skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Hydrogen-Bonding Interactions in Hybrid Aqueous/Nonaqueous Electrolytes Enable Low-Cost and Long-Lifespan Sodium-Ion Storage

Journal Article · · ACS Applied Materials and Interfaces
 [1]; ORCiD logo [1];  [1];  [1];  [2]; ORCiD logo [1];  [1];  [1];  [1];  [1];  [3];  [4];  [1]
  1. Nanyang Technological Univ. (Singapore)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Synchrotron Light Research Inst., Nakhon Ratchasima (Thailand)
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
+ Show Author Affiliations

Although “water-in-salt” electrolytes have opened a new pathway to expand the electrochemical stability window of aqueous electrolytes, the electrode instability and irreversible proton co-insertion caused by aqueous media still hinder the practical application, even when using exotic fluorinated salts. In this study, an accessible hybrid electrolyte class based on common sodium salts is proposed, and crucially an ethanol-rich media is introduced to achieve highly stable Na-ion electrochemistry. Here, ethanol exerts a strong hydrogen-bonding effect on water, simultaneously expanding the electrochemical stability window of the hybridized electrolyte to 2.5 V, restricting degradation activities, reducing transition metal dissolution from the cathode material, and improving electrolyte–electrode wettability. The binary ethanol–water solvent enables the impressive cycling of sodium-ion batteries based on perchlorate, chloride, and acetate electrolyte salts. Notably, a Na0.44MnO2 electrode exhibits both high capacity (81 mAh g–1) and a remarkably long cycle life >1000 cycles at 100 mA g–1 (a capacity decay rate per cycle of 0.024%) in a 1 M sodium acetate system. The Na0.44MnO2/Zn full cells also show excellent cycling stability and rate capability in a wide temperature range. The gained understanding of the hydrogen-bonding interactions in the hybridized electrolyte can provide new battery chemistry guidelines in designing promising candidates for developing low-cost and long-lifespan batteries based on other (Li+, K+, Zn2+, Mg2+, and Al3+) systems.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1635479
Report Number(s):
BNL-216101-2020-JAAM
Journal Information:
ACS Applied Materials and Interfaces, Vol. 12, Issue 20; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 15 works
Citation information provided by
Web of Science

References (52)

Recent Progress of Rechargeable Batteries Using Mild Aqueous Electrolytes journal September 2018
Advances and issues in developing salt-concentrated battery electrolytes journal March 2019
Aqueous Rechargeable Li and Na Ion Batteries journal September 2014
“Water-in-Salt” Electrolyte Makes Aqueous Sodium-Ion Battery Safe, Green, and Long-Lasting journal July 2017
A High-Voltage Aqueous Electrolyte for Sodium-Ion Batteries journal August 2017
Over 2 V Aqueous Sodium‐Ion Battery with Prussian Blue‐Type Electrodes journal September 2018
Sodium- and Potassium-Hydrate Melts Containing Asymmetric Imide Anions for High-Voltage Aqueous Batteries journal August 2019
Local hydrogen bonding dynamics and collective reorganization in water: Ultrafast infrared spectroscopy of HOD/D2O journal February 2005
Dielectric Constants of Water, Methanol, Ethanol, Butanol and Acetone: Measurement and Computational Study journal May 2010
NMR and FT-IR Studies of Hydrogen Bonds in Ethanol-Water Mixtures journal March 1995
Raman and IR spectroscopy research on hydrogen bonding in water-ethanol systems journal September 2010
Effects of Salts, Acids, and Phenols on the Hydrogen-Bonding Structure of Water−Ethanol Mixtures journal January 2004
Effect of Hydrogen Bonding on the Surface Tension Properties of Binary Mixture (Acetone-Water) by Raman Spectroscopy journal March 2019
Physical Properties and Hydrogen-Bonding Network of Water–Ethanol Mixtures from Molecular Dynamics Simulations journal January 2016
A sodium perchlorate-based hybrid electrolyte with high salt-to-water molar ratio for safe 2.5 V carbon-based supercapacitor journal December 2019
Study of hydrogen bonding in ethanol-water binary solutions by Raman spectroscopy journal January 2018
Raman spectra and structure of water from -10 to 90.deg. journal June 1974
Bifurcated hydrogen bonds in water journal October 1984
Vibrational spectra of water molecules at quartz/water interfaces journal January 1994
Hydrogen bonding of water–ethanol in alcoholic beverages journal October 2006
The frequency of the HOH bending fundamental in solids and liquids journal January 1984
Ti-substituted tunnel-type Na0.44MnO2 oxide as a negative electrode for aqueous sodium-ion batteries journal March 2015
A truncated octahedral spinel LiMn 2 O 4 as high-performance cathode material for ultrafast and long-life lithium-ion batteries journal July 2017
Ultrafast Zinc-Ion Diffusion Ability Observed in 6.0-Nanometer Spinel Nanodots journal August 2019
Diffusion behavior of sodium ions in Na0.44MnO2 in aqueous and non-aqueous electrolytes journal December 2013
A High-Rate Manganese Oxide for Rechargeable Lithium Battery Applications journal January 2001
Reversible Sodium Ion Insertion in Single Crystalline Manganese Oxide Nanowires with Long Cycle Life journal June 2011
Effects of the starting materials of Na0.44MnO2 cathode materials on their electrochemical properties for Na-ion batteries journal December 2016
Study of the Insertion/Deinsertion Mechanism of Sodium into Na 0.44 MnO 2 journal April 2007
Single-Crystal Synthesis and Structure Refinement of Na<sub>0.44</sub>MnO<sub>2</sub> journal April 2011
1.3 V superwide potential window sponsored by Na-Mn-O plates as cathodes towards aqueous rechargeable sodium-ion batteries journal August 2019
A layered-spinel lithium manganite hydrate for high-capacity and ultrafast lithium storage journal February 2019
Na4Mn9O18 as a positive electrode material for an aqueous electrolyte sodium-ion energy storage device journal March 2010
Preparation of MnCo 2 O 4 @Ni(OH) 2 Core-Shell Flowers for Asymmetric Supercapacitor Materials with Ultrahigh Specific Capacitance journal April 2016
The tunnel manganese oxide Na 4.32 Mn 9 O 18 : a new Na + site discovered by single-crystal X-ray diffraction journal January 2011
Ab Initio Study of the Sodium Intercalation and Intermediate Phases in Na 0.44 MnO 2 for Sodium-Ion Battery journal March 2012
VESTA 3 for three-dimensional visualization of crystal, volumetric and morphology data journal October 2011
Ionic Liquid Electrolytes with Various Sodium Solutes for Rechargeable Na/NaFePO 4 Batteries Operated at Elevated Temperatures journal October 2014
Rechargeable Na/Na0.44MnO2 cells with ionic liquid electrolytes containing various sodium solutes journal January 2015
Characteristics of an ionic liquid electrolyte for sodium-ion batteries journal January 2016
NaFSA–C1C3pyrFSA ionic liquids for sodium secondary battery operating over a wide temperature range journal September 2013
Electrochemical stability of non-aqueous electrolytes for sodium-ion batteries and their compatibility with Na 0.7 CoO 2 journal January 2014
Aqueous Processing of Na 0.44 MnO 2 Cathode Material for the Development of Greener Na-Ion Batteries journal September 2017
A pre-edge analysis of Mn K-edge XANES spectra to help determine the speciation of manganese in minerals and glasses journal July 2008
Low-cost and high safe manganese-based aqueous battery for grid energy storage and conversion journal December 2019
Na 3 V 2 O 2 (PO 4 ) 2 F-MWCNT nanocomposites as a stable and high rate cathode for aqueous and non-aqueous sodium-ion batteries journal August 2016
A low-cost and environmentally benign aqueous rechargeable sodium-ion battery based on NaTi2(PO4)3–Na2NiFe(CN)6 intercalation chemistry journal June 2013
Prussian blue nanocubes as cathode materials for aqueous Na-Zn hybrid batteries journal July 2017
Na3Ti2(PO4)3 as a sodium-bearing anode for rechargeable aqueous sodium-ion batteries journal July 2014
Electrolyte dependence of the performance of a Na2FeP2O7//NaTi2(PO4)3 rechargeable aqueous sodium-ion battery journal September 2016
A nanocomposite of MoO3 coated with PPy as an anode material for aqueous sodium rechargeable batteries with excellent electrochemical performance journal January 2014
Full open-framework batteries for stationary energy storage journal January 2014

Similar Records

1.3 V superwide potential window sponsored by Na-Mn-O plates as cathodes towards aqueous rechargeable sodium-ion batteries
Journal Article · Wed Mar 27 00:00:00 EDT 2019 · Chemical Engineering Journal · OSTI ID:1635479
+7 more
Structural water and disordered structure promote aqueous sodium-ion energy storage in sodium-birnessite
Journal Article · Thu Oct 31 00:00:00 EDT 2019 · Nature Communications · OSTI ID:1635479
+10 more
“Water‐in‐Salt” Electrolyte Makes Aqueous Sodium‐Ion Battery Safe, Green, and Long‐Lasting
Journal Article · Fri Jul 21 00:00:00 EDT 2017 · Advanced Energy Materials · OSTI ID:1635479
+11 more

Related Subjects

25 ENERGY STORAGE