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Title: Ball Milling-Enabled Fe2.4+ to Fe3+ Redox Reaction in Prussian Blue Materials for Long-Life Aqueous Sodium-Ion Batteries

Journal Article · · ACS Applied Materials and Interfaces
 [1];  [2];  [3];  [2]; ORCiD logo [2];  [4]; ORCiD logo [5];  [3];  [3]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [2]
  1. Oregon State University, Corvallis, OR (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  2. Oregon State University, Corvallis, OR (United States)
  3. Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)
  4. SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
  5. Argonne National Laboratory (ANL), Argonne, IL (United States)
+ Show Author Affiliations

Aqueous Na-ion batteries using Prussian blue materials have inherent advantages on safety, material sustainability, and economic cost. However, it is challenging to obtain long term cycling stability because many redox reactions have poor intrinsic stability in water. In this report we demonstrate reversible Fe2.4+ to Fe3+ redox reaction of Prussian blue electrodes cycled in 17 m NaClO4 water-in-salt electrolyte. The cubic phase c-Na1.17Fe[Fe(CN)6]·0.35H2O) derived from monoclinic Prussian blue (m-Na1.88Fe[Fe(CN)6]·0.7H2O) through ball milling delivers excellent cycling stability of >18,000 cycles with >90% capacity retention at 10C rate. The specific capacity is ~75 mAh/g and ~67 mAh/g at 1C and 10C rate, respectively. Systematic characterizations including electron microscopy, X-ray diffraction, Fourier-transform infrared spectroscopy, X-ray photoelectron spectroscopy, and X-ray absorption spectroscopy have verified the phase transition and iron oxidation state evolution, revealing the mechanism that enables the material’s high rate and long durability as the battery cathode.

Research Organization:
Pacific Northwest National Laboratory (PNNL), Richland, WA (United States); SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States); Argonne National Laboratory (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE Office of Science (SC); National Science Foundation (NSF); USDOE Office of Electricity (OE)
Grant/Contract Number:
AC05-76RL01830; AC02-06CH11357; CBET-2016192; 70247A
OSTI ID:
2222394
Report Number(s):
PNNL-SA-184322
Journal Information:
ACS Applied Materials and Interfaces, Vol. 15, Issue 30; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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25 ENERGY STORAGE
aqueous sodium-ion batteries
Prussian blue analogues
water-in-salt
ball milling
electrolytes
X-ray absorption spectroscopy