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Title: Route to high-energy density polymeric nitrogen t-N via He-N compounds

Abstract

Polymeric nitrogen, stabilized by compressing pure molecular nitrogen, has yet to be recovered to ambient conditions, precluding its application as a high-energy density material. Here we suggest a route for synthesis of a tetragonal polymeric nitrogen, denoted t-N, via He-N compounds at high pressures. Using first-principles calculations with structure searching, we predict a class of nitrides with stoichiometry HeN 4 that are energetically stable (relative to a mixture of solid He and N 2) above 8.5 GPa. At high pressure, HeN 4 comprises a polymeric channel-like nitrogen framework filled with linearly arranged helium atoms. The nitrogen framework persists to ambient pressure on decompression after removal of helium, forming pure polymeric nitrogen, t-N. t-N is dynamically and mechanically stable at ambient pressure with an estimated energy density of ~11.31 kJ/g, marking it out as a remarkable high-energy density material. As a result, this expands the known polymeric forms of nitrogen and indicates a route to its synthesis.

Authors:
 [1];  [2];  [3];  [1]; ORCiD logo [4];  [5];  [5];  [6]
  1. Jiangsu Normal Univ., Xuzhou (China)
  2. Jilin Univ., Changchun (China); Univ. of Cambridge, Cambridge (United Kingdom)
  3. Carnegie Inst. of Washington, Washington, D.C. (United States)
  4. Univ. of Cambridge, Cambridge (United Kingdom); Center for High Pressure Science and Technology Advanced Research (HPSTAR), Shanghai (China)
  5. Deakin Univ., Waurn Ponds, VIC (Australia)
  6. Jilin Univ., Changchun (China)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Energy Frontier Research in Extreme Environments (EFree)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470638
Grant/Contract Number:  
NA0002006; SC0001057
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 9; Journal Issue: 1; Related Information: EFree partners with Carnegie Institution of Washington (lead); California Institute of Technology; Colorado School of Mines; Cornell University; Lehigh University; Pennsylvania State University; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; catalysis (heterogeneous); solar (photovoltaic); phonons; thermoelectric; energy storage (including batteries and capacitors); hydrogen and fuel cells; superconductivity; charge transport; mesostructured materials; materials and chemistry by design; synthesis (novel materials)

Citation Formats

Li, Yinwei, Feng, Xiaolei, Liu, Hanyu, Hao, Jian, Redfern, Simon A. T., Lei, Weiwei, Liu, Dan, and Ma, Yanming. Route to high-energy density polymeric nitrogen t-N via He-N compounds. United States: N. p., 2018. Web. doi:10.1038/s41467-018-03200-4.
Li, Yinwei, Feng, Xiaolei, Liu, Hanyu, Hao, Jian, Redfern, Simon A. T., Lei, Weiwei, Liu, Dan, & Ma, Yanming. Route to high-energy density polymeric nitrogen t-N via He-N compounds. United States. doi:10.1038/s41467-018-03200-4.
Li, Yinwei, Feng, Xiaolei, Liu, Hanyu, Hao, Jian, Redfern, Simon A. T., Lei, Weiwei, Liu, Dan, and Ma, Yanming. Mon . "Route to high-energy density polymeric nitrogen t-N via He-N compounds". United States. doi:10.1038/s41467-018-03200-4. https://www.osti.gov/servlets/purl/1470638.
@article{osti_1470638,
title = {Route to high-energy density polymeric nitrogen t-N via He-N compounds},
author = {Li, Yinwei and Feng, Xiaolei and Liu, Hanyu and Hao, Jian and Redfern, Simon A. T. and Lei, Weiwei and Liu, Dan and Ma, Yanming},
abstractNote = {Polymeric nitrogen, stabilized by compressing pure molecular nitrogen, has yet to be recovered to ambient conditions, precluding its application as a high-energy density material. Here we suggest a route for synthesis of a tetragonal polymeric nitrogen, denoted t-N, via He-N compounds at high pressures. Using first-principles calculations with structure searching, we predict a class of nitrides with stoichiometry HeN4 that are energetically stable (relative to a mixture of solid He and N2) above 8.5 GPa. At high pressure, HeN4 comprises a polymeric channel-like nitrogen framework filled with linearly arranged helium atoms. The nitrogen framework persists to ambient pressure on decompression after removal of helium, forming pure polymeric nitrogen, t-N. t-N is dynamically and mechanically stable at ambient pressure with an estimated energy density of ~11.31 kJ/g, marking it out as a remarkable high-energy density material. As a result, this expands the known polymeric forms of nitrogen and indicates a route to its synthesis.},
doi = {10.1038/s41467-018-03200-4},
journal = {Nature Communications},
number = 1,
volume = 9,
place = {United States},
year = {2018},
month = {2}
}

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Figures / Tables:

Fig. 1 Fig. 1 : Thermodynamic stability of the predicted structures. Results from structure searching at 0 (a), 25 (b) and 50 (c) GPa. Convex hulls are shown as continuous lines, with (red) and without (black) the inclusion of vdW corrections. hcp-He at 0, 25 and 50 GPa, α-N2 at 0 GPamore » and ε-N2 at 25 and 50 GPa were adopted in the calculation. d Calculated enthalpy curves of the I41/a and P$\overline{1}$ structures with respect to the C2/c structure for HeN4 as a function of pressure. The decomposition enthalpy (blue triangles) into hcp-He plus molecular N2 (α-N2 at 0 GPa and ε-N2 above 0 GPa) was also plotted. Inset in d is an enlarged view of the decomposition enthalpy in pressure range 0–70 GPa. Black stars in inset represents the decomposition enthalpy curves of HeN4 into (He+ 4 N) as a function of pressure, where cg-N was considered at pressures above 54 GPa« less

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