery journal October 2019
Emerging Functional Porous Polymeric and Carbonaceous Materials for Environmental Treatment and Energy Storage journal November 2019
Current Status and Future Prospects of Metal–Sulfur Batteries journal May 2019
Single Nickel Atoms on Nitrogen‐Doped Graphene Enabling Enhanced Kinetics of Lithium–Sulfur Batteries journal August 2019
Engineering Oxygen Vacancies in a Polysulfide‐Blocking Layer with Enhanced Catalytic Ability journal January 2020
Graphene Oxide/Carbon Nanotube Bilayer Flexible Membrane for High‐Performance Li–S Batteries with Superior Physical and Electrochemical Properties journal February 2019
Boosting High‐Rate Li–S Batteries by an MOF‐Derived Catalytic Electrode with a Layer‐by‐Layer Structure journal June 2019
Electrospinning of Metal–Organic Frameworks for Energy and Environmental Applications journal December 2019
Nanosized ReS 2 Monolayers Embedded in Nitrogen‐Doped Carbon Nanotubes for High‐Rate Capacitive Lithium Storage journal February 2019
Metal Sulfide‐Decorated Carbon Sponge as a Highly Efficient Electrocatalyst and Absorbant for Polysulfide in High‐Loading Li 2 S Batteries journal April 2019
Separator Modified by Cobalt‐Embedded Carbon Nanosheets Enabling Chemisorption and Catalytic Effects of Polysulfides for High‐Energy‐Density Lithium‐Sulfur Batteries journal July 2019
Flexible and High‐Loading Lithium–Sulfur Batteries Enabled by Integrated Three‐In‐One Fibrous Membranes journal August 2019
A Multifunctional Separator Enables Safe and Durable Lithium/Magnesium–Sulfur Batteries under Elevated Temperature journal December 2019
Long‐Life, High‐Rate Lithium–Sulfur Cells with a Carbon‐Free VN Host as an Efficient Polysulfide Adsorbent and Lithium Dendrite Inhibitor journal December 2019
Developing A “Polysulfide‐Phobic” Strategy to Restrain Shuttle Effect in Lithium–Sulfur Batteries journal July 2019
Developing A “Polysulfide‐Phobic” Strategy to Restrain Shuttle Effect in Lithium–Sulfur Batteries journal July 2019
Three‐Dimensional Hierarchical Constructs of MOF‐on‐Reduced Graphene Oxide for Lithium–Sulfur Batteries journal July 2019
Ni 1‐x Co x O y , Ni 1‐x Co x S y and Ni 1‐x Co x P y Catalysts Prepared from Ni 1‐x Co x ‐ZIF‐67 for Hydrogen Production by Electrolysis in Alkaline Media journal September 2019
2 D Materials for Inhibiting the Shuttle Effect in Advanced Lithium–Sulfur Batteries journal March 2020
Constructing Patch‐Ni‐Shelled Pt@Ni Nanoparticles within Confined Nanoreactors for Catalytic Oxidation of Insoluble Polysulfides in Li‐S Batteries journal June 2019
Compactly Coupled Nitrogen‐Doped Carbon Nanosheets/Molybdenum Phosphide Nanocrystal Hollow Nanospheres as Polysulfide Reservoirs for High‐Performance Lithium–Sulfur Chemistry journal August 2019
Mo 2 C Nanodots Anchored on N-Doped Porous CNT Microspheres as Electrode for Efficient Li-Ion Storage journal October 2018
Electrocatalysis of polysulfide conversion via sulfur–cobalt CoS2 on a carbon nanotube surface as a cathode for high-performance lithium–sulfur batteries journal June 2019
Multifunctional hollow spheres as sulfur hosts for high-performance Li–S batteries journal December 2019
Carbon nanotubes/SiC prepared by catalytic chemical vapor deposition as scaffold for improved lithium-sulfur batteries journal May 2019
One-pot synthesis and shape control of metal selenides, sulfides and oxides with oxalic acid as the reducing reagent journal January 2019
Battery Separators Functionalized with Edge-Rich MoS2/C Hollow Microspheres for the Uniform Deposition of Li2S in High-Performance Lithium–Sulfur Batteries journal May 2019
Strong charge polarization effect enabled by surface oxidized titanium nitride for lithium-sulfur batteries journal June 2019
Improvement of the electrochemical performance of a nickel rich LiNi 0.5 Co 0.2 Mn 0.3 O 2 cathode material by reduced graphene oxide/SiO 2 nanoparticle double-layer coating journal January 2019
sp–sp 2 hybrid-conjugated microporous polymer-derived Pd-encapsulated porous carbon materials for lithium–sulfur batteries journal January 2019
A soluble single atom catalyst promotes lithium polysulfide conversion in lithium sulfur batteries journal January 2019
Frogspawn inspired hollow Fe 3 C@N–C as an efficient sulfur host for high-rate lithium–sulfur batteries journal January 2019
Revisiting the positive roles of liquid polysulfides in alkali metal–sulfur electrochemistry: from electrolyte additives to active catholyte journal January 2019
Rational design of NiFe 2 O 4 –rGO by tuning the compositional chemistry and its enhanced performance for a Li-ion battery anode journal January 2019
Self-supported hierarchical core–shell Co 9 S 8 @NiCo 2 O 4 hollow nanoneedle arrays for asymmetric supercapacitors journal January 2019
Highly stable lithium–sulfur batteries based on p–n heterojunctions embedded on hollow sheath carbon propelling polysulfides conversion journal January 2019
Sulfur-deficient MoS 2 grown inside hollow mesoporous carbon as a functional polysulfide mediator journal January 2019
Lithium bis(trifluoromethanesulfonyl)imide assisted dual-functional separator coating materials based on covalent organic frameworks for high-performance lithium–selenium sulfide batteries journal January 2019
Chelation-assisted formation of multi-yolk–shell Co 4 N@carbon nanoboxes for self-discharge-suppressed high-performance Li–SeS 2 batteries journal January 2019
Accelerated Li–S chemistry at a cooperative interface built in situ journal January 2019
MXene-engineered lithium–sulfur batteries journal January 2019
ZnS spheres wrapped by an ultrathin wrinkled carbon film as a multifunctional interlayer for long-life Li–S batteries journal January 2020
Bifunctional CdS@Co 9 S 8 /Ni 3 S 2 catalyst for efficient electrocatalytic and photo-assisted electrocatalytic overall water splitting journal January 2020
MnO 2 -Coated Sulfur-Filled Hollow Carbon Nanosphere-Based Cathode Materials for Enhancing Electrochemical Performance of Li-S Cells journal January 2019
How Far Away Are Lithium-Sulfur Batteries From Commercialization? journal November 2019
Lignin Nanoparticle-Coated Celgard Separator for High-Performance Lithium–Sulfur Batteries journal November 2019
Rationalizing Electrocatalysis of Li–S Chemistry by Mediator Design: Progress and Prospects journal July 2019
Simultaneous Cobalt and Phosphorous Doping of MoS 2 for Improved Catalytic Performance on Polysulfide Conversion in Lithium–Sulfur Batteries journal August 2019
Metal‐Organic Framework‐Templated Hollow Co 3 O 4 /C with Controllable Oxygen Vacancies for Efficient Oxygen Evolution Reaction journal October 2019
Rational design of polar/nonpolar mediators toward efficient sulfur fixation and enhanced conductivity journal January 2020