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Title: Sodium Peroxide Dihydrate or Sodium Superoxide: The Importance of the Cell Configuration for Sodium-Oxygen Batteries

Abstract

In sodium–oxygen (Na–O2) batteries, multiple discharge products have been observed by different research groups. Given the fact that different materials, gas supplies, and cell configurations are used by different groups, it is a great challenge to draw a clear conclusion on the formation of the different products. Here, two different cell setups are used to investigate the cell chemistries of Na–O2 batteries. With the same materials and gas supplies, a peroxide-based product is observed in a glass chamber cell and a superoxide-based product is observed in a stainless-steel cell. Ex situ high-energy X-ray diffraction (HEXRD) and Raman spectroscopy are performed to investigate the structure and composition of the product. In addition, in situ XRD is used to investigate the structure evolution of the peroxide-based product. The findings highlight the importance of the cell design and emphasize the critical environment of the formation of the discharge products of Na–O2 batteries.

Authors:
 [1];  [2];  [3];  [4];  [5]; ORCiD logo [5]
  1. Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Lemont IL 60439 USA; Department of Chemistry and Biochemistry, The Ohio State University, 100 West 18th Avenue Columbus OH 43210 USA
  2. Energy Systems Division, Argonne National Laboratory, 9700 South Cass Avenue Lemont IL 60439 USA
  3. X-ray Science Division, Argonne National Laboratory, 9700 South Cass Avenue Lemont IL 60439 USA
  4. HIGP, University of Hawaii at Manoa, 1680 East-West Rd Honolulu HI 96822 USA
  5. Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Avenue Lemont IL 60439 USA
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Energy Efficiency and Renewable Energy (EERE), Vehicle Technologies Office (EE-3V)
OSTI Identifier:
1395849
DOE Contract Number:
AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Small Methods; Journal Volume: 1; Journal Issue: 7
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; Na2O2·2H2O; NaO2; cell configuration; in situ XRD; sodium–oxygen batteries

Citation Formats

Bi, Xuanxuan, Wang, Rongyue, Ma, Lu, Zhang, Dongzhou, Amine, Khalil, and Lu, Jun. Sodium Peroxide Dihydrate or Sodium Superoxide: The Importance of the Cell Configuration for Sodium-Oxygen Batteries. United States: N. p., 2017. Web. doi:10.1002/smtd.201700102.
Bi, Xuanxuan, Wang, Rongyue, Ma, Lu, Zhang, Dongzhou, Amine, Khalil, & Lu, Jun. Sodium Peroxide Dihydrate or Sodium Superoxide: The Importance of the Cell Configuration for Sodium-Oxygen Batteries. United States. doi:10.1002/smtd.201700102.
Bi, Xuanxuan, Wang, Rongyue, Ma, Lu, Zhang, Dongzhou, Amine, Khalil, and Lu, Jun. Tue . "Sodium Peroxide Dihydrate or Sodium Superoxide: The Importance of the Cell Configuration for Sodium-Oxygen Batteries". United States. doi:10.1002/smtd.201700102.
@article{osti_1395849,
title = {Sodium Peroxide Dihydrate or Sodium Superoxide: The Importance of the Cell Configuration for Sodium-Oxygen Batteries},
author = {Bi, Xuanxuan and Wang, Rongyue and Ma, Lu and Zhang, Dongzhou and Amine, Khalil and Lu, Jun},
abstractNote = {In sodium–oxygen (Na–O2) batteries, multiple discharge products have been observed by different research groups. Given the fact that different materials, gas supplies, and cell configurations are used by different groups, it is a great challenge to draw a clear conclusion on the formation of the different products. Here, two different cell setups are used to investigate the cell chemistries of Na–O2 batteries. With the same materials and gas supplies, a peroxide-based product is observed in a glass chamber cell and a superoxide-based product is observed in a stainless-steel cell. Ex situ high-energy X-ray diffraction (HEXRD) and Raman spectroscopy are performed to investigate the structure and composition of the product. In addition, in situ XRD is used to investigate the structure evolution of the peroxide-based product. The findings highlight the importance of the cell design and emphasize the critical environment of the formation of the discharge products of Na–O2 batteries.},
doi = {10.1002/smtd.201700102},
journal = {Small Methods},
number = 7,
volume = 1,
place = {United States},
year = {Tue May 23 00:00:00 EDT 2017},
month = {Tue May 23 00:00:00 EDT 2017}
}
  • A viable Li/O 2 battery will require the development of stable electrolytes that do not continuously decompose during cell operation. In some recent experiments it is suggested that reactions occurring at the interface between the liquid electrolyte and the solid lithium peroxide (Li 2O 2) discharge phase are a major contributor to these instabilities. To clarify the mechanisms associated with these reactions, a variety of atomistic simulation techniques, classical Monte Carlo, van der Waals-augmented density functional theory, ab initio molecular dynamics, and various solvation models, are used to study the initial decomposition of the common electrolyte solvent, dimethoxyethane (DME), onmore » surfaces of Li 2O 2. Comparisons are made between the two predominant Li 2O 2 surface charge states by calculating decomposition pathways on peroxide-terminated (O 2 2–) and superoxide-terminated (O 2 1–) facets. For both terminations, DME decomposition proceeds exothermically via a two-step process comprised of hydrogen abstraction (H-abstraction) followed by nucleophilic attack. In the first step, abstracted H dissociates a surface O 2 dimer, and combines with a dissociated oxygen to form a hydroxide ion (OH ). In the remaining surface oxygen then attacks the DME, resulting in a DME fragment that is strongly bound to the Li 2O 2 surface. DME decomposition is predicted to be more exothermic on the peroxide facet; nevertheless, the rate of DME decomposition is faster on the superoxide termination. The impact of solvation (explicit vs implicit) and an applied electric field on the reaction energetics are investigated. Finally, our calculations suggest that surface-mediated electrolyte decomposition should out-pace liquid-phase processes such as solvent auto-oxidation by dissolved O 2.« less
  • No abstract prepared.
  • Activation of p-type III-V semiconductors with cesium and oxygen has been widely used to prepare negative electron affinity (NEA) photocathodes. However, the nature of the chemical species on the surface after the activation is not well understood. In this study, InP NEA photocathodes activated with cesium and oxygen are studied using synchrotron radiation photoelectron spectroscopy, also called photoemission. Based on the O 1s core level as well as the valence band spectra, Cs peroxide and Cs superoxide are identified on the InP surface. Transformation from Cs peroxide to Cs superoxide is observed after the activation, and is probably the majormore » reason for the decay of the quantum yield of the photocathode. The oxidation of the InP substrate is also observed with elapse of time, adding to the decay of the quantum yield.« less
  • An attempt is made to produce gas-phase singlet oxygen O{sub 2}(a{sup 1{Delta}}{sub g}) in a liquid-liquid reaction between acidic hydrogen peroxide (AHP) and sodium hypochlorite (NaOCl). The attempt arises from the fact that basic hydrogen peroxide (BHP) has long been the prime source for producing singlet delta oxygen through its reaction with chlorine. However, BHP suffers from the defect of being unstable during storage. Exploratory experiments were performed in a centrifugal flow singlet oxygen generator (CF-SOG) with two streams of solutions, AHP and NaOCl, mixed in a slit nozzle and then injected into the arc-shaped concavity in the CF-SOG tomore » form a rotating liquid flow with a remarkable centrifugal force. With the help of this centrifugal force, the product of the O{sub 2}({sup 1{Delta}}) reaction was quickly separated from the liquid phase. The gas-phase O{sub 2}({sup 1{Delta}}) was detected via the spectrum of O{sub 2}({sup 1{Delta}}) cooperative dimolecular emission with a CCD spectrograph. Experimental results show that it is feasible to produce gas-phase O{sub 2}({sup 1{Delta}}) from the AHP + NaOCl reaction, and the stronger the acidity, the more efficient the O{sub 2}({sup 1{Delta}}) production. However, since in the AHP + NaOCl reaction, Cl{sub 2} unavoidably appears as a byproduct, its catalytic action on the decomposition of H{sub 2}O{sub 2} into ground-state O{sub 2} remains a major obstacle to utilising the AHP + NaOCl reaction in producing gas-phase O{sub 2}({sup 1{Delta}}). Qualitative interpretation shows that the AHP + NaOCl reaction is virtually the reaction of interaction of molecular H{sub 2}O{sub 2} with molecular HOCl, its mechanism being analogous to that of reaction of BHP with Cl{sub 2}, where HOOCl is the key intermediate. It is difficult to form the intermediate HOOCl via the H{sub 2}O{sub 2} + NaOCl reaction in a basic medium, thus gas-phase O{sub 2}({sup 1{Delta}}) cannot be obtained in appreciable quantities. (active media)« less